The present invention relates to transparent molded articles such as lenses and methods of manufacturing the same. In particular, the present invention relates to transparent molded articles having good transparency and mold releasing property from a forming mold, comprising polyurea having intramolecular urethane bonds, that are suited to optical applications, and a method of manufacturing the same. The present invention further relates to optical members having an antireflective film on a polyurethane urea polymer substrate.
Compared to glass, plastics are lighter, more crack resistant, and lend themselves more readily to dyeing. Thus, they are employed in optical applications such as various lenses, including eyewear lenses. Typical examples are polydiethylene glycol bisallylcarbonate and polymethyl methacrylate. However, these have a low refractive index of about 1.50 and a specific gravity of about 1.2 or more. Thus, for example, when employed in eyewear lenses, as the degree of magnification becomes greater, the thickness near the center of the lens and the edge thickness must be made thicker, running the risk of compromising one of the superior properties of plastics in the form of light weight. Although they have a lesser tendency to crack than glass, there is great need for even better resistance to cracking. In response, to further utilize characteristics of plastics that is light and crack resistant, polycarbonate obtained by injection molding and polythiourethane obtained by cast polymerization have begun to be employed in optical applications. Despite having extremely high strength, polycarbonate has low resistance to solvents, a common drawback of injection molded materials. And although polythiourethane does not exhibit the common drawback of injection molded materials, it is presently inferior in strength to polycarbonate.
Accordingly, to avoid the common drawbacks of injection molded materials, there is a need for a material that can be obtained by cast polymerization and has strength comparable to that of polycarbonate. Materials having such characteristics are known in the form of materials obtained by cast polymerizing an isocyanate terminal prepolymer having intramolecular urethane bonds with an aromatic diamine (U.S. Pat. Nos. 5,962,617 and 6,127,505). A method of molding resin compositions comprising an isocyanate reactive polymer, a steric hindered aromatic diamine, and an internal mold releasing agent in the form of a fatty acid zinc salt is also known (Japanese Examined Patent Publication (KOKOKU) Heisei No. 3-39533).
However, the material disclosed in U.S. Pat. No. 5,962,617 has problems in that the aromatic diamine employed is solid at ordinary temperature and the polymerization reaction is rapid, resulting in residual melting and a molded article of low transparency. The material itself disclosed in U.S. Pat. No. 6,127,505 has adequate transparency as an optical material. However, when manufactured by cast polymerization, there remains a significant problem in the form of mold releasing properties.
Accordingly, the present inventors investigated polyurethane urea materials such as those disclosed in U.S. Pat. No. 6,127,505 with regard to improving the mold releasing property thereof by using various internal mold releasing agents together. They discovered that when silicone, fluorine, and metallic salt-based mold releasing agents commonly used for plastics or the acid phosphate alkyl esters disclosed in Japanese Unexamined Patent Publication (KOKAI) Heisei No. 1-163012 and Showa No. 64-45611 were employed as internal mold releasing agents, there were problems such as reduced transparency due to haze and the like, reduced strength, and inadequate mold releasing properties. Improvement of mold releasing properties with the fatty acid zinc disclosed in Japanese Examined Patent Publication (KOKOKU) Heisei No. 3-39533 was also investigated. Since the molded products disclosed in Japanese Examined Patent Publication (KOKOKU) No. 3-39533 are themselves opaque, there is no problem if incorporating fatty acid zinc to a degree where adequate mold releasing properties are achieved. However, since the fatty acid zinc is present in the molded article in crystalline form, it scatters light, precluding the use of fatty acid zinc as an internal mold releasing agent in transparent molded articles in practice.
The material disclosed in U.S. Pat. No. 6,127,505 is a polyurea having intramolecular urethane bonds that can be cast polymerized and having strength comparable to that of polycarbonate. However, as described above, there is a problem in that adequate mold releasing properties cannot be achieved with common internal mold releasing agents during cast polymerization.
Accordingly, the first object of the present invention is to provide a molded article with good transparency and good mold releasing property from a forming mold that is suited to optical applications, and a method of manufacturing the same.
Further, the material itself disclosed in U.S. Pat. No. 6,127,505 achieves adequate transparency as an optical material by devising an aromatic diamine that is a starting material. However, there is a major drawback in that yellowing caused by heat and light (particularly ultraviolet radiation) occurs during polymerization as the result of oxidation of the aromatic diamine
To commute for this point, U.S. Pat. No. 6,127,505 describes the use of UV-absorbing agents, light stabilizers, and anti-oxidants. However, only common products are listed and there is no mention of specific formulation quantities and the like. As a result, this does not amount to an adequate countermeasure in practice, with yellowing caused by heat and light during polymerization remaining as a major problem.
Accordingly, the second object of the present invention is to provide a transparent molded article having good transparency, tending not to yellow due to heat and light, and having suitability to optical applications, that is a material obtained by cast polymerizing an isocyanate terminal prepolymer having an intramolecular urethane bond with an aromatic diamine, and a method of manufacturing the same.
It is well known that an antireflective film is applied on a surface of a synthetic resin to improve surface refractive characteristics of an optical member composed of a synthetic resin. For example, Japanese Unexamined Patent Publication (KOKAI) Showa No. 56-116003 discloses an optical member comprising a substrate in the form of CR-39 (diethylene glycol bisallylcarbonate) resin and an antireflective film having, in sequence from the substrate, an underlayer comprised of SiO2 1.5λ in film thickness, a first layer about 0.25λ in total film thickness comprised of a two-layer equivalent film comprised of a ZrO2 layer and a SiO2 layer, a second layer about 0.50 in film thickness comprised of ZrO2, and a third layer about 0.25λ in film thickness comprised of SiO2, on a CR-39 resin.
However, in contrast to glass substrates, resin substrates do not permit the formation of an antireflective film by raising the substrate temperature during vapor deposition. Thus, the ZrO2 layer, for example, formed by vapor deposition does not have adequate heat resistance. Further, the heat resistance of the layer comprised of ZrO2 tends to decrease significantly over time. In some cases, such an optical member in which the overall heat resistance of an antireflective film is inadequate as well as the heat resistance drops significantly over time has a practical problem, for example, as eyewear lenses. This is because plastic eyewear frames are heated when the eyewear lenses are inserted into frame and this heat is transmitted to the eyewear lens. In antireflective films with low heat resistance, differences in thermal expansion coefficients sometimes cause cracks (fine fissures).
To solve such problems of heat resistance, Japanese Unexamined Patent Publication (KOKAI) Heisei No. 2-291502, for example, discloses an optical member having an antireflective film employing vapor deposition films comprising Ta2O5, ZrO2, and Y2O3 on a high refractive index layer, and a vapor deposition composition forming a vapor deposition film comprising Ta2O5, ZrO2, and Y2O3.
Particularly in the field of eyewear, there is a demand for a new optical member having a plastic lens substrate with an antireflective film of extremely good heat resistance that decreases as little as possible.
Since a resin substrate has better elasticity than a glass substrate, there is a demand for providing an antireflective film of high film strength that will not crack when force is exerted on the substrate causing it to flex.
