Patent Application
20140356591
The present invention relates to an ultraviolet-curable resin composition which is useful for laminating optical base materials.
In recent years, in display devices such as liquid crystal displays, plasma displays, organic EL displays, etc., a touch panel in which a position input device, for example, a touch input device is combined with a display unit is being widely utilized. This touch panel has a structure in which a display unit, a glass plate or resin-made film having a transparent electrode loaned thereon, and a glass- or resin-made transparent protective plate are stacked in this order and laminated to each other.
In the touch panel, for laminating a display unit, a glass plate or film having a transparent electrode formed thereon, and an optical base material such as a glass- or resin-made transparent protective plate, etc., there is a technique using a pressure sensitive adhesive double coated sheet. However, in using a pressure sensitive adhesive double coated sheet, there was involved such a problem that an air bubble is easily entrained. As a technique substituting for the pressure sensitive adhesive double coated sheet, there is proposed a technique for laminating them with a flexible ultraviolet-curable resin composition.
In a display device such as a liquid crystal display device having such a touch panel, etc., there is proposed a touch panel structure in which a display unit and a touch sensor in which a glass-made or resin-made transparent protective plate is laminated to an optical base material such as a glass plate having a transparent electrode formed thereon, etc. are laminated to each other.
In the transparent protective plate of a touch panel of a display device having the above-described structure, a stripe-like light-shielding portion is formed in an outermost edge for the purpose of enhancing a contrast of a displayed image. In the case of laminating the transparent protective plate or touch sensor unit with an ultraviolet-curable resin composition, a sufficient ultraviolet ray does not reach a light shielding area of the ultraviolet-curable resin that becomes a shade of the light-shielding portion by the light-shielding portion, so that curing of the resin in the light-shielding area becomes insufficient. If curing of the resin is insufficient, a problem such as uneven display in the displayed image in the vicinity of the instant light-shielding portion, etc. is generated.
As a technique for enhancing curing of the resin in the light-shielding area, Patent Document 1 discloses a technique in which an organic peroxide is contained in an ultraviolet-curable resin, and after irradiation with an ultraviolet ray, the resultant is heated to cure the resin in a light-shielding area. However, there is a concern that a heating step damages a liquid crystal display device or the like. Furthermore, since a time of 60 minutes or more is required for thoroughly curing the resin by heating, there was involved such a problem that productivity is poor. In addition, Patent Document 2 discloses a technique in which an ultraviolet ray is irradiated from the side of an outer side face of the surface on which a light-shielding portion is formed, thereby curing a resin in a light-shielding area. However, since it is difficult to irradiate an ultraviolet ray from the side face depending upon a shape of a liquid crystal display device, the shape of the liquid crystal display device to which the instant method is applicable was limited.
Then, as for the ultraviolet-curable resin which is used for laminating an optical base material having a light-shielding portion, an ultraviolet-curable resin capable of achieving thorough curing with an ultraviolet ray from one direction even in the light-shielding area in which the ultraviolet ray is shielded by the light-shielding portion was demanded to be developed.
Patent Document 1: Japanese Patent No. 4711354
Patent Document 2: JP-A-2009-186954 (the term “JP-A” as used herein means an “unexamined published patent application”)
In view of such problems of the conventional techniques, the present invention has been made, and its object is to provide an ultraviolet-curable adhesive which in laminating an optical base material such as a transparent protective plate, etc. with an ultraviolet-curable adhesive, even in the case where a light-shielding portion is formed in the optical base material, is capable of thoroughly curing a resin positioned in a light-shielding area where the light is shielded by the presence of the light-shielding portion by irradiation with an ultraviolet ray from one direction without damaging a liquid display device or the like.
In order to solve the above-described problem, the present inventors made extensive and intensive investigations. As a result, it has been found that the above-described problem can be solved by allowing a compound having a specified absorption maximum wavelength and a specified light emission maximum wavelength and capable of absorbing light (in particular, an ultraviolet ray) to emit light to coexist in an ultraviolet-curable adhesive, leading to accomplishment of the present invention. Specifically, the present invention relates to the following (1) to (29).
(1)
An optical member comprising an optical base material and an optical base material having a light-shielding portion on a surface thereof, the optical base materials being adhered to each other via a cured product layer made of an ultraviolet-curable adhesive containing
(A) an organic compound capable of absorbing an ultraviolet ray to emit light, which when measured in tetrahydrofuran, has a maximum wavelength of light absorption spectrum in the range of from 250 to 400 nm and a maximum wavelength of light emission spectrum in the range of from 300 to 500 nm.
(B) a photopolymerizable compound, and
(C) a photopolymerization initiator.
(2)
The ultraviolet-curable adhesive described in (1) above, wherein the ultraviolet-curable adhesive is one which when formed into a cured product having a film thickness of 200 μm, has a transmittance to light at 400 nm of 80% or more.
(3)
The optical member described in (1) or (2) above, wherein the photopolymerization initiator (C) has absorption at a wavelength of the light emitted by the organic compound (A).
(4)
The optical member described in any one of (1) to (3) above, wherein an absorption coefficient per unit weight at 365 nm as measured in acetonitrile of the photopolymerization initiator (C) is from 85 to 10,000 mL/(g·cm).
(5)
The optical member described in any one of (1) to (4) above, wherein the ultraviolet-curable adhesive contains, as the photopolymerizable compound (B), (B-1) a (meth)arylate compound.
(6)
The optical member described in (5) above, wherein the ultraviolet-curable adhesive contain, as the (meth)arylate compound (B-1), (B-1-1) at least one (meth)acrylate oligomer of any of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton.
(7)
The optical member described in (5) or (6) above, wherein the ultraviolet-curable adhesive contains, as the (meth)arylate compound (B-1), (B-1-2) a monofunctional (meth)acrylate monomer.
(8)
The optical member described in any one of (1) to (7) above, wherein the ultraviolet-curable adhesive further contains (D) a softening component.
(9)
A touch panel comprising the optical member described in any one of (1) to (8) above.
(10)
Use of an ultraviolet-curable adhesive, comprising:
(A) an organic compound capable of absorbing an ultraviolet ray to emit light, which when measured in tetrahydrofuran, has a maximum wavelength of light absorption spectrum in the range of from 250 to 400 nm and a maximum wavelength of light emission spectrum in the range of from 300 to 500 nm;
(B) a photopolymerizable compound; and
(C) a photopolymerization initiator;
for fabricating an optical member in which plural optical base materials including at least an optical bass material having a light-shielding portion on a surface thereof are adhered to each other.
(11)
An ultraviolet-curable adhesive to be used for laminating an optical base material and an optical base material having a light-shielding portion, on a surface thereof to each other, the ultraviolet-curable adhesive, comprising:
(A) an organic compound capable of absorbing an ultraviolet ray to emit light, which when measured in tetrahydrofuran, has a maximum wavelength of light absorption spectrum in the range of from 250 to 400 nm and a maximum wavelength of light emission spectrum in the range of from 300 to 500 nm;
(B) a photopolymerizable compound; and
(C) a photopolymerization initiator.
(12)
The ultraviolet-curable adhesive described in (11) above, wherein the maximum wavelength of light absorption spectrum is in the range of from 270 to 320 nm, and the maximum wavelength of light emission spectrum is in the range of from 350 to 400 nm.
(13)
The ultraviolet-curable adhesive described in (11) or (12) above, wherein the ultraviolet-curable adhesive is one which when formed into a cured product having a film thickness of 200 μm, has a transmittance to light at 400 nm of 80% or more.
(14)
The ultraviolet-curable adhesive described in any one of (11) to (13) above, wherein the photopolymerization initiator (C) has absorption at a wavelength of the light emitted by the organic compound (A).
(15)
The ultraviolet-curable adhesive described in (14) above, wherein an absorption coefficient per unit weight at 365 nm as measured in acetonitrile of the photopolymerization initiator (C) is from 85 to 10,000 mL/(g·cm).
(16)
The ultraviolet-curable adhesive described in (15) above, wherein the absorption coefficient per unit weight is from 400 to 10,000 mL/(g·cm).
(17)
The ultraviolet-curable adhesive described in any one of (11) to (16) above, which comprises, as the photopolymerizable compound (B), (B-1) a (meth)arylate compound.
(18)
The ultraviolet-curable adhesive described in (17) above, which comprises, as the (meth)arylate compound (B-1), (B-1-1) at least one (meth)acrylate oligomer of any of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton.
(19)
The ultraviolet-curable adhesive described in (17) or (18) above, which comprises, as the (meth)arylate compound (B-1), (B-1-2) a monofunctional (meth)acrylate monomer.
(20)
The ultraviolet-curable adhesive described in any one of (11) to (19) above, wherein- the organic compound (A) is dissolved in the ultraviolet-curable adhesive.
(21)
The ultraviolet-curable adhesive described in any one of (11) to (20) above, which comprises, as the photopolymerizable compound (B), (i) (B-1-1) at least one (meth)acrylate oligomer of any of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton and (ii) (B-1-2) a monofunctional (meth)acrylate monomer.
(22)
The ultraviolet-curable adhesive described in any one of (11) to (21) above, which further comprises other components than the compound (A), the photopolymerizable compound (B) and the photopolymerization initiator (C), and has a content of the organic compound (A) of from 0.001 to 5% by weight and a content of the photopolymerization initiator (C) of from 0.01 to 5% by weight relative to a total amount of the ultraviolet-curable adhesive, with the remainder being composed of the photopolymerizable compound (B) and other components.
(23)
The ultraviolet-curable adhesive described in (22) above, which comprises, as the photopolymerizable compound (B), (i) (B-1-1) at least one (meth)acrylate oligomer of any of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton and (ii) (B-1-2) a monofunctional (meth)acrylate monomer, and has a content of the (meth)acrylate oligomer (B-1-1) of from 5 to 90% by weight and a content of the monofunctional (meth)acrylate monomer of from 5 to 70% by weight in a total amount of the ultraviolet-curable adhesive.
(24)
The ultraviolet-curable adhesive described in any one of (11) to (23) above, which further comprises (D) a softening component.
(25)
The ultraviolet-curable adhesive described in (24) above, wherein a content of the softening component (D) is from 10 to 80% by weight in a total amount of the ultraviolet-curable adhesive.
(26)
The ultraviolet-curable adhesive described in any one of (11) to (25) above, wherein the optical base material and the optical base material having a light-shielding portion on a surface thereof are an optical base material for touch panel.
(27)
A cured product obtained by irradiating the ultraviolet-curable adhesive described in any one of (11) to (25) above with an active energy ray.
(28)
A method for producing an optical member, comprising: laminating an optical base material and an optical base material having the light-shielding portion to each other with the ultraviolet-curable adhesive described in any one of (11) to (25) above; and then curing the ultraviolet-curable adhesive by irradiating an active energy ray through the optical base material having the light-shielding portion.
(29)
An ultraviolet-curable adhesive, comprising:
(A) an organic compound capable of absorbing an ultraviolet ray to emit light, which when measured in tetrahydrofuran, has a maximum wavelength of light absorption spectrum, in the range of from 250 to 400 nm and a maximum wavelength of light emission spectrum in the range of from 300 to 500 nm;
(B) a photopolymerizable compound; and
(C) a photopolymerization initiator.
According to the present invention, in laminating an optical base material such as a transparent protective plate, etc. with an ultraviolet-curable adhesive, even in the case where a light-shielding portion is formed in the optical base material, it is possible to thoroughly cure the adhesive positioned in a light-shielding area where the light is shielded by the presence of the light-shielding portion by irradiation with an ultraviolet ray from one direction without damaging a liquid display device or the like. For this reason, even when an obtained optical member is used for a display device, a problem such as uneven display in a displayed image in the vicinity of the light-shielding portion, etc. is not generated.
The ultraviolet-curable adhesive of the present invention is an ultraviolet-curable adhesive which is used for the purpose of laminating an optical base material and an optical base material having a light-shielding portion to each other and comprises the above-described organic compound (A), photopolymerizable compound (B), and photopolymerization initiator (C).
It is to be noted that in the present specification, the term “(meth)acrylate” means “methacrylate or acrylate”. The terms “(meth)acrylic acid” and “(meth)acrylate polymer” and the like are also the same.
The ultraviolet-curable adhesive of the present invention contains the above-described organic compound (A) (in the present specification, this organic compound is hereinafter also referred to simply as “organic compound (A)”).
As the above-described organic compound (A), any compound can be used without being particularly limited so long as it is an organic compound which when measured in tetrahydrofuran, has a maximum wavelength of light absorption spectrum (hereinafter also referred to simply as “light absorption maximum wavelength”) in the range of from 250 to 400 nm and a maximum wavelength, of light emission spectrum (hereinafter also referred to simply as “light emission maximum wavelength”) in the range of from 300 to 500 nm.
Specific examples of the organic compound (A) include anthracene compounds, coumarin compounds, carbazole compounds, benzoxazole compounds, naphthalene compounds, stilbene compounds, benzidine compounds, oxadiazole compounds, pyrene compounds, perylene compounds, naphthalimide compounds, benzotriazole compounds, and the like.