Accordingly, the third object of the present invention is to provide an optical member comprising a substrate in the form of a material comprised of polyurethane urea polymer and having an antireflective layer that is suited to the substrate and has a good heat resistance and high film strength as well as that is undergone little reduction of heat resistance over time.
The present inventors conducted extensive research into the development of materials suited to optical applications that imparted good mold releasing properties without compromising the transparency of polyurethane urea materials such as those described in U.S. Pat. No. 6,127,505. As a result, they discovered that an optical material obtained by casting and curing a composition comprised of a component comprising a specific isocyanate terminal prepolymer, a component comprising a specific aromatic diamine, and a component in the form of a mixture of phosphoric acid monoester and phosphoric acid diester respectively having a specific structure was suited to the above-stated object; the first aspect of the present invention was achieved.
Further, the present inventors conducted extensive research into the development of a material suited to optical applications that imparted good resistance to oxidation (resistance to yellowing) without compromising transparency in materials obtained by cast polymerization of an isocyanate terminal prepolymer having an intramolecular urethane bond and an aromatic diamine, such as is disclosed in U.S. Pat. No. 6,127,505. As a result, they discovered that an optical material obtained by casting and curing a composition comprised of a component comprising specific isocyanate terminal prepolymer, a component comprising a specific aromatic diamine, and a component comprising a phosphorous peroxide decomposition agent was suited to the above-stated second object; the second aspect of the present invention was achieved.
Further, as a result of extensive research conducted by the present inventors to achieve the above-stated third object, they discovered that by providing on a polyurethane urea polymer substrate an antireflective film in the form of a multilayered antireflective film comprising a ½λ layer, where the ½λ layer comprised multiple high refractive index layers containing niobium oxide and layers of silicon dioxide positioned between the high refractive index layers, it was possible to obtain an optical member having a multilayer antireflective film having high heat resistance and film strength in which vapor deposition film could be formed rapidly; the third aspect of the present invention was achieved.
The first aspect of the present invention to achieve the above-mentioned first object is as follows;
(1) A transparent molded article comprised of a polymer of the following components (A) and (B), characterized in that said polymer further comprises the following components (C) and (D).
Component (A): isocyanate terminal prepolymer in the form of a reaction product of an aliphatic diisocyanate having an intramolecular cyclic structure and a diol having an average molecular weight of 300-2,500
Component (B): one or more aromatic diamines denoted by general formula (I). (In general formula (I), R1, R2 and R3 are each dependently any of a methyl, ethyl or thiomethyl group.)
Component (C): one or more phosphoric acid monoesters denoted by general formula (II). (In general formula (II), R4 is an alkyl group with a carbon number of 1-10 and n1 is 1 or 2.)
Component (D): one or more phosphoric acid diesters denoted by general formula (III). (In general formula R5 and R6 are each dependently an alkyl group with a carbon number of 1-10 and n2 and n3 are 1 or 2.)
(2) The transparent molded article according to (1), wherein the total weight of components (C) and (D) ranges from 0.005 to 0.1 percent of the total weight of components (A), (B), (C) and (D).
(3) The transparent molded article according to (1) or (2), wherein the weight of component (C) ranges from 30 to 70 percent of the total weight of components (C) and (I)).
(4) The transparent molded article according to any of (1)-(3), wherein the aliphatic diisocyanate having an intramolecular cyclic structure, that is a starting material of component (A), is an alicyclic diisocyanate.
(5) The transparent molded article according to (4), wherein the alicyclic diisocyanate is at least one selected from the group consisting of 4,4′-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane and norbornene diisocyanate.
(6) The transparent molded article according to any of (1)-(5), wherein the diol having an average molecular weight of 300-2,500, that is a starting material of component (A), is a polyether diol or polyester diol.
(7) The transparent molded article according to any of (1)-(6), wherein the isocyanate group content of component (A) ranges from 10 to 20 weight percent.
(8) The transparent molded article according to any of (1)-(7), wherein, in general formula (I), R1 is a methyl group, and R2 and R3 are dependently any of a ethyl group or thiomethyl group.
(9) The transparent molded article according to any of (1)-(8), wherein the molar ratio of the isocyanate group of component (A) to an amino group of component (B) ranges from 1.00 to 1.15.
(10) The transparent molded article according to any of (1)-(9), wherein R4 is an alkyl group with a carbon number of 2-6 in general formula (II), and R5 and R6 are each dependently an alkyl group with a carbon number of 2-6 in general formula (III).
(11) The transparent molded article according to any of (1)-(10), wherein the transparent molded article is a lens.
(12) The transparent molded article according to (11), wherein the lens is an eyewear lens.
(13) The transparent molded article according to any of (1)-(12), wherein said transparent molded article has a cured coating film on the surface.
(14) The transparent molded article according to (13), wherein said cured coating film is one obtained from a coating composition comprising components (E) and (F).
Component (E): an organic silicon compound denoted by general formula (IV) or a hydrolysis product thereof.
(R7)a(R9)bSi(OR8)4−(a+b) (IV)
(In general formula (IV), R7 denotes an organic group comprising an epoxy group, methacryloxy group, mercapto group, amino group, or phenyl group; R8 denotes an alkyl group with a carbon number of 1-4 or an acyl group with a carbon number of 1-4; R9 denotes an alkyl group with a carbon number of 1-6; and a and b denote an integer 1 or 0.)
Component (F): metal oxide colloid particles
(15) The transparent molded article according to any of (1)-(14), wherein said transparent molded article has an antireflective film on the surface or on said cured coating film
(16) The transparent molded article according to (15), characterized in that said antireflective film is a multilayer antireflective film, and at least one layer of the multilayer antireflective film is a high refractive index layer comprising niobium oxide.
(17) A method of manufacturing a transparent molded article, comprising forming a molded article by pouring a mixture of components (A), (B), (C) and (D) according to any of (1)-(10) into a forming mold, and then polymerizing components (A) and (B).
(18) The method of manufacturing a transparent molded article according to (17), wherein said mixture is prepared by further mixing component (B) with a mixture of components (A), (C) and (D).
The second aspect of the present invention to achieve the above-mentioned second object is as follows;
(19) A transparent molded article comprised of a polymer of the following components (A) and (B), characterized in that said polymer further comprises the following component (G).
Component (A): isocyanate terminal prepolymer in the form of a reaction product of an aliphatic diisocyanate having an intramolecular cyclic structure and a diol having an average molecular weight of 300-2,500
Component (B): one or more aromatic diamines denoted by general formula (I).
(In general formula (I), R1, R2 and R3 are each dependently any of a methyl, ethyl or thiomethyl group.)
Component (G): one or more phosphorous peroxide decomposing agents.
(20) The transparent molded article according to (19), wherein the weight of component (G) ranges from 0.02 to 5.0 percent of the total weight of components (A), (B) and (G).
(21) The transparent molded article according to (19) or (20), characterized in that said phosphorous peroxide decomposing agent of component (G) comprises a structure denoted by the following general formula (V).