In addition, the above-described organic compound (A) is more preferably a compound having a light absorption maximum wavelength in the range of from 250 to 380 mm and a light emission maximum wavelength in the range of from 330 to 430 nm, and especially preferably a compound having a light absorption maximum wavelength in the range of from 270 to 320 nm and a light emission maximum wavelength in the range of from 350 to 400 nm.
By using the above-described organic compound (A), there is no concern that a cured product absorbs external light and is colored to an extent of being visually confirmed, and curing properties of an adhered product in a light-shielding area are extremely excellent. In addition, in view of the fact that the light emission maximum wavelength falls within the above-described range, there is no concern that light emission of the organic compound (A) is visually confirmed. Furthermore, the organic compound (A) is able to efficiently act on a photopolymerization initiator, is particular, a photopolymerization initiator whose absorption wavelength falls within the range of from 350 nm to 400 nm, and therefore, the organic compound (A) is excellent in a curing action and suitable.
The above-described maximum wavelength of light absorption spectrum and maximum wavelength of light emission spectrum can be, for example, confirmed by preparing a solution of the organic compound (A) in tetrahydrofuran (concentration: 0.002 wt %) and measuring a light absorption spectrum and a light emission spectrum of the obtained solution. The absorption spectrum can be measured by using a spectrophotometer (for example, “UV-3150”, manufactured by Shimadzu Corporation, etc.), and the light emission spectrum can be measured by using a fluorophotometer (for example, “P-7000”, manufactured by Hitachi High-Technologies Corporation, etc.).
By allowing the ultraviolet-curable adhesive to contain the organic compound (A) having such specified light absorption maximum wavelength and light emission maximum wavelength, it is possible to achieve thorough curing of the adhesive in a light-shielding area where an ultraviolet ray is not irradiated directly by irradiation with an ultraviolet ray from one direction. Specifically, when the organic compound (A) absorbs the specified light absorption maximum wavelength, light having the specified light emission maximum wavelength is radially emitted from the organic compound (A). Since the emitted light having a specified light emission maximum wavelength reaches the above-described light-shielding area, the photopolymerization initiator works even in the light-shielding area, and polymerization is advanced. Thus, it is possible to achieve thorough curing of the adhesive.
In addition, in the invention of the present application, it is preferable that the above-described organic compound (A) exists in a compatibilized state in the ultraviolet-curable adhesive composition. This is because when the organic compound (A) exists in a compatibilized state, distribution of the organic compound (A) in the composition becomes uniform, and hence, it becomes possible to evenly cure the adhesive, whereby curing of the light-shielding area is more accelerated, too.
In order to make the above-described compatibilization easy, a melting point of the organic compound (A) is preferably from 0 to 500° C., more preferably from 25 to 400° C., and especially preferably from 25 to 300° C.
Then, from the instant viewpoint, it is preferable that the ultraviolet-curable adhesive composition containing the organic compound (A) is in a compatibilized state (a state where the organic compound (A) is dissolved in the composition) at from ordinary temperature (25° C.) to 80° C.
Although the ultraviolet-curable adhesive containing the organic compound (A) according to the present invention varies with an application, from the viewpoint of an enhancement of visibility, for example, when formed into a cured product having a film thickness of 200 μm, its transmittance to light at 400 nm is preferably 80% or more, and especially preferably 90% or more.
The organic compound (A) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). A content proportion of the organic compound (A) in the ultraviolet-curable adhesive of the present invention is usually from 0.001 to 5% by weight, and preferably from 0.001 to 1% by weight.
With respect to the anthracene compound, coumarin compound, carbazole compound, benzoxazole compound, stilbene compound, oxadiazole compound, and benzidine compound, which are used as the organic compound (A), specific examples of preferred skeletons and compounds, and the like are hereunder exemplified.
As the anthracene compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (1) can be suitably used. It is to be noted that in the following structural formula, the * symbol represents a bond to each main skeleton.
Formula (1)
(In the formula, each R1 independently represents a hydrogen atom, a phenyl group, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylethynyl group; each X independently represents a hydrogen atom or a halogen atom; and each n independently represents an integer of from 1 to 4.)
Specifically, the phenyl group represented by R1 in the formula (1) represents a structure represented by the following formula (12).
Formula 912) (Phenyl Group)
(In the formula, each R11 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and k1 represents an integer of from 1 to 5.)
Specific examples of the phenylmethylene group, phenylethylene group, phenylpropylene group, and phenylethynyl group represented by R1 in the formula (1) include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylethynyl group, in which the benzene ring does not have a substituent; or a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylethynyl group, in which the benzene ring has an alkyl group having from 1 to 3 carbon atoms as a substituent. In addition, it is preferable that all of R11s in the foregoing formula (12) are a hydrogen atom.
It is especially preferable that R1 in the foregoing formula (1) is the phenyl group represented by the formula (12), and in addition, it is preferable that all of Xs in the foregoing formula (1) are a hydrogen atom.
Preferred specific examples of the anthracene compound which is used as the organic compound (A) include a halogenated anthracene, 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene, and 2-chloro-9,10-bis(phenylethynyl)anthracene. As the anthracene compound, 9,10-diphenylanthracene and 9,10-bis(phenylethynyl)anthracene are especially preferable.
As the coumarin compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (2) can be suitably used. It is to be noted that in the following structural formulae, the * symbol represents a bond to each main skeleton.
Formula (2)
(In the formula, each R2 independently represents a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, a benzimidazolyl group, or a benzothiazolyl group; each R3 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k independently represents an integer of 1 or 2.)
Each of the benzimidazolyl group and the benzothiazolyl group represented by R2 in the formula (2) may have a substituent, and specifically, they represent structures represented by the following formula (21) and the following formula (22), respectively.
Formula (21) (Benzimidazolyl Group)
(In the formula, each R21 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and q1 represents an integer of from 1 to 4.)
Formula (22) (Benzothiazolyl Group)
(In the formula, each R22 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and q2 represents an integer of from 1 to 4.)
It is preferable that R2 and R3 in the foregoing formula (2) are an alkyl group having from 1 to 3 carbon atoms; and it is more preferable that among R2s, R2 that substitutes on the benzene ring is a hydrogen atom, with the other R2 being an alkyl group having from 1 to 3 carbon atoms, all of ks are 1, and all of R3s are an alkyl group having from 1 to 3 carbon atoms.
Preferred specific examples of the coumarin compound which is used as the organic compound (A) include 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, and 7-diethylamino-4-methylcoumarin. As the coumarin compound, 7-diethylamino-4-methylcoumarin is especially preferable.
As the carbazole compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (3) can be suitably used. It is to be noted that in the following structural formulae, the * symbol represents a bond to each main skeleton.
Formula (3)
(In the formula, R4 represents an alkoxy group having from 1 to 3 carbon atoms, a phenyl group, a biphenyl group, a biphenyldiyl group, or a benzene-1,3,5-triyl group represented by the following formula (4):
each R5 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; 1 represents an integer of from 1 to 3; and each m independently represents an integer of from 1 to 4.)
In the formula (3), when R4 is an alkoxy group having from 1 to 3, a phenyl group, or a biphenyl group, then 1 is 1; when R4 is a biphenyldiyl group, then 1 is 2; and when R4 is the group represented by the formula (4), then 1 is 3.
Each of the phenyl group, the biphenyl group, and the biphenyldiyl group represented by R4 in the formula (3) may have a substituent and specifically, they represent structures represented by the following formula (41), formula (42), and formula (43), respectively.
Formula (41) (Phenyl Group)
(In the formula, each R41 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and k41 represents an integer of from 1 to 5.)
Formula (42) (Biphenyl Group)
(In the formula, each R42 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k42 independently represents an integer of from 1 to 4.)
Formula (43) (Biphenyldiyl Group)
(In the formula, each R43 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k43 independently represents an integer of from 1 to 4.)
It is preferable that all of R41s in the foregoing formula (41), R42s in the foregoing formula (42), and R43s in the foregoing formula (43) are a hydrogen atom.
Since the ultraviolet-curable adhesive having such a carbazole compound added thereto according to the present invention is excellent in curing properties in the light-shielding area, the carbazole compound can be suitably used as the organic compound (A).
R4 in the foregoing formula (3) is preferably the phenyl group represented by the formula (41) or the biphenyldiyl group represented by the formula (43), and more preferably the biphenyldiyl group represented by the formula (43). In addition, it is preferable that all of R5s in the foregoing formula (3) are a hydrogen atom.
Preferred specific examples of the carbazole compound which is used as the organic compound (A) include 1,3,5-tri(9H-carbazol-9-yl)benzene, 4,4′-bis(9H-carbazol-9-yl)biphenyl, 9,9′-(2,2′-dimethylbiphenyl-4,4′-diyl)bis(9H-carbazole), and 9-phenylcarbazole. As the carbazole compound, 4,4′-bis(9H-carbazol-9-yl)biphenyl and 9-phenylcarbazole are especially preferable.
It is to be noted that in view of the fact that the above-described carbazole compound is weak in light emission of visible light or weak in light absorption of visible light, even by adding the carbazole compound to the ultraviolet-curable adhesive, its cured product is able to ensure extremely high transparency, and visibility of a displayed image is extremely high, too. For this reason, the above-described carbazole compound can be suitably used in the ultraviolet-curable adhesive of the present invention.
As the benzoxazole compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (5) can be suitably used. It is to be noted that in the following structural formula, the * symbol represents a bond to each main skeleton.
Formula (5)
(In the formula, each R6 independently represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; R7 represents an alkylene group having from 1 to 3 carbon atoms or a group represented by the following formula (6):
and p represents an integer of from 1 to 4.)
R6 in the foregoing formula (5) is preferably an alkyl group having from 1 to 6 carbon atoms, more preferably a branched alkyl group having from 4 to 6 carbon atoms, and still more preferably a tert-butyl group. In addition, R7 in the foregoing formula (5) is preferably the group represented by the foregoing formula (6). p in the foregoing formula (5) is preferably 1.
Preferred specific examples of the benzoxazole compound which is used as the organic compound (A) include 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole).
As the stilbene compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (7) can be suitably used.
Formula (7)
(In the formula, each R8 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each r independently represents an integer of from 1 to 5.)
It is preferable that all of R8s in the foregoing formula (7) are a hydrogen atom.
Preferred specific examples of the stilbene compound which is used as the organic compound (A) include trans-1,2-diphenylethylene.
It is to be noted that in view of the fact that the above-described stilbene compound is weak in light emission of visible light or weak in light absorption of visible light, even by adding the stilbene compound to the ultraviolet-curable adhesive, its cured product is able to ensure extremely high transparency, and visibility of a displayed image is extremely high, too. For this reason, the above-described stilbene compound can be suitably used in the ultraviolet-curable adhesive of the present invention.
As the benzidine compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (8) can be suitably used. It is to be noted that in the following structural formulae, the * symbol represents a bond to each main skeleton.
Formula (8)
(In the formula, each R9 independently represents a hydrogen atom, a phenyl group, or a naphthyl group; each R10 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each s independently represents an integer of from 1 to 4.)
Each of the phenyl group and the naphthyl group represented by R9 in the formula (8) may have a substituent, and specifically, they represent structures represented by the following formula (81) and formula (82), respectively.
Formula (81) (Phenyl Group)
(In the formula, each R101 independency represents a hydrogen, atom or an alkyl group having from 1 to 6 carbon atoms; and k81 represents an integer of from 1 to 5.)
formula (82) (Naphthyl Group)
(In the formula, each R102 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k4 independently represents an integer of from 1 to 3.)
It is preferable that all of R101s in the foregoing formula (81) and R102s in the foregoing formula (82) are a hydrogen atom.
R9 in the foregoing formula (8) is preferably the phenyl group represented by the formula (81) or the naphthyl group represented by the formula (82), and the benzidine compound represented by the foregoing formula (8) is more preferably a compound having both the phenyl group and the naphthyl group in a molecule thereof together.
Preferred specific examples of the benzidine compound which is used as the organic compound (A) include N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine.
It is to be noted that in view of the fact that the above-described benzidine compound is weak in light emission of visible light or weak in light absorption of visible light, even by adding the benzidine compound to the ultraviolet-curable adhesive, its cured product is able to ensure extremely high transparency, and visibility of a displayed image is extremely high, too. For this reason, the above-described benzidine compound can be suitably used in the ultraviolet-curable adhesive of the present invention.
As the oxadiazole compound which is used as the organic compound (A), a compound having a skeleton represented by the following formula (9) can be suitably used.
Formula (9)
(In the formula, R201 represents an alkyl group having from 1 to 4 carbon atoms; W Represents a direct bond or a coupling group represented by the following formula (10); and Y represents CH or a nitrogen atom.)
Formula (10)
In the foregoing formula (10), Z represents a phenylene group, a bipyridine residue, or a fluorene residue.
The “bipyridine residue” and the “fluorene residue” represented by Z in the foregoing formula (10) mean divalent residues obtained by eliminating two hydrogen atoms in bipyridine and fluorene, respectively. In the formula (10), each of t3 and t4 represents an integer of from 0 to 2, and t3 and t4 are not 0 at the same time. It is to be noted that * in the formulae (9) and (10) represents a coupling site. The coupling site in the formula (9) is bonded to a carbon atom of the oxadiazole skeleton. In the coupling sites in the formula (10), the left end is bonded to the oxadiazole skeleton, and the right end is bonded to the benzene skeleton or the pyridine skeleton (the benzene ring having R1 at the 4-position or the Y-containing 6-membered ring in the formula (9)).
Here, the phenylene group can be represented by the following formula (90) or formula (91); the bipyridine residue can be represented by the following formula (92); and the fluorene residue can be represented by the following formula (93).
formula (90) (Phenylene Group)
(In the formula, each R200 independently represents a hydrogen atom or an alkyl group Having from 1 to 3 carbon atoms; and k50 represents an integer of from 1 to 4.)
R200 in the formula (90) is preferably a hydrogen atom.
Formula (91) (Phenylene Group)
(In the formula, each R202 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and k5 represents an integer of from 1 to 4.)
R202 in the formula (91) is preferably a hydrogen atom.
Formula (92) (Bipyridine Residue)
(In the formula, each R203 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k6 independently represents an integer of from 1 to 3.)
R203 in the formula (92) is preferably a hydrogen atom.
Formula (93) (Fluorene Residue)
(In the formula, each R204 independently represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms; and each k7 independently represents an integer of from 1 to 3.)
R204 in the formula (93) is preferably a hydrogen atom.
In the compound represented by the foregoing formula (9), It is preferable that W is a direct bond or the coupling group represented by the foregoing formula (10 ) wherein Z is a phenylene group from the standpoint that the compound represented by the foregoing formula (9) can be easily dissolved in the ultraviolet-curable adhesive at from ordinary temperature (25° C.) to 80° C.
With respect to t3 and t4, as is clear from the structure of the oxadiazole skeleton as well as the fact that t3 and t4 are not 0 at the same time, a total sum of t3 and t4 is an integer of 1 or 2. It is preferable that the total sum of t3 and t4 is 2, and it is especially preferable that both t3 and t4 are 1. In addition, in the case where the compound represented by the foregoing formula (9) has the coupling group represented by the foregoing formula (10) as W, a compound wherein any one of t3 or t4 is 2, with the other being 0 is preferable.
Y in the foregoing formula (9) is preferably CH.
In the foregoing formula (9), when the number of residues is represented by t3, as for the residue composed of W and two Y containing 6-membered rings, a residue in which all of the two 6-membered rings are a benzene ring, or all of the two 6-membered rings are a pyridine ring is preferable, and a residue composed of W and a 4-biphenyl group is especially preferable.
Specific examples of the alkyl group having from 1 to 4 carbon atoms in R201 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. R201 is preferably a branched alkyl group, and especially preferably a t-butyl group.
The number of W in the foregoing formula (9) is coincident with the number of a total sum of t3 and t4 and is 1 or 2. When the total sum of t3 and t4 is 2, it is preferable that one of Ws is a direct bond. When t3 or t4 is 2, it is preferable that one of Ws is a direct bond, and the other is the coupling group represented by the foregoing formula (10); and it is more preferable that the other is the coupling group represented by the foregoing formula (10) wherein Z is a phenylene group.
Among the compounds represented by the foregoing formula (9), 2-(4-bipheny)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole represented by the following formula (11) can be especially suitably used.
Formula (11)
It is to be noted that in view of the fact that the above-described oxadiazole compound is weak in light emission of visible light or weak in light absorption of visible light, even by adding the oxadiazole compound to the ultraviolet-curable adhesive, its cured product is able to ensure extremely high transparency, and visibility of a displayed image is extremely high, too. For this reason, the above-described oxadiazole compound can be suitably used in the ultraviolet-curable adhesive of the present invention.
In the ultraviolet-curable adhesive of the present invention, it is preferable to use, as the organic compound (A), a compound selected from the anthracene compound represented by the foregoing formula (1), the coumarin compound represented by the foregoing formula (2), the carbazole compound represented by the foregoing formula (3), the benzoxazole compound represented by the foregoing formula (5), the stilbene compound represented by the foregoing formula (7), the benzidine compound represented by the foregoing formula (8), and the oxadiazole compound represented by the foregoing formula (9).
From the viewpoint of curing properties of the light-shielding portion, it is more preferable to use, as the organic compound (A), a compound selected from the anthracene compound represented by the foregoing formula (1),the carbazole compound represented by the foregoing formula (3), the benzoxazole compound represented by the foregoing formula (5), and the oxadiazole compound represented by the foregoing formula (9).
From the viewpoint of transparency, it is more preferable to use, as the organic compound (A), the carbazole compound represented by the foregoing formula (3), the stiibene compound represented by the foregoing formula (7), the benzidine compound represented by the foregoing formula (8), and the oxadiazole compound represented by the foregoing formula (9).
As the organic compound (A), the carbazole compound represented by the foregoing formula (3) and the oxadiazole compound represented by the foregoing formula (9) are especially preferable, and 4,4′-bis(9H-carbazol-9-yl)biphenyl or 2-(4-bipheny)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole is the most preferable.
In addition, the ultraviolet-curable adhesive of the present invention contains (B) a photopolymerizable compound.
As the photopolymerizable compound (B), any compound can be used without being particularly limited so long as it is a compound which is polymerized with an ultraviolet ray. Examples thereof include (B-1) a (meth)acrylate compound, (B-2) an epoxy compound, (B-3) an oxetane compound, and the like.
In the ultraviolet-curable adhesive of the present invention, the (meth)acrylate compound (B-1) can be used as the photopolymerizable compound (B).
Examples of the (meth)acrylate compound (B-1) which can be used in the ultraviolet-curable adhesive of the present invention include (B-1-1) at least one (meth)acrylate oligomer of any of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton. For the ultraviolet-curable adhesive of the present invention, such (meth)acrylate oligomer (B-1-1) can be used solely or in combination of two or more kinds thereof.
By using such (meth)acrylate oligomer (B-1-1) as the photopolymerizable compound (B), it is possible to obtain an ultraviolet-curable adhesive which is excellent in flexibility and low in curing shrinkage ratio in terms of a cured product thereof. Therefore, it is preferable that the ultraviolet-curable adhesive of the present invention contains the (meth)acylate oligomer (B-1-1).
In order to make the cured product have flexibility, an average molecular weight of the (meth)acrylate oligomer (B-1-1) is usually from about 2,000 to 100,000, and preferably from about 5,000 to 50,000.
Above all, (B-1-1a) a urethane (meth)acrylate oligomer can be suitably used as the photopolymerizable compound (B) because it is able to increase a curing performance of the resin in the light-shielding area while ensuring flexibility at the time of curing.
As for the above-described (meth)acrylate oligomer (B-1-1), the urethane (meth)acrylate oligomer (B-1-1a) is described.
Although the urethane (meth)acrylate oligomer (B-1-1a) which can be used for the ultraviolet-curable adhesive of the present invention is not particularly limited, a urethane (meth)acrylate oligomer which is obtained through a reaction among three members of a polyhydric alcohol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate, and the like can be exemplified.
Examples of the above-described polyhydric alcohol include alkylene glycols having from 1 to 10 carbon atoms, such as neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediel, 1,6-hexanediol, etc.; triols such as trimethylolpropane, pertaerythritol, etc.; alcohols having a cyclic skeleton, such as tricyclodecanedimethylol, bis-[hydroxymethyl]-cyclohexane, etc.; polyester polyols obtained through a reaction between such a polyhydric alcohol and a polybasic acid (for example, succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride, etc.); caprolactone alcohols obtained through a reaction between such a polyhydric alcohol and ε-caprolactone; polycarbonate polyols (for example, polycarbonate diol obtained through a reaction between 1,6-hexanediol and diphenyl carbonate, etc.); polyether polyols (for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide-modified bisphenol A, etc.); and the like. From the viewpoint of adhesion to the base material, C2-C4-alkylene glycols having a molecular weight of 1,000 or more, and preferably from 1,000 to 5,000 are preferable. Above all, polypropylene glycol having a molecular weight of 2,000 or more, for example, from about 2,000 to 5,000, is especially preferable.
Examples of the above-described organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, dicyclopentanyl isocyanate, and the like, with isophorone diisocyanate being preferable.
As the above-described hydroxyl group-containing (meth)acrylate, for example, hydroxy-C2-C4-alkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.; dimethylol cyclohexyl mono(meth)acrylate; hydroxycaprolactone (meth)acrylate; and the like can be used. Of these, 2-hydroxyethyl (meth)acrylate is preferable.
The above-described reaction is, for example, carried out in the following manner. That is, the above-described polyhydric alcohol is mixed with the above-described organic polyisocyanate such that a proportion of the isocyanate group of the above-described organic polyisocyanate is preferably from 1.1 to 2.0 equivalents, and more preferably from 1.1 to 1.5 equivalents to one equivalent of the hydroxyl group of the polyhydric alcohol, and the reaction is carried out at a reaction temperature of preferably from 70 to 90° C., thereby synthesizing a urethane oligomer. Subsequently, the above-described hydroxyl group-containing (meth)acrylate is mixed such that a proportion of the hydroxyl group of the above-described hydroxyl group-containing (meth)acrylate is preferably from 1 to 1.5 equivalents to one equivalent of the isocyanate group of the obtained urethane oligomer, and the mixture is allowed to react at from 70 to 90° C., whereby the desired urethane (meth)acrylate oligomer (B-1-1a) can be obtained.
A weight average molecular weight of the urethane (meth)acrylate oligomer (B-1-1a) which can be used for the ultraviolet-curable adhesive of the present invention is preferably from about 7,000 to 25,000, and more preferably from about 10,000 to 20,000. When the weight average molecular weight is too low, at the time of curing the adhesive, shrinkage becomes large, whereas when the weight average molecular weight is too high, curing properties of the adhesive become poor.
In the ultraviolet-curable adhesive of the present invention, such urethane (meth)acrylate oligomer (B-1-1a) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). When the urethane (meth)acrylate oligomer is contained, its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight.
As for the (meth)acrylate oligomer (B-1-1), a (meth)acrylate oligomer (B-1-1b) having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton is described.
As the (meth)acrylate oligomer (B-1-1b) having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton (hereinafter also referred, to as “the above-described oligomer (B-1-1b)”), which can be used for the ultraviolet-curable adhesive of the present invention, any (meth)acrylate oligomer can be used without being particularly limited so long as it is a known oligomer that is an oligomer having a polyisoprene skeleton and has a (meth)acryloyl group in an end thereof; a known oligomer that is an oligomer having a polybutadiene skeleton and has a (meth)acryloyl group in an end thereof; a known oligomer having both a polyisoprene skeleton and a polybutadiene skeleton and having a (meth)acryloyl group in an end thereof; or the like.
As the above-described (meth)acrylate oligomer (B-1-1b) having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton, an oligomer obtained by the following production method (a) or production method (b) can be suitably used.
A method in which an isoprene polymer, a butadiene polymer, or a copolymer thereof is first synthesized, subsequently, an unsaturated acid anhydride is allowed to react with the obtained polymer, and thereafter, a hydroxy (meth)acrylate compound is allowed to react with a part or the whole of the obtained polymer.
A method in which an unsaturated carboxylic acid or its derivative is allowed to react with a hydroxyl group-terminated isoprene polymer, a hydroxyl group-terminated butadiene polymer, or an isoprene-butadiene copolymer having a hydroxyl group in an end thereof.
The oligomer obtained by the above-described production method (a) (a method in which an isoprene polymer, a butadiene polymer, or a copolymer thereof is first synthesized, subsequently, an unsaturated acid anhydride is allowed to react with these polymers, and thereafter, a hydroxy (meth)acrylate compound is allowed to react with a part or the whole of the obtained polymer) is described.
As the polymer which is first synthesized in the above-described production method (a), an isoprene polymer or a butadiene polymer obtained by polymerizing one kind of isoprene or butadiene solely may be used, or an isoprene-butadiene copolymer obtained by copolymerizing a mixture of isoprene and butadiene may be used.
Examples of a method for polymerizing isoprene, butadiene, or a mixture of the both include a method in which isoprene and/or butadiene is subjected to anionic polymerization by using, as an initiator, an alkyllithium such as methyllithium, ethyllithium, s-butyllithium, n-butyllithium, pentyllithium, etc., a sodium naphthalene complex, or the like. In addition, such a polymer can also be produced by a method in which isoprene and/or butadiene is subjected to radical polymerization by using, as an initiator, a peroxide such as benzoyl peroxide, etc., or an azobisnitrile compound such as azobisisobutyronitrile, etc.