(In general formula (V), R10 and R11 are each independently any of a phenyl group optionally substituted with an alkyl group with a carbon number of 1-6 or an alkyl group with a carbon number of 1-16, and R12 and R13 are each independently any of a hydrogen atom or an alkyl group with a carbon number of 1-10.)
(22) The transparent molded article according to any of (19)-(21), wherein, in general formula (V), R10 and R11 are an alkyl group with a carbon number of 12-14.
(23) The transparent molded article according to any of (19)-(22), wherein the aliphatic diisocyanate having an intramolecular cyclic structure, that is a starting material of component (A), is an alicyclic diisocyanate.
(24) The transparent molded article according to (23), wherein the alicyclic diisocyanate is at least one selected from the group consisting of 4,4′-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane and norbornene diisocyanate.
(25) The transparent molded article according to any of (19)-(24), wherein the diol having an average molecular weight of 300-2,500, that is a starting material of component (A), is a polyether diol or polyester diol.
(26) The transparent molded article according to any of (19)-(25), wherein the isocyanate group content of component (A) ranges from 10 to 20 weight percent.
(27) The transparent molded article according to any of (19)-(26), wherein, in general formula (I), R1 is a methyl group, and R2 and R3 are dependently any of an ethyl group or thiomethyl group.
(28) The transparent molded article according to any of (19)-(27), wherein the molar ratio of the isocyanate group of component (A) to an amino group of component (B) ranges from 1.00 to 1.15.
(29) The transparent molded article according to any of (19)-(28), wherein the transparent molded article is a lens.
(30) The transparent molded article according to (29), wherein the lens is an eyewear lens.
(31) The transparent molded article according to any of (19)-(30), wherein said transparent molded article has a cured coating film on the surface.
(32) The transparent molded article according to (31), wherein said cured coating film is one obtained from a coating composition comprising components (E) and (F).
Component (E): an organic silicon compound denoted by general formula (IV) or a hydrolysis product thereof.
(R7)a(R9)bSi(OR8)4−(a+b) (IV)
(In general formula (IV), R7 is an organic group comprising an epoxy group, methacryloxy group, mercapto group, amino group, or phenyl group; R8 is an alkyl group with a carbon number of 1-4 or an acyl group with a carbon number of 1-4; R9 is an alkyl group with a carbon number of 1-6; and a and b denote an integer 1 or 0.)
Component (F): metal oxide colloid particles
(33) The transparent molded article according to any of (19)-(32), wherein said transparent molded article has an antireflective film on the surface or on said cured coating film.
(34) The transparent molded article according to (33), characterized in that said antireflective film is a multilayer antireflective film, and at least one layer of the multilayer antireflective film is a high refractive index layer comprising niobium oxide.
(35) A method of manufacturing a transparent molded article, comprising forming a molded article by pouring a mixture of components (A), (B), and (G) according to any of (19)-(28) into a forming mold, and then polymerizing components (A) and (B).
(36) The method of manufacturing a transparent molded article according to (35), wherein said mixture is prepared by further mixing component (B) with a mixture of components (A) and (G).
The third aspect of the present invention to achieve the above-mentioned third object is as follows;
(37) An optical member comprising an antireflective layer directly or indirectly on a polyurethane urea polymer substrate, characterized in that said antireflective layer is a multilayer antireflective layer comprising a ½ λ layer, and said ½λ layer comprises a plural high refractive index layers comprising niobium oxide and a layer comprised of silicon dioxide positioned between the high refractive index layers.
(38) The optical member according to (37), wherein said high refractive index layer comprised in said ½λ layer further comprises zirconium oxide and/or yttrium oxide.
(39) The optical member according to (38), wherein said high refractive index layer comprises 90-100 weight percent of niobium oxide, 0-5 weight percent of zirconium oxide and 0-5 weight percent of yttrium oxide based on the total weight of the layer.
(40) The optical member according to any of (37)-(39), wherein said polyurethane urea polymer substrate is a molded article comprised of a polymer of the following components (A) and (B), as well as further comprising the following components (C) and (D).
Component (A): isocyanate terminal prepolymer in the form of a reaction product of an aliphatic diisocyanate having an intramolecular cyclic structure and a diol having an average molecular weight of 300-2,500
Component (B): one or more aromatic diamines denoted by general formula (I). (In general formula (I), R1, R2 and R3 are each dependently any of a methyl, ethyl or thiomethyl group.)
Component (C): one or more phosphoric acid monoesters denoted by general formula (ID. (In general formula (II), R4 is an alkyl group with a carbon number of 1-10 and n1 is 1 or 2.)
Component (D): one or more phosphoric acid diesters denoted by general formula (III). (In general formula R5 and R6 are each dependently an alkyl group with a carbon number of 1-10 and n2 and n3 are 1 or 2.)
(41) The optical member according to any of (37)-(40), wherein said substrate is a lens.
(42) The optical member according to (41), wherein said lens is an eyewear lens.
(43) The optical member according to any of (37)-(42), wherein said antireflective layer is provided on said substrate through a hard coat layer.
(44) The optical member according to (43), wherein said hard coat layer is obtained by curing a coating composition comprising components (E) and (F).
Component (E): an organic silicon compound denoted by general formula (IV) or a hydrolysis product thereof.
(R7)a(R9)bSi(OR8)4−(a+b) (IV)
(In general formula (IV), R7 denotes an organic group comprising an epoxy group, methacryloxy group, mercapto group, amino group, or phenyl group; R8 denotes an alkyl group with a carbon number of 1-4 or an acyl group with a carbon number of 1-4; R9 denotes an alkyl group with a carbon number of 1-6; and a and b denote an integer 1 or 0.)
Component (F): metal oxide colloid particles
The transparent molded article of the first aspect of the present invention is comprised of a polymer of components (A) and (B).
Component (A) is an isocyanate terminal prepolymer in the form of a reaction product of an aliphatic diisocyanate having an intramolecular cyclic structure and a diol having an average molecular weight of 300-2,500. Making the diisocyanate, one starting material of the aforementioned isocyanate terminal prepolymer, an aliphatic diisocyanate having an intramolecular cyclic structure facilitates control of the reaction during manufacturing or polymerizing the prepolymer and imparts suitable elasticity to the molded article finally obtained. Further, it imparts high heat resistance and good mechanical characteristics to the molded article obtained.
The aliphatic diisocyanate having an intramolecular cyclic structure is an aliphatic diisocyanate having a cyclic structure in the main chain or in the side chain. The cyclic structure may be alicyclic, aromatic, or heterocyclic. However, the aliphatic diisocyanate having an intramolecular cyclic structure is desirably an alicyclic diisocyanate from the perspective of preventing yellowing and maintaining adequate elasticity and hardness. Molded articles obtained with isocyanate having an aromatic ring tend to yellow more than those obtained with alicyclic diisocyanate; molded articles obtained with aliphatic chain-structured isocyanate tend to be softer and lose their shape more readily.
Examples of alicyclic diisocyanates are: 4,4′-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 1,2-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, 1,2-diisocyanate cyclohexane, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, and norbornene diisocyanate. Examples of diisocyanates having aromatic rings are: m-xylylene diisocyanate, o-xylylene diisocyanate, p-xylylene diisocyanate, and m-tetramethylxylylene diisocyanate. It is particularly preferable that it is at least one selected from the group consisting of 4,4′-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, and norbornene diisocyanate.