It is to be noted that such a polymerization reaction can be carried out through a reaction at from −100° C. to 200° C. for from 0.5 to 100 hours in the presence of a solvent such as hexane, heptane, toluene, xylene, etc.
From the viewpoint of imparting flexibility, a number average molecular weight of the above-described polymer which is used in the present invention is usually in the range of from 2,000 to 100,000, preferably in the range of from 5,000 to 50,000, and especially preferably in the range of from 20,000 to 50,000.
Subsequently, an unsaturated acid anhydride is allowed to react with the polymer obtained by the above-described method. This reaction can be, for example, carried out through a reaction between the above-described polymer and unsaturated acid anhydride usually at a reaction temperature of from ordinary temperature to 300° C. for from 0.5 to 100 hours in the presence of a solvent which is inert to the reaction, such as hexane, heptane, toluene, xylene, etc., or in the absence of a solvent.
As the unsaturated acid anhydride in the above-described reaction, for example, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., can be used.
In general, a use amount of the above-described unsaturated acid anhydride is preferably in the range of from 0.1 to 200 parts by weight, and more preferably in the range of from 0.1 to 100 parts by weight based on 100 parts by weight of the above-described polymer.
When reacted under the above-described conditions, an addition number of the acid anhydride group to the above-described polymer is usually in the range of from 1 to 30, and preferably in the range of from 2 to 20 per molecule.
Subsequently, by allowing a hydroxy (meth)acrylate compound to react with a part or the whole of the acid anhydride group introduced into the above-described polymer, it is possible to obtain a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton.
In general, the above-described reaction can be carried out by mixing a hydroxy (meth)acrylate compound such that a proportion of the hydroxyl group of the hydroxy (meth)acrylate compound is preferably from 1 to 1.5 equivalents to one equivalent of the acid anhydride group in the above-described polymer and allowing the mixture to react at a reaction temperature of from 20 to 200° C. for from 0.1 to 100 hours in the presence of a solvent such as hexane, heptane, etc. or under a solvent-free condition.
As the hydroxy (meth)acrylate compound which is used for the above-described reaction, for example, hydroxy-C2-C4-alkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylates etc.; dimethylol cyclohexyl mono(meth)acrylate; hydroxycaprolactone (meth)acrylate; and the like can be used.
Next, the oligomer obtained by the above-described production method (b) (a method of allowing an unsaturated carboxylic acid or its derivative to react with a hydroxyl group-containing isoprene polymer, a butadiene polymer, or a copolymer thereof) is described.
By allowing an unsaturated carboxylic acid or its derivative to react with a part or the whole of a hydroxyl group-terminated isoprene polymer, a hydroxyl group-terminated butadiene polymer, or an isoprene-butadiene copolymer having a hydroxyl group in an end thereof, it is possible to obtain a (meth)acrylate oligomer having a polyisoprene skeleton or a (meth)acrylate oligomer having a polybutadiene skeleton.
In general, the above-described reaction can be carried out through a reaction of an unsaturated carboxylic acid or its derivative at a reaction temperature of from 20 to 200° C. for from 0.1 to 100 hours in the presence of a solvent such as hexane, heptane, etc. or under a solvent-free condition.
As the unsaturated carboxylic acid or its derivative which is used for the above-described reaction, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, α-ethylacrylic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydropthalic acid, methyltetrahydrophthalic acid, etc.; and derivatives thereof such as their acid halides, amides, imides, anhydrides, or esters, etc. can be used.
As specific examples of the oligomer (B-1-1b), UC-203, manufactured by Kuraray Co., Ltd. (a product name; an esterification product oligomer between a maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl methacrylate), NISSO-PB TE-2000, manufactured by Nippon Soda Co., Ltd. (a both ends methacrylate-modified butadiene-based oligomer), and the like can be exemplified.
In the ultraviolet-curable adhesive of the present invention, the oligomer (B-1-1b) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). When the oligomer (B-1-1b) is contained, its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight.
In view of the fact that a cured product having excellent flexibility and low curing shrinkage ratio can be obtained, it is preferable that the ultraviolet-curable adhesive of the present invention contains, as the photopolymerizable compound (B), such (meth)acrylate oligomer (B-1-1), namely at least one of the above-described urethane (meth)acrylate oligomer (B-1-1a) and the above-described oligomer (B-1-1b).
At that time, a content proportion of the (meth)acrylate oligomer (B-1-1) in the ultraviolet-curable adhesive of the present invention is usually from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight.
In the ultraviolet-curable adhesive, of the present invention, (B-1-2) a monofuuctional (meth)acrylate monomer can be used as the (meth)acrylate compound (B-1).
Although the monofunctional (meth)acrylate monomer (B-1-2) which is contained in the ultraviolet-curable adhesive of the present invention is not particularly limited, for example, alkyl (meth)acrylates having from 5 to 20 carbon atoms, such as isooctyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, cetyl (meth)acrylate, isomyristyl (meth)acrylate, tridecyl (meth)acrylate, etc.; (meth)acrylates having a cyclic skeleton, such as benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acryloyl morpholine, phenylglycidyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, 1-adamantyl methacrylate, polypropylene oxide-modified nonylphenyl (meth)acrylate, dicyclopentadieneoxyethyl (meth)acrylates etc.: hydroxyl group-containing alkyl (meth)acrylates having from 1 to 5 carbon atoms, such as 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)actylate, etc.; polyalkylene glycol (meth)acrylates such as ethoxydiethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polypropylene oxide-modified nonylphenyl (meth)acrylate, etc.; phosphoric acid (meth)acrylates such as ethylene oxide-modified phenoxylated phosphoric acid (meth)acrylate, ethylene oxide-modified butoxylated phosphoric acid (meth)acrylate, ethylene oxide-modified octyloxylated phosphoric acid (meth)acrylate, etc.; and the like can be exemplified.
Above all, alkyl (meth)acrylates having from 10 to 20 carbon atoms, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, hydroxyl group-containing alkyl (meth)acrylates having from 1 to 5 carbon atoms, such as 4-hydroxybutyl (meth)acrylate, etc., tetrahydrofurfuryl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and polypropylene oxide-modified nonylphenyl (meth)acrylate are exemplified as the preferred monofunctional (meth)acrylate monomer (B-1-2).
In particular, from the viewpoint of flexibility of a cured product, a compound selected from the group consisting of an alkyl (meth)acrylate having from 10 to 20 carbon atoms, dicyclopentenyloxyethyl (meth)acrylate, polypropylene oxide-modified nonylphenyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate is preferable as the monofunctional (meth)acrylate monomer (B-1-2).
Meanwhile, from the viewpoint of enhancing adhesion to glass, it is preferable to use a hydroxyl group-containing alkyl (meth)acrylate having from 1 to 5 carbon atoms, acryloyl morpholine, or dicyclopentanyl (meth)acrylate as the monofunctional (meth)acrylate monomer (B-1-2).
It is the most preferable to use dicyclopentenyloxyethyl (meth)acrylate or dicyclopentanyl (meth)acrylate as the monofunctional (meth)acrylate monomer (B-1-2) which is contained in the ultraviolet-curable adhesive of the present invention.
In the ultraviolet-curable adhesive of the present invention, such monofunctional (meth)acrylate monomer (B-1-2) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary).
It is preferable that the ultraviolet-curable adhesive of the present invention contains the above-described monofunctional (meth)acrylate monomer (B-1-2) as the photopolymerizable compound (B). A content proportion of the above-described monofunctional (meth)acrylate monomer (B-1-2) in the ultraviolet-curable adhesive of the present invention is usually from 5 to 70% by weight, and preferably from 5 to 50% by weight.
The ultraviolet-curable adhesive of the present invention can contain (B-1-3) a (meth)acrylate monomer other than the monofunctional (meth)acrylate monomer (B-1-2), for example, a polyfunctional (meth)acrylate monomer (hereinafter also referred to as “polyfunctional (meth)acrylate monomer (B-1-3)”) or (B-1-4) an epoxy (meth)acrylate monomer, or the like within the range where properties of the present invention are not impaired. In general, in the ultraviolet-curable adhesive of the present invention, such a monomer may not be contained, and it may be added, if desired.
As the polyfunctional (meth)acrylate monomer (B-1-3), bifunctional to hexafunctional (meth)acrylate monomers having, from 2 to 6 (meth)acryloyl groups can be exemplified.
Examples of a bifunctional (meth)acrylate monomer include tricyclodecanedimethylol di(meth)acrylate, dioxane glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, an alkylene oxide-modified bisphenol A type di(meth)acrylates caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, and the like.
Examples of a trifunctional (meth)acrylate monomer include trimethylol C2-C10-alkane tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, etc.; trimethylol C2-C10-alkane polyalkoxy tri(meth)acrylates such as trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxypolypropoxy tri(meth)acrylate, etc.; alkylene oxide-modified trimethylolpropane tri(meth)acrylates such as tris[(meth)acryloyloxyethyl]isocyanurate, pentaerythrtol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, etc.; and the like.
Examples of a tetrafunctional or multifunctional (meth)acrylate monomer include pentaerthritol polyethoxy tetra(meth)acrylate, pentaerythritol polypropoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
In the present invention, in the case of using the poly functional (meth)acrylate monomer (B-1-3) in combination, from the viewpoint of suppressing curing shrinkage at the time of curing of the ultraviolet-curable adhesive, it is preferable to use a bifunctional (meth)acrylate.
In the ultraviolet-curable adhesive of the present invention, the polyfunctional (meth)acrylate monomer (B-1-3) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). In the case of containing the (meth)acrylate monomer (B-1-3), its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 5 to 70% by weight, and preferably from 5 to 50% by weight.
Meanwhile, from the viewpoint of not impairing flexibility, a content proportion of the above-described polyfunctional (meth)acrylate monomer (B-1-3) in the ultraviolet-curable adhesive is preferably not more than 20% by weight, and especially preferably not more than 10% by weight.
In the ultraviolet-curable adhesive of the present invention, (B-1-4) an epoxy (meth)acrylate can be used within the range where properties of the present invention are not impaired. The epoxy (meth)acrylate (B-1-4) has functions of not only enhancing curing properties of the obtained ultraviolet-curable adhesive but enhancing curing rate and hardness of a cured product.
As the epoxy (meth)acrylate (B-1-4) which can be used for the ultraviolet-curable adhesive of the present invention, any compound which is obtained through a reaction between a glycidyl ether type epoxy compound and (meth)acrylic acid can be used. As the glycidyl ether type epoxy compound for the purpose of obtaining a preferred epoxy (meth)acrylate, a diglycidyl ether of bisphenol A or an alkylene oxide adduct thereof, a diglycidyl ether of bisphenol F or an alkylene oxide adduct thereof, a diglycidyl ether of hydrogenated bisphenol A or an alkylene oxide adduct thereof, a diglycidyl ether of hydrogenated bisphenol F or an alkylene oxide adduct thereof, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like can be exemplified.
The above-described epoxy (meth)acrylate (B-1-4) is obtained by allowing such a glycidyl ether type epoxy compound and (meth)acrylic acid to react with each other under the following conditions.
(Meth)acrylate acid is allowed to react in a ratio of preferably from 0.9 to 1.5 moles, and more preferably from 0.95 to 1.1 moles relative to one equivalent of the epoxy group of the glycidyl ether type epoxy compound. A reaction temperature is preferably from 80 to 120° C., and a reaction time is from about 10 to 35 hours. In order to accelerate this reaction, for example, it is preferable to use a catalyst such as triphenyl phosphine, 2,4,6-tris(dimethyaminomethyl)phenol (TAP), triethanolamine, tetraethylammonium chloride, etc. In addition, in order to prevent polymerization during the reaction from occurring, for example, p-methoxyphenol, methylhydroquinone, etc. can be used as a polymerization inhibitor, too.
Examples of the epoxy (meth)acrylate (B-1-4) which can be suitably used in the present invention include bisphenol A type epoxy (meth)acrylate which is obtained from the above-described bisphenol A type epoxy compound.
A weight average molecular weight of the epoxy (meth)acrylate (B-1-4) which can be used in the present invention is preferably from 500 to 10,000.
In the ultraviolet-curable adhesive of the present invention, such epoxy (meth)acrylate (B-1-4) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). In the case of containing the epoxy (meth)acrylate (B-1-4), its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight.
Meanwhile, from the viewpoint of not impairing flexibility, a content proportion of the above-described epoxy (meth)acrylate (B-1-4) in the ultraviolet-curable adhesive is preferably not more than 20% by weight, and especially preferably not more than 10% by weight.
In the ultraviolet-curable adhesive of the present invention, (B-2) an epoxy compound can be used as the photopolymerizable compound (B).