The average molecular weight of the diol that is the other starting material of the isocyanate terminal prepolymer of component A is 300-2,500. When the average molecular weight of the diol is less than 300, toughness cannot be imparted to the molded article obtained, and when greater than 2,500, the molded article obtained becomes soft and does not retain its shape. The average molecular weight of the diol is desirably 400-1,000. Examples of diols having an average molecular weight of 300-2,500 are polyether diols and polyester diols. These diols are preferred because of good compatibility with the other component. In the case of a diol of poor compatibility, it becomes necessary to add another component in the form of a compatibility enhancer to maintain the transparency of the molded article obtained, potentially resulting in loss of transparency.
Examples of such diols are: polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyester diol comprised of ethylene glycol and adipic acid, polyester diol comprised of propylene glycol and adipic acid, polyester diol comprised of diethylene glycol and adipic acid, polyester diol comprised of 1,4-butane diol and adipic acid, polyester diol comprised of neopentyl glycol and adipic acid, polyester diol comprised of 1,6-hexanediol and adipic acid, polyester diol comprised of 1,10-decanediol and adipic acid, polyester diol comprised of 1,4-butanediol and sebacic acid, polycaprolactone diol comprised of ethylene glycol and ε-caprolactone, polycaprolactone diol comprised of propylene glycol and ε-caprolactone, polycaprolactone diol comprised of ethylene glycol and ε-caprolactone, polycaprolactone diol comprised of 1,4-butane diol and ε-caprolactone, polycaprolactone diol comprised of neopentyl glycol and ε-caprolactone, polycaprolactone diol comprised of 1,6-hexane diol and ε-caprolactone, polycaprolactone diol comprised of 1,10-decane diol and ε-caprolactone, and polycarbonate glycol. Preferred examples are: polyoxypropylene glycol, polyoxytetramethylene glycol, polyester diol comprised of 1,4-butane diol and adipic acid, polyester diol comprised of neopentyl glycol and adipic acid, polyester diol comprised of 1,6-hexane diol and adipic acid, and polyester diol comprised of 1,10-decane diol and adipic acid.
The isocyanate group content of isocyanate terminal prepolymer component (A) desirably falls within a range of 10-20 weight percent. When the above-stated isocyanate group content falls below the above-stated range, the hardness of the molded article obtained tends to decrease, and when the above-stated range is exceeded, it tends to become difficult to obtain toughness (adequate strength) of a molded article obtained. The above-stated isocyanate group content further preferably falls within a range of 11-15 weight percent.
Component (B) is one or more aromatic diamines denoted by general formula (I).
In general formula (I), R1, R2, and R3 are each independently any of a methyl, ethyl, or thiomethyl group. Employing substituents R1, R2, and R3 mentioned above can suppress crystallinity and enhance compatibility with the other components. When these substituents are absent or present in low numbers, crystallinity rises, resulting in handling difficulty. When employing the other substituents, compatibility with the other components deteriorates, resulting in apprehensively decreasing the transparency of the material obtained.
The following compounds are more specific examples of the above-stated aromatic diamines: 1,3,5-trimethyl-2,4-diaminobenzene, 1,3,5-trimethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 1,3,5-trithiomethyl-2,4-diaminobenzene, 1,3,5-trithiomethyl-2,6-diaminobenzene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3,5-dithiomethyl-2,4-diaminotoluene, 3,5-dithiomethyl-2,6-diaminotoluene, 1-ethyl-3,5-dimethyl-2,4-diaminobenzene, 1-ethyl-3,5-dimethyl-2,6-diaminobenzene, 1-ethyl-3,5-dithiomethyl-2,4-diaminobenzene, 1-ethyl-3,5-dithiomethyl-2,6-diaminobenzene, 1-thiomethyl-3,5-dimethyl-2,4-diaminobenzene, 1-thiomethyl-3,5-dimethyl-2,6-diaminobenzene, 1-thiomethyl-3,5-diethyl-2,4-diaminobenzene, 1-thiomethyl-3,5-diethyl-2,6-diaminobenzene, 3-ethyl-5-thiomethyl-2,4-diaminotoluene, 3-ethyl-5-thiomethyl-2,6-diaminotoluene, and 3-thiomethyl-5-ethyl-2,4-diaminotoluene.
In the above-listed aromatic diamines, R1 is desirably a methyl group and R2 and R3 each desirably represent either an ethyl group or thiomethyl group, in which case the molded article obtained tends not to fog and can be imparted with adequate toughness.
More specific examples of the above-stated aromatic diamines are: 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3,5-dithiomethyl-2,4-diaminotoluene, and 3,5-dithiomethyl-2,6-diaminotoluene.
As for the ratio of components (A) and (B), the molar ratio of the isocyanate group of component (A) with respect to the amino group of component (B) desirably falls within a range of 1.00-1.15 from the perspective of achieving adequate toughness (strength). The-above-stated molar ratio further preferably falls within a range of 1.02-1.12.
The molded article of the first aspect of the present invention is the above-described polymer, into which components (C) and (D) described below are further incorporated.
Component (C) is one or more phosphoric acid monoesters denoted by general formula (II). In general formula (II), R4 denotes an alkyl group with a carbon number of 1-10 and n1 is 1 or 2. Phosphoric acid monoesters within this range yield a molded product that does not fog and has good transparency. From the perspective of achieving optimal compatibility with other components, preferred is a phosphoric acid monoester in which R4 in general formula (II) is an alkyl group with a carbon number of 2-6. Further, n1 is desirably 1.
Examples of phosphoric acid monoesters denoted by general formula (II) are: methoxyethyl acid phosphate, ethoxyethyl acid phosphate, propoxyethyl acid phosphate, butoxyethyl acid phosphate, pentyloxyethyl acid phosphate, hexyloxyethyl acid phosphate, heptyloxyethyl acid phosphate, octyloxyethyl acid phosphate, nonyloxyethyl acid phosphate, and decyloxyethyl acid phosphate. Particularly preferred phosphoric acid monoesters are, for example, ethoxyethyl acid phosphate, propoxyethyl acid phosphate, butoxyethyl acid phosphate, pentyloxyethyl acid phosphate, and hexyloxyethyl acid phosphate.
Component (D) is one or more phosphoric acid diesters denoted by general formula (III). In general formula (III), since R5 and R6 are each independently an alkyl group with a carbon number of 1-10, and n2 and n3 are 1 or 2, fogging of the molded article obtained can be prevented and a molded article with good transparency can be obtained. From the perspective of achieving optimal compatibility with other components, it is desirable that R5 and R6 in general formula (III) are each independently an alkyl group with a carbon number of 2-6.