Specific examples of the epoxy compound (B-2) include polycondensates between a bisphenol (tor example, bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or a phenol (for example, phenol, an alkyl-substituted phenol, an aromatic substituted phenol, naphthol, an alky-substituted naphthol, dihydoxybenzene, an alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and an aldehyde of every kind (for example, formaldehyde, acetaldehyde, an alkyl aldehyde, benzaldehyde, an alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polycondensates between the above-described phenol and a diene compound of every kind (for example, dicyclopentadiene, a terpene, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); polycondensates between the above-described phenol and a ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, beozophenone, etc.); polycondensates between the above-described phenol and an aromatic dimethanol (for example, benzenedimethanol, biphenyldimethanol, etc.); polycondensates between the above-described phenol and an aromatic dichloromethyl (for example, α,α′-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates between the above-described phenol and an aromatic bisalkoxymethyl (for example, bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); polycondensates between the above-described bisphenol and an aldehyde of every kind; glycidyl ether-based epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resins, and glycidyl ester-based epoxy resins, which are obtained by glycidylating an alcohol or the like; and the like. The epoxy compound (B-2) is not limited to these materials so long as it is a usually used epoxy resin. These materials may be used solely or in combination of two or more kinds thereof.
In the ultraviolet-curable adhesive of the present invention, such epoxy compound (B-2) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). In the case of containing the epoxy compound (B-2), its content proportion, in the ultraviolet-curable adhesive of the present invention is usually from 5 to 70% by weight, and preferably from 5 to 50% by weight.
In the ultraviolet-curable adhesive of the present invention, (B-3) an oxetane compound can be used as the photopolymerizable componnd (B).
Specific examples of the oxetane compound (B-3) include 4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-bis[(3-methyl-3-oxetanylmethoxy)methyl]bezene, 3-methyl-3-glycidyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, di(1-ethyl(3-oxetanyl))methyl ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-(cyclohexyloxy)methyl-3-ethyloxetane, xylylene bisoxetane, phenol novolac oxetane, and the like. The oxetane compound (B-3) is not limited to these materials so long as it is a usually used oxetane compound.
In the ultraviolet-curable adhesive of the present invention, such oxetane compound (B-3) can be used solely or in combination of two or more kinds thereof (a proportion in the combination is arbitrary). In the case of containing the oxetane compound (B-3), its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 5 to 70% by weight, and preferably from 5 to 50% by weight.
In the ultraviolet-curable adhesive of the present invention, it is preferable to use a combination of the above-described (meth)acrylate oligomer (B-1-1) and the above-described monofunctional (meth)acrylate monomer (B-1-2) as the photopolymerizable compound (B).
At that time, a urethane (meth)acrylate oligomer which is obtained through a reaction among three members of a polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate, or an oligomer which is obtained by allowing a hydroxy (meth)acrylate compound to react with a part or the whole of an isoprene polymer, a butadiene polymer, or an unsaturated acid anhydride adduct of a copolymer of these polymers is preferable as the (meth)acrylate oligomer (B-1-1). In addition, at that time, the monofunctional (meth)acrylate monomer (B-1-2) is preferably a compound selected from the group consisting of an alkyl (meth)acrylate having from 10 to 20 carbon atoms, 2-ethylhexyl carbitol acrylate, acryloyl morpholine, a hydroxyl group-containing alkyl (meth)acrylate having from 1 to 5 carbon atoms, tetrahydrofurfuryl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and polypropylene oxide-modified nonylphenyl (meth)acrylate.
The ultraviolet-curable adhesive of the present invention not only containing, as the (meth)acrylate oligomer (B-1-1), a urethane (meth)acrylate oligomer which is obtained through a reaction among three members of polypropylene glycol, isophorone diisocyanate, and 2-hydroxyethyl (meth)acrylate, or an esterification product oligomer between a maleic anhydride adduct of an isoprene polymer and 2-hydroxyethyl methacrylate but containing, as the monofunctional (meth)acrylate monomer (B-1-2), dicyclopentenyloxyethyl (meth)acrylate or dicyclopentanyl (meth)acrylate is especially preferable.
A content proportion of the photopolymerizable compound (B) in a total amount of the ultraviolet-curable adhesive of the present invention may be the remainder obtained by subtracting the contents of both the organic compound (A) and the photopolymerization initiator (C) from the total amount of the ultraviolet-curable adhesive.
Specifically, the content of the photopolymerizable compound (B) (in the case where plural compounds are used, the content means a total content thereof) in the total amount of the ultraviolet-curable adhesive is usually from 5 to 99.8% by weight, more preferably from 5 to 95% by weight, still more preferably from 20 to 90% by weight, and most preferably from 30 to 80% by weight. Of these, the ultraviolet-curable adhesive of the present invention containing, as the photopolymerizable compound (B), not only from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight of at least one (meth)acrylate oligomer (B-1-1) selected from the group consisting of a urethane (meth)acrylate oligomer and a (meth)acrylate oligomer having at least one skeleton of a polyisoprene skeleton or a polybutadiene skeleton but from 5 to 70% by weight and preferably from 5 to 50% by weight of the monofunctional (meth)acrylate monomer (B-1-2) is more preferable.
The ultraviolet-curable adhesive of the present invention contains (C) a photopolymerization initiator.
The photopolymerization initiator (C) which is contained in the ultraviolet-curable adhesive of the present invention, is not particularly limited, and known radical polymerization initiators and catonic polymerization initiators, and the like can be used.
As for specific examples of the radical polymerization initiator and product names thereof, for example, 1-hydroxycyclohexyl phenyl ketone (IRGACURE (a registered trademark, hereinafter the same) 184; manufactured by BASF), a 2-hydroxy-2-methyl-[4-(1-methyvinyl)phenyl]propanol oligomer (ESACURE ONE; manufactured by Lamberti), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-one (IRGACURE 2959; manufactured by BASF), 2-hydroxy-1{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (IRGACURE 127: manufactured by BASF), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651; manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR (a registered trademark) 1173; manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907; manufactured by BASF), a mixture of oxyphenylacetic acid 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid 2-[2-hydroxyethoxy]ethyl ester (IRGACURE 754; manufactured by BASF), bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium (IRGACURE 784; manufactured by BASF), 2-benzyl-2-dimethyamino-1-(4-morpholinophenyl)butan-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like can be exemplified.
As for specific examples of the cationic polymerization initiator, for example, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium triflate, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonic acid, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, and the like can be exemplified.
It is preferable that the photopolymerization initiator (C) which is contained in the ultraviolet-curable adhesive of the present invention has absorption at a wavelength of the light emitted by the above-described organic compound (A). The terms “has absorption at a wavelength of the light emitted by the above-described organic compound (A)” as referred to herein mean that the photopolymerization initiator (C) may absorb the light emitted by the organic compound (A) to be used, whereby activation of the photopolymerization initiator (C) is assisted. In view of the facts that the above-described organic compound (A) emits light having a light emission maximum wavelength in the above-described specified range, the photopolymerization initiator (C) which is used for the ultraviolet-curable resin composition is preferably one capable of absorbing a light emission maximum wavelength in the above-described specified range. For example, an absorption coefficient per unit weight of the photopolymerization initiator (C) at a light emission maximum wavelength of the organic compound (A) is 50 mL/(g·cm) or more, preferably 300 mL/(g·cm) or more, and more preferably 400 mL/(g·cm) or more.
Preferred specific examples of the photopolymerization initiator (C) which is used for the ultraviolet-curable adhesive of the present invention include the following compounds.
From the viewpoints of transparency and curing properties, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184; manufactured by BASF) and a 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer (ESACURE KIP-150; manufactured by Lamberti) are exemplified as the preferred photopolymerization initiator (C). From the viewpoint of making curing properties of the inside of the adhesive good, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO; manufactured by LAMBSON) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819; manufactured by BASF) are exemplified as the preferred photopolymerization initiator (C). From the viewpoint of suppressing discoloration of the adhesive, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO); manufactured by LAMBSON) is exemplified as the preferred photopolymerization initiator (C).
Furthermore, in view of the facts that handling under a specified circumference such as a yellow lamp circumference, etc. is not required; and internal curing properties are excellent, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO) is exemplified as the especially preferred photopolymerization initiator (C).
Such photopolymerization initiator (C) can be used solely or in combination of two or more kinds thereof (a proportion of the combination is arbitrary).
As for the photopolymerization initiator (C), its absorption coefficient per unit weight at 365 nm as measured in acetonitrile is preferably from 85 to 10,000 mL/(g·cm), more preferably from 150 to 10,000 mL/(g·cm), and especially preferably from 400 to 10,000 mL/(g·cm). The measurement of the absorption coefficient can be carried out by a usual method by using a spectral photometer or the like. In addition, as for the solvent for measurement, under certain circumstances, the measurement may also be carried out in methanol, and even in that case, the foregoing range of the absorption coefficient does not change.
In addition, as for the photopolymerization initiator (C), its absorption coefficient per unit weight at 405 nm as measured in acetonitrile is preferably from 5 to 3,000 mL/(g·cm), more preferably from 100 to 3,000 mL/(g·cm), and especially preferably from 200 to 3,000 mL/(g·cm).
A photopolymerization initiator which is satisfied with both the above-described conditions of absorption coefficient is extremely preferable as the photopolymerization initiator (C) of the present invention.
In addition, a photopolymerization initiator having a molar absorption coefficient at 400 nm as measured in acetonitrile of from 200 M−1·cm−1 to 100,000 M−1·cm−1 is also preferable.
By using the photopolymerization initiator (C) not only having an absorption coefficient falling within the foregoing range but having absorption at a wavelength of the light emitted by the above-described organic compound (A), curing of the ultraviolet-curable resin composition existing in the light-shielding area is more accelerated. This is because in view of the fact that an ultraviolet ray of a long wavelength as from 350 nm to 410 nm is large in properties of causing diffraction, so that it is able to go around to the rear side of the light-shielding portion, even in the case where the light-shielding portion that disturbs irradiation with an ultraviolet ray exists, the ultraviolet ray of a long wavelength is able to reach the light-shielding area.
For that reason, not only in view of the fact that the photopolymerization initiator (C) has an absorption-coefficient of the foregoing range, it is able to absorb an ultraviolet ray of a long wavelength, but even when the photopolymerization initiator (C) having absorption at a wavelength of the light emitted by the above-described organic compound (A) exists in the light-shielding area, it is able to absorb the light emitted by the above-described organic compound (A) and also absorb light of a long wavelength diffracted upon irradiation from a light source. A decomposition reaction of the photopolymerization initiator (C) is accelerated due to such a synergistic effect, and therefore, even in the case where the light-shielding area spreads over a wide range, it becomes possible to thoroughly cure the ultraviolet-curable adhesive existing in the light-shielding area.
Furthermore, by using a combination of the organic compound (A) whose maximum wavelength of light absorption spectrum as measured in tetrahydrofuran falls within the above-described suitable range with the photopolymerization initiator (C) whose absorption coefficient falls within the above-described suitable range, curing of the ultraviolet-curable adhesive existing in the light-shielding area is more accelerated, and therefore, the above-described combination of the above-described organic compound (A) with the photopolymerization initiator (C) is especially preferable.
Examples of the photopolymerization initiator whose absorption coefficient per unit weight at 365 nm is in an especially preferred range of from 400 to 10,000 mL/(g·cm) include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819; manufactured by BASF), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO: manufactured by LAMBSON), and bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium (IRGACURE 784; manufactured by BASF), and the like.
As the photopolymerization initiator (C) of the present invention, 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO), or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819) is preferable; 2,4,6-trimethylbenzoyldiphenylphospine oxide (SPEEDCURE TPO) or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819) is more preferable; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (SPEEDCURE TPO) is especially preferable.
In the ultraviolet-curable adhesive of the present invention, such photopolymerization initiator (C) can be used solely or in combination of two or more kinds thereof (a proportion of the combination is arbitrary). A content proportion of the photopolymerization initiator (C) in the ultraviolet-curable adhesive of the present invention is usually from 0.01 to 5% by weight, and preferably from 0.2 to 3% by weight. In addition, when the content of the photopolymerization initiator (C) is defined as 100 parts by weight, the content of the above-described organic compound (A) is usually from about 0.1 to 100 parts by weight, preferably from about 0.5 to 50 parts by weight, and more preferably from about 1 to 20 parts by weight. In the case of using two or more kinds of the photopolymerization initiator (C), a content proportion of a total amount thereof may fall within the foregoing range.
In the ultraviolet-curable adhesive of the present invention, a photopolymerization initiation assistant as described below, (D) a softening component as described later, additives as described later, and the like can be contained as other components than the above-described compound (A), the photopolymerizable compound (B), and photopolymerization initiator (C). A total amount of these other components in the total amount of the ultraviolet-curable adhesive is from about 0 to 80% by weight, and preferably from about 5 to 70% by weight.
In the ultraviolet-curable adhesive of the present invention, an amine that may work as the photopolymerization initiation assistant, or the like can also be used as one of the above-described other components in combination with the above-described photopolymerization initiator (C). Examples of the amine or the like which can be used include 2-dimethyaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like. In the case of using the photopolymerization initiation assistant such as an amine, etc., its content amount in the ultraviolet-curable adhesive of the present invention is usually from 0.005 to 5% by weight, and preferably from 0.01 to 3% by weight.