Examples of the phosphoric acid diesters denoted by general formula (III) are: methoxyethyl-ethoxyethyl acid phosphate, methoxyethyl-propoxyethyl acid phosphate, ethoxyethyl-propoxyethyl acid phosphate, ethoxyethyl-butoxyethyl acid phosphate, propoxyethyl-butoxyethyl acid phosphate, di(methoxyethyl) acid phosphate, di(ethoxyethyl) acid phosphate, di(propoxyethyl) acid phosphate, di(butoxyethyl) acid phosphate, di(pentyloxyethyl) acid phosphate, di(hexyloxyethyl) acid phosphate, di(heptyloxyethyl) acid phosphate, di(octyloxyethyl) acid phosphate, di(nonyloxyethyl) acid phosphate, and di(decyloxyethyl) acid phosphate. Preferred examples of phosphoric acid diesters are di(ethoxyethyl) acid phosphate, di(propoxyethyl) acid phosphate, di(butoxyethyl) acid phosphate, di(pentyloxyethyl) acid phosphate, and di(hexyloxyethyl) acid phosphate.
The total weight of components (C) and (I)) desirably falls with a range of 0.005-0.1 percent of the total weight of components (A), (B), (C), and (D). When the total weight of components (C) and (D) falls below the above-stated range, it is difficult to achieve good mold releasing properties, and when the above-stated range is exceeded, molding defects sometimes occur due to peeling during polymerization and transparency is sometimes lost. More preferably, the total weight of components (C) and (D) falls within a range of 0.01-0.1 percent of the total weight of components (A), (B), (C), and (D).
The weight of component (C) desirably falls within a range of 30-70 percent of the total weight of components (C) and (D). When the weight of component (C) exceeds this range, there is a risk of foaming during polymerization, and when below this range, transparency sometimes decreases due to fogging. The weight of component (C) more preferably falls within a range of 35-65 percent of the total weight of components (C) and (D).
The transparent molded article of the first aspect of the present invention can be manufactured, for example, by a method comprising forming a molded article by pouring a mixture of components (A), (B), (C), and (D) mentioned above into a forming mold, and then polymerizing components (A) and (B).
However, since the polymerizing property (reactivity) of components (A) and (B) is high and the reaction progresses even at ordinary temperature, it is preferred that the mixture (mixture of components (A), (B), (C), and (D)) is prepared by first adding components (C) and (D) to component (A), mixing, and further mixing component (B) with the uniformly melted product (mixture), and after preparation, it is rapidly poured into the forming mold.
For the polymerization reaction condition and the like, suitable reference can be made to the conditions and the like recorded at column 5 of U.S. Pat. No. 6,127,505; these will also be explained in detail in embodiments described further below herein.
In the molded article of the first aspect of the present invention, in addition to components (C) and (D), as needed, additives such as anti-oxidants, ultraviolet stabilizers, and color blockers may be added to the extent that the transparency and strength of the molded article of the first aspect of the present invention are not lost. Suitable examples of additives are described at columns 6-7 of U.S. Pat. No. 6,127,505.
The transparent molded article of the first aspect of the present invention may be employed in optical applications such as lenses such as eyewear lenses and optical lenses; prisms, optical fiber; recording medium substrates employed in optical disks, magnetic disks and the like; and filters. The transparent molded article of the present invention is employed in lenses, with particular preference in eyewear lenses.
A cured coating film can be present on the surface of the transparent molded article of the first aspect of the present invention. Examples of cured coating films are coating films obtained by curing a coating composition comprising components (E) and (F).
Component (E): an organic silicon compound denoted by general formula (IV) or a hydrolysis product thereof.
(R7)a(R9)bSi(OR8)4−(a+b) (IV)
(In general formula (IV), R7 denotes an organic group comprising an epoxy group, methacryloxy group, mercapto group, amino group, or phenyl group; R8 denotes an alkyl group with a carbon number of 1-4 or an acyl group with a carbon number of 1-4; R9 denotes an alkyl group with a carbon number of 1-6; and a and b denote an integer 1 or 0.)
Component (F): metal oxide colloid particles
Specific examples of the organic silicon compound denoted by general (IV) are given below:
methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate, t-butyl silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethykliethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyl-triethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N-(β-aminoethyl) γ-aminopropyltrimethoxysilane, N-(β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethoxydiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.
Examples of the metal oxide colloid particles of component (F) are tungsten oxide (WO3), zinc oxide (ZnO), silicon oxide (SiO2), aluminum oxide (Al2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), tin oxide (SnO2), beryllium oxide (BeO), and antimony oxide (Sb2O5); these may be employed singly or in combinations of two or more.
As for the quantity employed in the above-described coating composition, desired are 1-500 weight parts of the metal oxide colloid particles of component (F) per 100 weight parts of the organic silicon compound of component (E). At less than one weight part of the metal oxide colloid particles of component (F), no improvement in scratch resistance is achieved in the cured coating film. Conversely, at more than 500 weight parts, cracks tend to form between the cured coating film and the substrate and transparency tends to decrease.
Into the above-described coating composition, (1) curing agents to promote the reaction and (2) various surfactants to enhance wetting properties during coating and to increase the smoothness of the cured coating film can be suitably incorporated. Ultraviolet-absorbing agents, anti-oxidants and the like may also be added to the extent that they do not affect the physical properties of the cured coating film.
Examples of the above-mentioned curing agent are: amines such as allyl amine and ethyl amine; salts and metal salts comprising various acids and bases including Lewis acids and Lewis bases, such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, perchloric acid, bromic acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminic acid, and carbonic acid; and metal alkoxides comprising aluminum, zirconium, and titanium, and metal chelate compounds thereof.
The above-described coating composition is applied to the surface of the transparent molded article of the first aspect of the present invention and cured to form a cured coating film. The coating composition is cured by hot air drying or activation energy irradiation. As for the curing conditions, Curing is desirably conducted in hot air at a temperature of 70-200° C., preferably 90-150° C. An example of activation energy radiation is far infrared radiation, which makes it possible to adjust a damage caused by heat at a low level.
As a method of forming a cured coating film comprised of the above-described coating composition on the substrate, applied are usual methods such as dipping, spinning, and spraying. From the perspective of surface precision, dipping and spinning are particularly preferred. Prior to applying the coating composition to the substrate, adhesion between the substrate and the cured coating film can be enhanced by chemical processing with an acid, alkali, or various organic solvents; physical treatments by plasma, ultraviolet radiation, ozone, and the like; cleaning employing various cleaning agents; and primer treatment employing various resins.
On the transparent molded article of the first aspect of the present invention, an antireflective film may be present either directly on the molded article or on the above-described cured coating film
The type of antireflective film employed is not specifically limited; conventionally known inorganic oxides, MgF2, and the like may be employed in single layers or multiple layers. Examples of antireflective films suitable for use are disclosed in Japanese Unexamined Patent Publication (KOKAI) Heisei No. 2-262104 and Japanese Unexamined Patent Publication (KOKAI) Showa No. 56-116003. The cured coating film of the present invention may also be employed as a multifunctional film by the addition of functional components such as antifogging, photochromic, and antigrime agents.
The above-mentioned antireflective film is a multilayer antireflective film, with at least one layer of the multilayer antireflective film being a high refractive index layer comprising niobium oxide. The high refractive index layer may also comprise zirconium oxide and/or yttrium oxide.
The transparent molded article of the second aspect of the present invention is a polymer of components (A) and (B), and further comprising component (G). The same components (A) and (B) are employed as in the first aspect.
Component (G) is one or more phosphorus peroxide decomposing agents having the effect of inhibiting yellowing by decomposing peroxides generated by heat and light during the oxidation process. Although sulfur peroxide decomposing agents are known to exhibit the same effect, they are unsuitable because they react with the amine compounds present in the above-mentioned component (B) and other stabilizing agents, diminishing activity and causing coloration. Thus, the use of phosphorus-based compounds is important. Of these, from the perspective of compatibility with other components, those comprising the structure denoted by general formula (V) above, where R10 and R11 are each independently a phenyl group optionally substituted with an alkyl group with a carbon number of 1-6, or an alkyl group with a carbon number of 1-16, and R12 and R13 are each independently a hydrogen atom or an alkyl group with a carbon number of 1-10, are preferred. Those in which R12 and R13 in general formula (V) are each independently an alkyl group with a carbon number of 12-14 are of even greater preference from the perspective of high solubility in components (A) and (B).
Examples of such a phosphorus peroxide decomposing agents are given below.
Further, particular preferred phosphorus peroxide decomposing agents are given below.
Further preferred phosphorus peroxide decomposing agents are given below.
The weight of component (G) desirably falls within a range of 0.02-5.0 percent of the total weight of components (A), (B), and (G). When the weight of component (G) is below the above-stated range, it becomes difficult to achieve an inhibiting effect on yellowing. When exceeding the above-stated range, transparency sometimes decreases. More preferably, the weight of component (G) falls within a range of 0.1-2.0 percent of the total weight of components (A), (B), and (G).
The transparent molded article of the second aspect of the present invention can be manufactured, for example, by a method comprising forming a molded article by pouring a mixture of components (A), (B) and (G) mentioned above into a forming mold, and then polymerizing components (A) and (B).
However, since the polymerizing property (reactivity) of components (A) and (B) is high and reaction progresses even at ordinary temperature, it is preferred that the mixture (mixture of components (A), (B) and (G)) is prepared by first adding component (G) to component (A), mixing, and further mixing component (B) with the uniformly melted product (mixture), and after preparation, it is rapidly poured into the forming mold.
For the polymerizing reaction condition and the like, suitable reference can be made to the conditions and the like recorded at column 5 of U.S. Pat. No. 6,127,505; these conditions will also be explained in detail in embodiments described further below herein.
Additives such as ultraviolet-absorbing agents, anti-oxidants, light stabilizers, mold releasing agents, and decolorants may be added as needed to the molded article of the second aspect of the present invention in addition to component (G) to the extent that the transparency and mechanical characteristics of the molded article of the present invention are not lost.
Among these, examples of additives in the form of mold releasing agents include mixtures of components (C) and (D) that are used in the first aspect.
The use of a mixture of components (C) and (D) yields a molded article without fogging, with good transparency, and with good mold releasing properties. From the perspective of maximizing compatibility with other components, R4 in general formula (II) and R5 and R6 in general formula (III) are preferably each independently alkyl groups with a carbon number of 2-6.
The transparent molded article of the second aspect of the present invention may be employed in optical applications such as lenses such as eyewear lenses and optical lenses; prisms, optical fiber; recording medium substrates employed in optical disks, magnetic disks and the like; and filters. The transparent molded article of the present invention can be employed in lenses, with particular preference in eyewear lenses.
A cured coating film may be present on the surface of the transparent molded article of the second aspect of the present invention. In the case of a lens, it is particularly desirable for a cured coating film to be present on optically functioning surfaces. Examples of cured coating films include the coating film obtained by curing the coating composition comprising components (E) and (F) employed in the first aspect. The quantity of coating composition employed, the additives that can be added to the coating composition, application and curing of the coating composition, and the method of forming a cured coating film comprised of the coating composition on a substrate are identical to those in the first aspect.
On the transparent molded article of the second aspect of the present invention, an antireflective film may be present directly on the molded article or on the above-described cured coating film. The type of antireflective film is not specifically limited; conventionally known inorganic oxides, MgF2, and the like, may be employed in single or multiple layers. The antireflective films disclosed in Japanese Unexamined Patent Publication (KOKAI) Heisei No. 2-262104 and Japanese Unexamined Patent Publication (KOKAI) Showa No. 56-116003 may be employed. The cured coating film may also be employed as a multifunctional film by the addition of functional components such as antifogging, photochromic, and antigrime agents.
The antireflective film is a multilayer antireflective film, with at least one layer of the multilayer antireflective film being a high refractive index layer comprising niobium oxide. The high refractive index layer comprising niobium oxide may also comprise zirconium oxide and/or yttrium oxide.
The optical member of the third aspect of the present invention comprises an antireflective film directly or indirectly on a polyurethane urea polymer substrate, particularly, the above-mentioned antireflective layer is a multilayer antireflective film comprising a ½λ layer.
The above-mentioned ½λlayer is characterized by comprising plural high refractive index layers comprising at least niobium oxide and layers comprised of silicon dioxide positioned between the high refractive index layers.
In general, the antireflective layer is configured of, from the substrate side, a ¼λlayer (corresponding to a medium refractive index layer), a ½ λ layer (corresponding to a high refractive index layer), and a ¼λ layer (corresponding to a low refractive index layer); a ¼λ layer (corresponding to a medium refractive index layer), a ¼λ layer (corresponding to a medium refractive index layer), a ½λ layer (corresponding to a high refractive index layer), and a ¼λ layer (corresponding to a low refractive index layer); or a ¼λ layer (corresponding to a medium refractive index layer), a ¼λlayer (corresponding to a high refractive index layer), and a ¼λ layer (corresponding to a low refractive index layer). However, since the antireflective wavelength region of the third configuration is narrow when the refractive index of the substrate or hard coat layer is about 1.8 or less, the first and second configurations are preferred in the optical member of the third aspect of the present invention.
In the film configuration of the antireflective film present on the optical member of the third aspect of the present invention, the above-mentioned ½λ layer corresponding to a high refractive index layer comprises plural high refractive index layers containing at least niobium oxide, and SiO2 layers of a substance having a low refractive index positioned between them.
More specifically, the above-mentioned ½λlayer may have the following configuration. Since the strength-increasing effect decreases when the thickness of the SiO2 layers is less than 0.02λ, the number of layers can be increased to the extent that this does not occur. Here, the high refractive index layer refers to high refractive index layers comprising at least niobium oxide.
(1) High refractive index layer—SiO2 layer—high refractive index layer
(2) High refractive index layer—SiO2 layer—high refractive index layer—SiO2 layer—high refractive index layer
(3) High refractive index layer—SiO2 layer—high refractive index layer—SiO2 layer—high refractive index layer—SiO2 layer—high refractive index layer
Since the high refractive index layer in the form of a metal oxide layer has poorer structural strength and heat resistance than the SiO2 layer, in the ½λ layer with the thickest high refractive index layer, strength and heat resistance tend to be relatively low.