In the ultraviolet-curable adhesive of the present invention, (D) a softening component can be contained, if desired. In the present invention, known softening components and plasticizers which are usually used in an ultraviolet-curable adhesive can be used as the softening component (D).
Specific examples of the softening component (D) include oligomers and polymers which are not included in the above-described component (B); and compounds which are used as a plasticizer or the like, such as phthalic acid esters, phosphoric acid esters, glycol esters, glycol ethers, aliphatic dibasic acid esters, fatty acid esters, citric acid esters, epoxy-based plasticizers, castor oils, terpene-based hydrogenated resins, etc.
As for examples of the oligomer and polymer which are used as the softening component (D), polyisoprene skeleton-containing, polybutadiene skeleton-containing, or xylene skeleton-containing oligomers and polymers, which may have a hydroxyl group in an end thereof or the like; polyether compounds; and the like can be exemplified. Of these, polyisoprene skeleton- or polybutadiene skeleton-containing polymers which have a hydroxyl group in an end thereof or the like; and polyether compounds can also be exemplified as preferred materials.
Of these, polyisoprene skeleton- or/and polybutadiene skeleton-containing polymers which have a hydroxyl group in an end thereof or the like; and polyether compounds can also be exemplified as preferred materials.
As for specific examples of the polyether compound, di(allyl or/and C1-C4-alkyl) ethers of poly-C2-C4-alylene glycols, such as polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl butyl ether, polyethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol-polypropylene glycol dibutyl ether, polyethylene glycol-polypropylene glycol allyl butyl ether, etc., can be exemplified.
A weight average molecular weight of such a polymer is preferably from about 500 to 30,000, more preferably from about 500 to 25,000, and still more preferably from about 500 to 20,000. It is especially preferably from about 500 to 15,000.
Examples of other compounds which are used as a plasticizer or the like include phthalic acid esters, phosphoric acid esters, glycol esters, glycol ethers, aliphatic dibasic acid esters, fatty acid esters, citric add esters, epoxy-based plasticizers, castor oils, terpene-based hydrogenated resins, and the like.
In the case of using such softening component (D), its content proportion in the ultraviolet-curable adhesive of the present invention is usually from 10 to 80% by weight, and preferably from 10 to 70% by weight.
In addition, in the ultraviolet-curable adhesive of the present invention, a (meth)acrylic polymer can be used as the softening component (D).
Examples of the (meth)acrylic polymer which can be used in the present invention include polymers obtained by polymerizing an acrylic methacrylic monomer as a raw material; and copolymers between the instant monomer and a polymerizable monomer other than the instant monomer. These (meth)acrylic polymers can be produced by a usual method such as solution polymerization, suspension polymerization, bulk polymerization, etc.
Examples of the production method which is especially preferable include a method for undergoing the production by continuously carrying out radical polymerization at a high temperature. Specifically, the (meth)acrylic polymer is produced by the following process. First of all, an acrylic or methacrylic monomer is mixed with a minute amount of a polymerization initiator and a minute amount of a solvent. Then, the mixture is allowed to react at a temperature of 150° C. or higher for 10 minutes or more under a high pressure. Thereafter, by separating unreached components and a (meth)acrylic polymer obtained by the reaction from each other using a separator, it is possible to obtain the (meth)acrylic polymer.
Here, if the polymerization initiator is incorporated into the obtained (meth)acrylic polymer, there is a concern that the resultant is inferior in storage stability. For that reason, it is preferable that the above-described reaction is carried out while distilling off the solvent, or after separating the (meth)acrylic polymer, the solvent is distilled off.
Examples of the acrylic or methacrylic monomer which is used as the raw material of the (meth)acrylic polymer include (meth)acrylic acid; α-ethylacrylic acid; ester based (meth)acrylates such as methyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 1,3-dimethylbutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 3-ethoxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, α-(hydroxymethyl)ethyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, etc.; and the like. The above-described acrylic or methacrylic monomers can be used solely or in combination of two or more kinds thereof.
As other polymerizable monomer which may be copolymerized with the acrylic or methacrylic monomer, a known compound having an unsaturated double bond can be used. Examples thereof include styrene; 3-nitrostyrene; 4-methoxystyrene; alkylstyrenes such as α-methylstyrene, β-methylstyrene, 2,4-dimethylstyrene, vinyltoluene, α-ethylstyrene, α-butylstyrene, α-hexylstyrene, etc.; halogenated styrenes such as 4-chlorostyrene, 3-chlorostyrene, 3-bromostyrene, etc.; and carboxylic acids having an unsaturated double bond, such as crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, etc.
Of these, from the standpoints of solubility with other components of the composition and adhesion of a cured product, as the acrylic or methacrylic monomer, C1-C10-alkyl (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylates etc., and C1-C10-alkyl (meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc., are preferable; and as the other polymerizable monomer, styrene or the like is preferable.
In the present invention, a weight average molecular weight of the (meth)acrylic polymer is from 1,500 to 30,000, preferably from 3,000 to 20,000, and especially preferably from 5,000 to 15,000. In the case where the weight average molecular weight is less than 1,500, adhesion of a cured product tends to be inferior, whereas in the case where it is more than 30,000, the (meth)acrylic polymer is hardly dissolved in other monomers or becomes cloudy, and hence, such is not preferable.
The (meth)acrylic polymer is also easily available as a goods on the market. Examples thereof include “ARUFON Series”, manufactured by Toagosei Co., Ltd., which are available as a product name of UP-1170 or UH-2190.
In the case of using the (meth)acrylic polymer, a content proportion of the (meth)acrylic polymer in the ultraviolet-curable adhesive of the present invention is usually from 20% by weight to 95% by weight, preferably from 50% by weight to 95% by weight, more preferably from about 70% by weight to 95% by weight, and especially preferably from 70% by weight to 90% by weight.
In the ultraviolet-curable adhesive of the present invention, it is preferable to contain the softening component (D); and as for the softening component (D), it is more preferable to contain at least one member of a polyether compound and a hydroxyl group-containing polyisoprene-based oligomer or polymer, and it is especially preferable to contain polyethylene glycol-polypropylene glycol allyl butyl ether or hydroxyl group-containing polyisoprene.
In the case of containing, as the softening component (D), preferably at least one member of a polyether compound and a hydroxyl group-containing polyisoprene-based oligomer or polymer, and more preferably polyethylene glycol-polypropylene glycol allyl butyl ether or hydroxyl group-containing polyisoprene, its content proportion in the ultraviolet-curable adhesive of the present invention, is usually from 10 to 80% by weight, preferably from 10 to 70% by weight, and more preferably from 30 to 70% by weight.
In the ultraviolet-curable adhesive of the present invention, in addition to the above-described components, additives such as an organic solvent, a coupling agent, a polymerization inhibitor, a levelling agent, an antistatic agent, a surface lubricant, a light stabilizer (for example, a hindered amine compound, etc.), etc. may be further added, if desired.
Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, etc., dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, xylene, and the like.
Examples of the coupling agent include a silane coupling agent, a titanium-based coupling agent, a zirconium-based coupling agent, an aluminum-based coupling agent, and the like.
Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like.
Specific examples of the tianium-based coupling agent include isopropyl (N-ethyaminoethylamino)titanate, isopropyltriisostearoyl titanate, titanium Di(dioctylpyrophosphate) oxyacetate, tetraisopropyl di(dioctylphosphite)titanate, a neoalkoxytri(p-N-(β-aminoethyl)aminophenyl)titanate, and the like.
Specific examples of the zirconium-based or alumlnum-based coupling agent include Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, a neoalkoxy zirconate, a neoalkoxy trisneodecanoyl zirconate, a neoalkoxytris(dodecanoyl)benzenesulfonyl zirconate, a neoalkoxytris(ethylenediaminoethyl)zirconate, a neoalkoxytris(m-aminophenyl)zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al-propionate, and the like.
Specific examples of the polymerization inhibitor include p-methoxyphenol, methylhydroquinone, and the like.
Specific examples of the light stabilizer include hindered amine-based compounds such as 1,2,2,6,6-pentamethyl-4-piperidyl alcohol, 2,2,6,6-tetramethyl-4-piperidyl alcohol, 1,2,2,6,6-pentamethy4-piperidyl (meth)acrylate (a product name: LA-82, manufactured by ADEKA Corporation), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, a mixed esterification product of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,3,8,10-tetraoxaspiro[5,5]undecane, decanediole acid bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)proplonyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidnyl (meth)acrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl) ester, a reaction product of 1,1-dimethylethyl hydroperoxide and octane, N,N′,N″,N′″-tetrakis(4,6-bis(butyl(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine, a polycondensate of dibutylamine-1,3,5-triazine-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylene diamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], a polymerization product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5·1·11·1]heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo[5,1,11,2]heneicosane-20-propanoic acid dodecyl ester/tetradecyl ester, propanedioic acid-[(4-methoxyphenyl)methylene]bis(1,2,6,6-pentamethyl-4-piperidinyl) ester, a higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxyamide-N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl), etc.; benzophenone-based compounds such as octabenzone, etc.; benzotriazole-based compounds; such as 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[(2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydoxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, a reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, etc.; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc.; triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, etc.; and the like.
In particular, hindered amine-based compounds are preferable as the light stabilizer.
A content of the above-described various additives which are added, if desired, in a total amount of the ultraviolet-curable adhesive is from about 0 to 3% by weight in terms of a total amount of the above-described additives, in the case of using the additives, a content proportion of the additives in a total amount of the ultraviolet-curable adhesive is from 0.01 to 3% by weight, preferably from 0.01 to 1% by weight, and more preferably from 0.02 to 0.5% by weight in terms of a total amount of the above-described additives.
A preferred composition of the ultraviolet-curable adhesive of the present invention is as follows. It is to be noted that the term “% by weight” in the content of each component expresses a content proportion relative to the total amount of the ultraviolet-curable adhesive.
An ultraviolet-curable adhesive containing
from 0.001 to 5% by weight, preferably from 0.001 to 1% by weight, and more preferably from 0.001 to 0.1 % by weight of the compound (A);
from 5 to 99.8% by weight, preferably from 10 to 95% by weight, more preferably from 20 to 90% by weight, and most preferably from 30 to 80% by weight of the photopolymerizable compound (B) (in the case of using, as the photopolymerizable compound (B), both the (meth)acrylate oligomer (B-1-1) and the monofunctional (meth)acrylate monomer (B-1-2) in combination, a content proportion of the (meth)acrylate oligomer (B-1-1) is usually from 5 to 90% by weight, preferably from 20 to 80% by weight, and more preferably from 25 to 50% by weight, and a content proportion of the monofunctional (meth)acrylate monomer (B-1-2) is usually from 5 to 70% by weight, and preferably from 5 to 50% by weight, with a total sum of the both being preferably within the above-described range of the content of (B)); and
from 0.01 to 5% by weight, and preferably from 0.2 to 3% by weight of the photopolymerization initiator (C).
In the above-described case, a total sum of the component (A) and the component (C) is preferably at least 0.2% by weight, and more preferably from 0.2 to 5% by weight.
In the above-described case, when the total sum of the combination of preferred members is less than 100% by weight is corresponding to the case where the remainder is costs posed of components other than those described above (for example, the above-described component (D), etc.) or the above-described various additives are contained.
The ultraviolet-curable adhesive of the present invention in which the above-described ultraviolet-curable adhesive further contains the softening component (D) in a content proportion of from 10 to 80% by weight, and preferably from 10 to 70% by weight is more preferable. In the case of containing the softening component (D), a proportion of the component (D) is usually from about 30 to 200 parts by weight, and preferably from about 50 to 150 parts by weight based on 100 parts by weight of the above-described component (B). In addition, a total sum of the component (A) and the component (C) is usually from about 0.1 to 5 parts by weight, and preferably from about 0.2 to 2 parts by weight based on 100 parts by weight of a total sum of the component (B) and the component (D).
Some preferred embodiments in the ultraviolet-curable adhesive of the present invention are described below. The term “% by weight” in the content of each component expresses a content proportion relative to the total amount of the ultraviolet-curable adhesive.
An ultraviolet-curable adhesive in which the content of the organic compound (A) is from 0.001 to 5% by weight, and the content of the photopolymerization initiator (C) is from 0.01 to 5% by weight, with the remainder being composed of the photopolymerizable compound (B) and other components.
The ultraviolet-curable adhesive as set forth above in (I), in which a total sum of the organic compound (A) and the photopolymerization initiator (C) is from 0.1 to 5 parts by weight based on 100 parts by weight of the content of the photopolymerizable compound (B).
The ultraviolet-curable adhesive as set forth above in any one of (11) to (26) in the section of “Means for Solving the Problem” and (I) and (II), which contains, as the organic compound (A), at least one compound selected from an anthracene compound, a coumarin compound, a carbazole compound, a benzoxazole compound, a stilbene compound, a benzidine compound, and an oxadiazole compound.