Dividing the high refractive index layer in the form of a metal oxide layer into plural layers as is done in the third aspect of the present invention reduces the thickness of the single layers, and sandwiching strong, highly heat resistant SiO2 layers between each of the layers increases the strength of the ½λ layer.
The above-mentioned high refractive index layer sometimes comprises only niobium oxide, and sometimes further comprises zirconium oxide and/or yttrium oxide in addition to niobium oxide. The plural high refractive index layers of all of the aspects may be of identical composition or may each have a different composition. The film thickness of plural high refractive index layers of the various aspects may be identical or different, but smaller differences in film thickness are desirable. This is because it is possible to make the film thickness of the high refractive index layers thinnest and to achieve high refractive index substance layers without optical irregularities.
The thickness of the SiO2 layer is desirably 0.02λ-0.15λ. When the thickness of the SiO2 layer is 0.02λ or more, the effect in raising the strength of the ½λ layer can be adequately achieved, and when 0.15λ or less, a high refractive index can be maintained.
The above-mentioned high refractive index layer constituting the ½ λ layer comprises niobium oxide (Nb2O5). The above-mentioned high refractive index layer constituting the ½λ layer may comprise zirconium oxide (ZrO2) and/or yttrium oxide (Y2O3) in addition to niobium oxide (Nb2O5).
The above-mentioned high refractive index layer desirably comprises 90-100 weight percent niobium oxide, 0-5 weight percent zirconium oxide, and 0-5 weight percent yttrium oxide based on the total weight of the layer. When the above-mentioned high refractive index layer constituting the ½λ layer consists of only niobium oxide (Nb2O5), as well as when zirconium oxide (ZrO2) and/or yttrium oxide (Y2O3) is comprised in the niobium oxide (Nb2O5), a highly transparent layer in which absorption tends not to occur results. However, when the quantity of niobium oxide (Nb2O5) is less than 90 weight percent, it becomes difficult to achieve a high refractive index. When the content of zirconium oxide (ZrO2) exceeds five weight percent, heat resistance tends to decrease. And when the content of yttrium oxide (Y2O3) exceeds 5 weight percent, heat resistance tends to decrease.
To the extent that the above-described effects are not compromised, metal oxides such as aluminum oxide (Al2O3), tantalum oxide (Ta2O3), and titanium oxide (TiO2) may be added to the evaporation composition of the third aspect of the present invention.
The ¼λ layer (corresponding to a medium refractive index layer) of the multilayer antireflective film in the third aspect of the present invention is not specifically limited. Examples are the above-described high refractive index layer and an SiO2 layer; a high refractive index layer comprising aluminum oxide (Al2O3) in addition to the above-described niobium oxide and the like and an SiO2 layer; and a known high refractive index oxide layer (for example, ZrO2, TaO5, TiO2, and Nb2O5) and an SiO2 layer. Further, the ¼λ layer (corresponding to the low refractive index layer) is not specifically limited. Examples are an SiO2 layer and an MgF2 layer. However, from the perspective of strength, an SiO2 layer is preferred. The undercoating layer is not specifically limited. Examples are an SiO2 layer; a layer comprised of a mixture of SiO2 and Al2O3; a metal layer (Nb, Ta, Cr, and the like); an SiO2 layer, a metal layer, and an SiO2 layer; or an SiO2 layer, a metal oxide layer, and an SiO2 layer.
To form the above-described antireflective layer, powders of niobium oxide, zirconium oxide, and yttrium oxide (including further oxides-(aluminum oxide, tantalum oxide, titanium oxide and the like) as needed) are sintered, a vapor of the mixed oxides is generated from the sintered product obtained, and the vapor product generated is deposited onto the substrate.
The above-mentioned high refractive index layer is desirably formed by mixing niobium oxide (Nb2O5) powder, zirconium oxide (ZrO2) powder, and yttrium oxide (Y2O3) powder (hereinafter, these powders are sometimes simply referred to as the “mixed powder”), pressing the mixed powder, and heating it with an electron beam, for example, to deposit the vapor product on the substrate. Following pressing, it is further desirable for the sintered product to be employed in pellet form by sintering to shorten the evaporation time. The quantity of the various oxides in the mixed powder and sintered product may be suitably varied based on the composition of the high refractive index layer being formed.
The evaporation composition obtained by sintering the mixed powder of Nb2O5 powder, ZrO2 powder, and Y2O3 powder forms an evaporated film more rapidly and has better production properties than the conventional evaporation composition obtained by sintering ZrO2.
The three-component vapor deposition composition mentioned above will be briefly described.
Splashing occurs in an evaporation starting material consisting solely of niobium oxide in the course of heating pellets with an electron gun. Splashing has the effect of adhering microparticles to the lens surface, resulting in defective product. Further, coloration (absorption) of thin films tends to occur, and resistance to chemicals such as acids and alkalis tends to decrease. To achieve improvement in these regards, ZrO2 and Y2O3 are employed in combination.
The addition of ZrO2 has the effect of reducing the splashing that causes defects of film stripping and adhesion of impurities during the heating of pellets of niobium oxide alone with an electron gun. Thus, it is suitable for forming a evaporated film of stable quality.
The addition of Y2O3 has the effect of changing the state of oxidation of thin films that are evaporated by heating with an electron gun and inhibiting coloration (absorption) occurring in thin films that formed by evaporation of niobium oxide alone or mixed pellets of niobium oxide and zirconium oxide.
In the present invention, the use of a evaporation composition in which the three components set forth above are mixed gives an unanticipated effect that the degree of the loss of heat resistance over time is markedly reduced in the antireflective film obtained, while an individual effect is maintained.
The antireflective layer may be formed by, as set forth above, sintering powders of niobium oxide, zirconium oxide, and yttrium oxide together with other oxides (such as aluminum oxide, tantalum oxide, and titanium oxide) as needed, generating a mixed oxide vapor from the sintered product obtained, and depositing the vapor product on a substrate. The use of ion assist in combination is desirable in this method of forming antireflective films.
The advantage of employing ion assist in combination is that, by a method employing assist-processing by oxygen ions during evaporation of the above-described high refractive index layer, lens absorption can be further inhibited. Further, alkali resistance can be improved by using ion assist with a mixed gas of oxygen and argon. The composition of the mixed gas is desirably 90-95 percent of oxygen gas and 10-5 percent of argon gas. When the ratio of oxygen gas is low, optical properties cannot be retained. The use of a suitable amount of argon gas can increase film density.
The pressure of press forming to obtain the above-mentioned evaporation composition is applied by a conventional method. For example, a pressure of 200-400 kg/cm2 (19.6-39.2 MPa) is desirable. Although the sintering temperature varies with the composition ratio of each component or the like, for example, a temperature of 1,000-1,400° C. is suitable. The sintering time can be suitably varied with the sintering temperature or the like, and normally ranges from 1-48 hours.
A high refractive index film can be formed under normal conditions using a method such as vacuum evaporation, sputtering, or ion plating using the above-described evaporation composition as the evaporation source. That is, a vapor of the mixed oxides is generated from the evaporation composition and the vapor product generated is deposited on the substrate. The temperature to which the synthetic resin substrate is heated differs with the heat resistance temperature of the synthetic resin, but, for example, a temperature of 70-85° C. is suitable.