The ultraviolet-curable adhesive as set forth above in (III), which contains, as the organic compound (A), at least one compound selected from the group consisting of an anthracene compound represented by the foregoing formula (1), a coumarin compound represented by the foregoing formula (2), a carbaxole compound represented by the foregoing formula (3), a benzoxazole compound represented by the foregoing formula (5), a stilbene compound represented by the foregoing formula (7), a benzidine compound represented by the foregoing formula (8), and an oxadiazole compound represented by the foregoing formula (9).
The ultraviolet-curable adhesive as set forth above in (IV), which contains, as the organic compound (A), at least one compound selected from the group consisting of an anthracene compound represented by the foregoing formula (1), a carbaxole compound represented by the foregoing formula (3), a benzoxazole compound represented by the foregoing formula (5), and an oxadiaxole compound represented by the foregoing formula (9).
The ultraviolet-curable adhesive as set forth above in (V), winch contains, as the organic compound (A), at least one compound selected, from the group consisting of 9,10-diphenylanthracene, 9,10-bis(phenylethynyl)anthracene, 4,4′-bis(9H-carbazol-9-yl)biphenyl, 2,5-thiophenediyl bis(5-tert-butyl-1,3-benzoxazole), and 2-(4-bipheny)-5-(4-tert-butylphenyl)-3,4-oxadiazole.
The ultraviolet-curable adhesive as set forth above in any one of (I) to (VI), which contains, as the photopolymerizable compound (B), both the above-described (meth)acrylate oligomer (B-1-1) and the above-described monofunctional (meth)acrylate monomer (B-1-2).
The ultraviolet-curable adhesive as set forth above in (VII), which contains, as the (meth)acrylate oligomer (B-1-1), at least one (meth)acrylate oligomer (B-1-1) selected from the group consisting of a urethane (meth)acrylate oligomer, a (meth)acrylate oligomer having a polyisoprene skeleton, and a (meth)acrylate oligomer having a polybutadiene skeleton.
The ultraviolet-curable adhesive as forth above in (VII) or (VIII), which contains, as the (meth)acrylate oligomer (B-1-1), a urethane (meth)acrylate oligomer which is obtained through a reaction among three members of polypropylene glycol, isophorone diisocyanate, and 2-hydroxyethyl (meth)acrylate, or an esterification product oligomer between a maleic anyhydride adduct of an isoprene polymer and 2-hydroxyethyl methacrylate; and contains, as the monofunctional (meth)acrylate mononer (B-1-2), dicyclopentenyloxyethyl (meth)acrylate or dicyclopentanyl (meth)acrylate.
The ultraviolet-curable adhesive as set forth above in any one of (VII) to (IX), in which the (meth)acrylate oligomer (B-1-1) has an average molecular weight of from 2,000 to 100,000.
The ultraviolet-curable adhesive as set form above in any one of (I) to (X), in which the photopolymerization initiator (C) has an absorption coefficient per unit weight at 365 nm as measured in acetonitrile of from 85 to 109,000 mL/(g·cm) and an absorption coefficient per unit weight at 405 nm as measured in acetonitrile of from 5 to 3,000 mL/(g·cm).
The ultraviolet-curable adhesive as set forth above in any one of (I) to (XI), in which the photopolymerization initiator (C) is at least one compound selected from 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenxoyl)phenylphosphine oxide.
The ultraviolet-curable adhesive as set forth above in any one of (I) to (XII), which further contains the softening component (D) in a proportion of from 10 to 80% by weight.
The ultraviolet-curable adhesive as set forth above in (XIII), in which a proportion of the softening component (D) is from 50 to 150 parts by weight based on 100 parts by weight of the photopolymerizable compound (B).
The ultraviolet-curable adhesive as set forth above in (XIII) or (XIV), in which a total sum of the organic compound (A) and the photopolymerization initiator (C) is from 0.1 to 5 parts by weight based on 100 parts by weight of a total sum of the photopolymerizable compound (B) and the softening component (B).
The ultraviolet-curable adhesive as set forth above in any one of (XIII) to (XV), which contains, as the softening component (D), a polymer having a weight average molecular weight of from 1,500 to 30,000.
The ultraviolet-curable adhesive as set forth above in (XVI), which contains, as the softening component (D), polyethylene glycol-polypropylene glycol allyl butyl ether or hydroxyl group-containing polyisoprene.
The ultraviolet-curable adhesive as set forth above in any one of (VI) to (XVII), in which
the content proportion of the organic compound (A) is from 0.001 to 5% by weight;
the content proportion of the (meth)acrylate oligomer (B-1-1) is from 5 to 90% by weight;
the content proportion of the monofunctional (meth)acrylate monomer (B-1-2) is from 5 to 70% by weight;
the content proportion of the photopolymerization initiator (C) is from 0.01 to 5% by weight; and
the softening component (D) is further contained in a proportion of from 10 to 80% by weight.
The ultraviolet-curable adhesive as set forth above in any one of (I) to (XVIII), in which the content of the organic compound (A) is from 0.1 to 100 parts by weight based on 100 parts by weight of the photopolymerization initiator (C).
The ultraviolet-curable adhesive of the present invention can be obtained by mixing and dissolving the compound (A) capable of absorbing an ultraviolet ray to emit light, the photopolymerizable compound (B), and the photopolymerization initiator (C), and if desired, further the softening component (D) and the above-described arbitrary additive at from ordinary temperature (25° C.) to 80° C. In addition, if desired, impurities may be removed by means of an operation such as filtration, etc.
Taking into consideration coating properties, it is preferable that the ultraviolet-curable adhesive of the present invention has a viscosity at 25° C. of from 100 mPa·s to 100 Pa·s, and it is especially preferable to properly control a blending ratio of the components such that the viscosity is in the range of from 300 to 50,000 mPa·s.
The ultraviolet-curable adhesive of the present invention can be formed into a cured product of the present invention by irradiation with an ultraviolet ray. In general, as described later, the ultraviolet-curable adhesive of the present invention is coated on at least one surface of at least one base material of plural optical base materials to be laminated, and after laminating the base materials, the adhesive is cured by irradiation with an ultraviolet ray from the side of the transparent base material.
In the present invention, from the viewpoint of ensuring high image visibility, a proportion of an insoluble solid component contained in the ultraviolet-curable adhesive is preferably not more than 10% by weight, more preferably not more than 5% by weight, and especially preferably not more than 1% by weight relative to the ultraviolet-curable adhesive.
A curing shrinkage ratio of the cured product of the ultraviolet-curable adhesive of the present invention is preferably not more than 5.0%, and especially preferably not more than 3.0%. According to this, on the occasion of curing of the ultraviolet-curable adhesive, it is possible to decrease an internal stress to be accumulated in the resin cured product, and it is possible to effectively prevent formation of a strain at an interface between the base material and the layer made of the cured product of the ultraviolet-curable adhesive. In addition, in the case where the base material such as glass, etc. is thin, if the curing shrinkage ratio is large, warpage at the time of curing becomes large, and therefore, the display performance is significantly adversely affected. From this viewpoint, it is also preferable that the curing shrinkage ratio is smaller.
In the case where it is required to obtain an optical member having high transparency and good visibility of a displayed image or the like by using the ultraviolet-curable adhesive of the present invention, it is preferable that the cured product of the ultraviolet-curable adhesive of the present invention (a cured product having a film thickness of, for example, 200 μm, which, however, varies with an application) has a transmittance of light in its wavelength region of from 400 nm to 800 nm of 80% or more. This is because in the case where the transmittance of light in the wavelength region of from 400 nm to 800 nm is too low, the visible light hardly transmits, so that visibility of a displayed image in a display device containing the instant cured product is lowered.
In addition, when the transmittance of light at 400 nm in the cured product is high, an enhancement of the image visibility can be much more expected. Therefore, the transmittance of light at 400 nm of the cured product of the ultraviolet-curable adhesive of the present invention (a cured product having a film thickness of, for example, 200 μm, which, however, varies with an application) is preferably 80% or more, and especially preferably 90% or more.
An optical member of the present invention which is obtained by using the above-described ultraviolet-curable adhesive of the present invention can be obtained in the following manner.
The optical member of the present invention can be obtained by coating the ultraviolet-curable adhesive of the present invention on one of base materials by using a coating apparatus such a slit coaler, a roll coater, a spin coater, an apparatus for screen printing method, etc., such that a film thickness of the coated resin is from 10 to 300 μm, laminating the other optical base material on the coated surface, and curing the adhesive by irradiation with an active energy ray from the side of the transparent base material, thereby adhering the optical base materials to each other. At that time, examples of the active energy ray include ultraviolet to near-ultraviolet light rays (wavelength: from around 200 to 400 nm). An irradiation dose of the active energy ray is preferably from about 100 to 4,000 mJ/cm2, and especially preferably from 200 to 3,000 mJ/cm2.
A light source which is used for the irradiation with ultraviolet to near-ultraviolet light rays is not limited with respect to the kind of a light source so long as it is a lamp capable of irradiating ultraviolet to near-ultraviolet light rays, and preferably light rays at a wavelength of from around 200 to 400 nm. Examples thereof include a low-pressure, high-pressure, or ultrahigh-pressure mercury vapor lamp, a metal halide lamp, a (pulsed) xenon lamp, an electrodeless lamp, and the like. In view of the facts that an output at a wavelength of from 300 nm to 400 nm is high; curing of the ultraviolet-curable resin composition becomes fast; and excitation of the compound (A) is easy to occur, it is preferable to use a metal halide lamp as the light source.
As the optical base material for which the ultraviolet-curable adhesive for optical base material lamination of the present invention can be used, a transparent plate, a sheet, a touch panel, and a display body can be exemplified.
A thickness of a plate-like or sheet-like optical base material such as a transparent plate or sheet (preferably a transparent sheet), etc. is not particularly limited, and it is usually from about 5 μm to about 5 cm, preferably from about 10 μm to about 10 mm, and more, preferably from about 50 μm to 3 mm.
In particular, the ultraviolet-curable adhesive of the present invention can be suitably used as an adhesive for laminating plural transparent plates or sheets constituting a touch panel.
In the case where the term “optical base material” is merely referred to in the present specification, the instant optical base material includes both an optical base material not having a light-shielding portion on a surface thereof and an optical base material having a light-shielding portion on a surface thereof. In the optical base material having a light-shielding portion on a surface thereof, the light-shielding portion may be formed on both surfaces or one surface of the optical base material, and it may be formed in a part or the whole of both surfaces or one surface of the optical base material. It is to be noted that it is preferable that the light-shielding portion is not formed in at least a part of the laminated optical base materials, but an exposing portion through which an ultraviolet ray transmits exists.
One of preferred embodiments of the present invention is concerned with the case where at least one of two optical base materials to be laminated is an optical base material having a light-shielding portion in a part of a surface thereof. In that case, it is possible to obtain the optical member of the present invention, such as a touch panel, etc., by laminating the two optical base materials to each other with the ultraviolet-curable adhesive of the present invention and then irradiating an ultraviolet ray from the side where the optical base material having a light-shielding portion exists, thereby curing the adhesive. In the thus obtained optical member of the present invention, even in the case where an ultraviolet ray is irradiated from one direction, the adhesive in the light-shielding area where the ultraviolet ray does not reach is thoroughly cured. For that reason, in various display devices having the instant optical member, it is possible to suppress generation of uneven display or the like in the vicinity of the light-shielding portion.
In the optical base material having a light-shielding portion in a part of a surface thereof, a position of the light-shielding portion is not particularly limited. A preferred embodiment is concerned with the case where a stripe-like light-shielding portion having a width of from 0.05 mm to 20 mm, preferably from about 0.05 mm to 10 mm, more preferably from 0.1 mm to 8 mm, and still more preferably from about 0.1 mm to 6 mm is provided in the periphery of the optical base material.
As the transparent plate or sheet for which the ultraviolet-curable adhesive of the present invention is used, transparent plates or sheets using a variety of materials can be used. Specifically, it is possible to use a transparent plate or sheet which is made of a resin such as polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), a composite of PC and PMMA, glass, a cycloolefln copolymer (COC), a cycloolefin polymer (COP), triacetyl cellulose (TAC), an acrylic resin, etc., or a functional transparent laminated plate or sheet prepared by laminating a plurality of the foregoing transparent plates or sheets, such as a polarising plate, etc.; a transparent plate made of inorganic glass (for example, an inorganic glass plate or its processed goods (e.g., a lens, a prism, or an ITO glass)); or the like.
In addition, in the present invention, the plate-like or sheet-like optical base material includes, in addition to the above-described polarizing plate and the like, a laminate of plural functional plates or sheets (hereinafter also referred to as “functional laminate”), such as a touch panel, a display body, e.g., a liquid crystal display plate or LED, etc.
A plate-like or sheet-like optical base material is preferable as the optical base material in the present invention.
Examples of the sheet for which the ultraviolet-curable adhesive of the present invention can be used (for example, a sheet to be laminated on a touch panel, etc., or the like) include an icon sheet, a decorative sheet, and a protective sheet. Examples of the plate for which the ultraviolet-curable adhesive of the present invention can be used (transparent plate: for example, a transparent plate to be laminated on a touch, panel, etc., or the like) include a decorative plate and a protective plate. As a material of the instant sheet or plate, those exemplified as the material of the transparent plate as described above can be applied.
Examples of the material of the surface of the touch panel, for which the ultraviolet-curable adhesive of the present invention can be used, include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.
As one of the preferred optical members obtained by the present invention, an optical member in which a plate-like or sheet-like transparent optical base material having a light-shielding portion in a part thereof (preferably the periphery) is laminated to the above-described functional laminate with the cured product of the ultraviolet-curable resin of the present invention can fee exemplified. As preferred examples thereof, a touch panel (or a touch panel sensor) in which the above-described transparent plate or sheet having a stripe-like light-shielding portion in the periphery is laminated on a surface on the side of a touch sensor of a touch panel with a cured product of the ultraviolet-curable resin of the present invention; or a display device in which a plate-like or sheet-like transparent optical base material having a light-shielding portion in a part thereof (preferably the periphery), such as a protective plate, etc., is laminated on a display screen of a display body with the cured product of the ultraviolet-curable resin of the present invention can be exemplified.
The ultraviolet-curable adhesive of the present invention can also be suitably used for the production of a display body having an optical functional material stuck thereto (hereinafter also referred to as “display panel”), which is obtained by laminating a display body such as a liquid crystal display device, etc. and an optical functional material (optical base material in the present invention) to each other. At that time, examples of the display body which can be used include display devices having a polarizing plate laminated thereon, such as LCD, EL display, EL Illumination, electronic paper, plasma display, etc. In addition, examples of the above-described optical functional material include a transparent plastic plate such as an acrylic plate, a PC plate, a PET plate, a PEN (polyethylene naphthalate) plate, etc.; tempered glass, and a touch panel input sensor (touch panel sensor). Such a functional material preferably has a light-shielding portion in a part thereof (usually the periphery).
In the case of laminating a display body and a transparent plate or a transparent sheet to each other with the ultraviolet-curable adhesive of the present invention, when a refractive index of a cured product obtained by curing the ultraviolet-curable adhesive of the present invention is from 1.45 to 1.55, visibility of a displayed image is more improved, and therefore, such is more preferable.
So long as the refractive index falls within the foregoing range, a difference in the refractive index from the base material which is used as a transparent plate can be decreased, and it becomes possible to decrease a light loss by suppressing diffuse reflection of light.
As preferred embodiments of the optical member of the present invention, the following embodiments (i) to (iv) can be exemplified.
The optical member obtained by using the ultraviolet-curable adhesive of the present invention can be suitably used for a display device such as a liquid crystal display, a plasma display, an organic EL display, etc., and in particular, it can be suitably used for a display device combined with a touch panel.
In addition, the optical member obtained by using the ultraviolet-curable adhesive of the present invention, such as the above-described display panel, etc., can be incorporated into an electronic appliance (electronic appliance for display), for example, a television, a small-sized game machine, a cellular phone, a personal computer, etc.
The present invention is more specifically described below by reference to the following Examples, but it should be construed that the present invention is not limited to these Examples by any means.
Ultraviolet-curable resin compositions each composed of a composition shown in Table 1 were prepared. Melting points of all of the respective compounds used as the organic compound (A) fall within the range of from 25 to 300° C.
It is to be noted that each of the components expressed with abbreviations in Table 1 are as follows.
An esterification product between a maleic anhydride adduct of a polyisoprene polymer and 2-hydroxyethyl methacrylate (average molecular weight: 35,000), manufactured by Kuraray Co., Ltd.
A reaction product prepared through a reaction among three components of polypropylene glycol (molecular weight: 3,000), isophorone diisocyanate, and 2-hydroxyethyl acrylate in a molar ratio of 1/1.3/2
Dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.
Dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd.
1-Hydroxycyclohexyl phenyl ketone, manufactured by BASF
2,4,6-Trimethylbenzoyldiphenylphosphine oxide, manufactured by LAMBSON
Bis(2,4,6-trimethylbenxoyl)phenylphosphine oxide, manufactured by BASF
Hydroxyl group-terminated liquid polyisoprene, manufactured by Idemitsu Kosan Co., Ltd.
Polyethylene glycol-polypropylene glycol allyl butyl ether, manufactured by NOF Corporation
2,5-Thiophenediyl bis(5-tert-butyl-1,3-benzoxazole), manufactured by BASF, absorption maximum wavelength: 375 nm, light emission maximum wavelength: 438 nm (“TINOPAL” is a registered trademark)
Trans-1,2-diphenylethylene, manufactured by Tokyo Chemical Industry Co., Ltd., absorption maximum wavelength: 321 nm, light emission maximum wavelength: 353 nm
9,10-Diphenylanthracene, manufactured by Tokyo Chemical Industry Co., Ltd., absorption maximum wavelength: 279 nm, light emission maximum wavelength: 429 nm
4,4′-Bis(9H-carbazol-9-yl)biphenyl, manufactured by Tokyo Chemical Industry Co., Ltd., absorption maximum wavelength: 302 nm, light emission maximum wavelength: 369 nm
2-(4-Biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, manufactured by Wako Pure Chemical Industries, Ltd., absorption maximum wavelength: 272 nm, light emission maximum wavelength: 364 nm
7-Diethylamino-4-methylcoumarin, manufactured by Nippon Kayaku Co., Ltd., absorption maximum wavelength: 332 nm, light emission maximum wavelength: 416 nm (“KAYALIGHT” is a registered trademark)
N,N′-Di(1-naphthyl)-N,N′-diphenylbenzidine, manufactured by Dojindo Laboratories, absorption maximum wavelength: 339 nm, light emission maximum wavelength: 450 nm
The following evaluations were carried out by using the ultraviolet-curable adhesives obtained in Examples 1 to 13 and Comparative Examples 1 to 3.
A tetrahydrofuran solution of each of the compounds used as the organic compound (A) (concentration: 0.002 wt %) was prepared, and an absorption spectrum of each of the compounds was measured by using a spectrophotometer “UV-3150” (a product name, manufactured by Shimadzu Corporation). A light emission spectrum of each of the compounds used as the compound (A) in the Examples was measured by using a fluorophotometer “P-7000” (a product name, manufactured by Hitachi High-Technologies Corporation, etc.).
First of all a substrate obtained by subjecting the entire surface of one of surfaces of a glass plate having a thickness of 1 mm to a black printing processing to form an ultraviolet light-shielding portion as shown in
Subsequently, the adhesive layer was irradiated with an ultraviolet ray from the side of the substrate in which a half of the area of the one-sided surface was subjected to a black printing processing as shown in
A result of measurement of the curing distance of light-shielding portion in each of the Examples and Comparative Examples and a result of evaluation of transmission properties of light-shielding portion according to the following criteria are shown in Table 1.
A: The curing distance of light-shielding portion is 1,000 μm or more.
B: The curing distance of light-shielding portion is 400 μm or more and less than 1,000 μm.
C: The curing distance of light-shielding portion is less than 400 μm.
Two 1 mm-thick slide glasses having a fluorine-based release agent coated thereon were prepared, and the ultraviolet-curable adhesive obtained in each of the Examples and Comparative Examples was coated on the release agent-coated surface of one of the slide glasses such that a film thickness after curing was 200 μm. Thereafter, the two slide glasses were laminated in such a manner that the respective release agent-coated surfaces faced each other. The adhesive layer sandwiched by the slide glasses was irradiated with an ultraviolet ray in an accumulated light amount of 2,000 mJ/cm2 through the glass by using a high-pressure mercury vapor lamp (80 W/cm, ozone-less). Thereafter, the two slide glasses were separated from each other, thereby fabricating a cured product for measurement of transparency. With respect to the transparency of the cured product, a transmittance in the range of from 400 to 800 nm was measured by using a spectrophotometer (a product name: U-3310, manufactured by Hitachi High-Technologies Corporation). As a result, in all of Examples 1 to 13, the transmittance in the range of from 400 to 800 nm was 80% or more.
A result of measurement of the transmittance at 400 nm of the cured product of each of the Examples and Comparative Examples and a result of evaluation of transmittance at 400 nm according to the following criteria are shown in Table 1.
A: The transmittance of light at 400 nm is 90% or more.
B: The transmittance of light at 400 nm is 80% or more and less than 90%.
C: The transmittance of light at 400 nm is less than 80%.
It was confirmed from the results of Table 1 that the ultraviolet-curable adhesives of Examples 1 to 13 of the present invention, each of which contains the organic compound (A), the photopolymerizable compound (B), and the photopolymerization initiator (C), are an ultraviolet-curable adhesive which even in the case where a light-shielding portion is formed in a transparent protective plate, is able to advance curing of the adhesive positioned in a light-shielding area where an ultraviolet ray is shielded by the light-shielding portion. Furthermore, it was confirmed that the cured product of the ultraviolet-curable adhesive of the present invention, which contains the organic compound (A), the photopolymerizable compound (B), and the photopolymerization initiator (C), has a practically useful and preferable transmittance.
In addition, the following performance evaluations were carried out by using the ultraviolet-curable compositions of the present invention obtained in Examples 1 to 13.
Two 1 mm-thick slide glasses having a fluorine-based release agent coated thereon were prepared, and the ultraviolet-curable adhesive obtained in each of the Examples was coated on the release agent-coated surface of one of the slide glasses such that a film thickness after curing was 200 μm. Thereafter, the two slide glasses were laminated in such a manner that the respective release agent-coated surfaces faced each other. The adhesive layer sandwiched by the slide glasses was irradiated with an ultraviolet ray in an accumulated light amount of 2,000 mJ/cm2 through the glass by using a high-pressure mercury vapor lamp (80 W/cm, oxone-less). Thereafter, the two slide glasses were separated from each other, thereby fabricating a cured product for measurement of film specific gravity.
A specific gravity (DS) of the obtained cured product was measured by the method in conformity with JIS K7112, Method B. More specifically, an appropriate amount of the cured product was put into a pycnometer; a weight of the pycnometer was measured; an immersion liquid was then added thereto to fill the pycnometer; and a weight of the pycnometer containing the cured product and the immersion liquid was measured. In addition, a weight of the pycnometer filed with only the immersion liquid was separately measured. From these results of measurement, a specific gravity of the cured product obtained in each of the Examples was calculated. In addition, with respect to the ultraviolet-curable adhesive before curing of each of the Examples, a liquid specific gravity (DL) at 25° C. was measured. From the results of measurement of DS and DL, a curing shrinkage ratio was calculated according to the following formula.
Curing shrinkage ratio (%)=(DS−DL)/DS×100
As a result, in all of Examples 1 to 13, the curing shrinkage ratio was less than 1.5%.
The obtained ultraviolet-curable resin composition was thoroughly cured and evaluated for flexibility by measuring a durometer E hardness by using a durometer hardness meter (Type E) by the method in conformity with JIS K7215. More specifically, the ultraviolet-curable adhesive of each of the Examples 1 to 13 was poured into a cylindrical mold such that a film thickness alter curing was 1 cm; subsequently, an ultraviolet ray was irradiated to thoroughly cure the ultraviolet-curable adhesive; and a hardness of the obtained cured product was measured by using a durometer hardness meter (type E). As a result, all of the cured products of the ultraviolet-curable adhesives obtained in Examples 1 to 13 had a durometer E hardness of less than 10 and exhibited excellent flexibility.
Each of the ultraviolet-curable adhesives prepared in Examples 2 to 13 was coated on a surface of a resin-made film of a liquid crystal display unit having an area of 3.5 inches such that a film thickness after curing was 250 μm. Subsequently, a glass substrate having a touch sensor was placed on each of the ultraviolet-curable adhesives and laminated onto the liquid crystal display unit. Finally, an ultraviolet ray was irradiated in an accumulated light amount in the range of from 20 to 1,500 mJ/cm2 from the side of the glass substrate having the touch sensor by using an ultrahigh-pressure mercury vapor lamp (TOSCURE (a registered trademark) 752, manufactured by Harison Toshiba Lighting Corporation) to cure the adhesive layer, thereby fabricating an optical member of the present invention.
Then, the optical member was cut with a metal-made wire, thereby separating the resin cured product from the glass substrate having the liquid crystal display unit and the touch sensor. Thereafter, the surface of the resin-made film of the liquid crystal display unit and the surface of the glass substrate were wiped off by a fabric impregnated with isopropyl alcohol, and the presence or absence of the resin cured product attached to the resin-made film and the glass substrate was observed through visual inspection. As a result, even in the case of using the ultraviolet-curable adhesive of any of the Examples, attachment of the resin cured product on the resin-made film or the glass substrate was not confirmed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-005251 | Jan 2012 | JP | national |
| 2012-062990 | Mar 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2012/006836 | 10/25/2012 | WO | 00 | 7/10/2014 |