Even when a film must be formed at a low substrate heating temperature of 70-85° C. during evaporation as on a synthetic resin substrate by the above-described method, an antireflective film with good heat resistance that tends not to be lost over time can be obtained.
The substrate employed in the optical member of the third aspect of the present invention is comprised of polyurea having an intramolecular urethane bond (referred to in the specification of the present application as polyurethane urea polymer). In particular, the polyurethane urea polymer disclosed in U.S. Pat. No. 6,127,505 can be cast polymerized and is a polyurea having intramolecular urethane bonds, and is a material having strength comparable to that of polycarbonate.
Further, the polyurethane urea polymer substrate is desirably a molded article comprised of a polymer of components (A) and (B) employed in the first and second aspects, further comprising components (C) and (D) employed in the first aspect.
The substrate comprised of the above-mentioned molded article can be manufactured, for example, by a method comprising forming a molded article by pouring components (A), (B), (C), and (D) mentioned above into a forming mold, and then polymerizing components (A) and (B).
However, since the polymerizing property (reactivity) of components (A) and (B) is high and the reaction progresses even at ordinary temperature, it is preferred that the mixture (mixture of components (A), (B), (C), and (D)) is prepared by first adding components (C) and (D) to component (A), mixing, and further mixing component (B) with the uniformly melted product (mixture), and after preparation, it is rapidly poured into the forming mold.
For the polymerization reaction condition and the like, suitable reference can be made to the descriptions in U.S. Pat. No. 6,127,505; these will also be explained in detail in embodiments described further below herein. Additives such as anti-oxidants, ultraviolet stabilizers, coloring preventing agents and the like may be added as needed in addition to components (C) and (D) to the extent that the transparency and strength of the molded article of the third aspect of the present invention are not lost. Examples of the additives are those described in U.S. Pat. No. 6,127,505.
In the course of providing an antireflective film on a substrate in the third aspect of the present invention, it is desirable that a hard coat layer comprising the organic silicon polymer is formed on the substrate surface by a coating method such as dipping or spin-coating, and an antireflective film is provided on the hard coat layer. To improve adhesion between the substrate and antireflective film, scratch resistance and the like, an undercoating layer is desirably inserted between the substrate and the antireflective film or between the hard coat layer formed on the substrate surface and the antireflective film. For example, an evaporated film of silicon oxide or the like can be employed as such an undercoating layer.
An example of the above-mentioned hard coat layer is a coating film obtained by curing a coating composition comprising components (E) and (F) employed in the first and second aspects. The quantity of coating composition employed, additives that can be added to the coating composition, application and curing of the coating composition, and method of forming the hard coat layer comprised of the coating composition on the substrate are identical to those employed when forming the cured coating film in the first and second aspects.
The antireflective film can be present directly on the substrate or on the above-mentioned hard coat layer.
The optical member having an antireflective layer of the third aspect of the present invention may be employed in optical applications such as lenses such as eyewear lenses and camera lenses; prisms, optical fiber; recording medium substrates employed in optical disks, magnetic disks and the like; and filters. It may also be employed in automobile window glass and the optical filters mounted on the displays of word processors. The optical member of the third aspect of the present invention can be employed in lenses, with particular preference, in eyewear lenses.
The present invention is specifically described by embodiments below. However, the present invention is not limited to the embodiments.
The various physical properties of plastic lenses obtained in embodiments and comparative examples of the first aspect were evaluated by the evaluation methods indicated below.
Denoted as UA were those in which stripping during polymerization, which caused molding failures such as a deformation of a lens surface and the like, did not occur, as well as releasing from a forming mold could be done without damages of a lens and a glass mold during peeling a glass obtained from a glass mold even if not applying a force. Denoted as A were those in which releasing from a forming mold required a little force, but could be easily done. These had good mold releasing properties and were acceptable on manufacturing. Conversely, denoted as B were those in which damages of a lens and a glass mold did not occur, but molding failures such as a deformation of a lens surface occurred. Denoted as C were those in which a lens and a glass mold were damaged. These had poor mold releasing properties and were unacceptable on manufacturing.
The lens obtained was visually inspected under fluorescent lighting in a dark location. Lenses without fogging or precipitation of opaque substances were denoted as A. Those exhibiting slight fogging and the like were denoted as B. And those with severe fogging or clearly visible precipitation of opaque substances were denoted as C. Clearly, C were unsuitable as lenses.
Steel balls weighing 16 g were allowed to drop naturally from a height of 1.27 m, as FDA standard, on the center of an S-4.00 lens with a center thickness of 1.3 mm. Those in which all test samples were unscathed were denoted as A, those in which fewer than 30 percent (but at least one piece) of the test samples were destroyed, for example, cracked or broke through were denoted as B, and those in which 30 percent or more samples were broken were denoted as C. A test was also conducted where the weight of the steel ball was increased to 1 kg and the same evaluations were made.
To 100 weight parts of isocyanate terminal prepolymer (denoted as ITP-1 in Table 1) having an isocyanate group content of 13 percent and comprised of polytetramethylene glycol with an average molecular weight of 400 and 4,4′-methylenebis(cyclohexyl isocyanate), 0.024 weight part of monobutoxyethyl acid phosphate (denoted as MBP in Table 1) and 0.036 weight part of di(butoxyethyl) acid phosphate (denoted as DBP in Table 1) were added in advance. The mixture was uniformly mixed and defoamed. Next, 25.5 weight parts of a mixture (denoted as DETDA in Table 1) of 3,5-diethyl-2,4-toluene diamine and 3,5-diethyl-2,6-toluene diamine were uniformly admixed at 60-70° C. and stirred in a short time at high speed. Immediately after stirring, the mixture was poured into a lens-forming glass mold and polymerized with heating for 15 hours at 120° C. to obtain a plastic lens (transparent molded article). The various physical properties of the plastic lens obtained are given in Table 1. Table 1 reveals that the obtained plastic lens exhibited no damage of lens and glass mold, and had an excellent mold releasing property from the glass mold. Further, the lens was excellent in transparency without fogging caused by cloud or scattering due to microcrystallization. The lenses also had good impact resistance, remaining undamaged in ball drop tests employing not only 16 g balls, as FDA standard, but also 1 kg balls.
With the exception that the components shown in Table 1 were employed, plastic lenses (transparent molded articles) were obtained by the same operation as in Embodiment 1. The various physical properties of these plastic lenses are shown in Table 1. Table 1 shows that the plastic lenses obtained exhibited no damage of lens and glass mold, had an excellent mold releasing property from the glass mold. Further, the lens was excellent in transparency without fogging caused by cloud or scattering due to microcrystallization. The lenses also had good impact resistance, remaining undamaged in ball drop tests employing not only 16 g balls, as FDA standard, but also 1 kg balls.
With the exception that MBP and DBP were not employed, the same operation was conducted as in Embodiment 1. However, mold releasing property from the glass mold was poor, the glass mold broke, and a portion thereof remained adhered to the plastic lenses. When an attempt was made to peel it off, the lens surface was scratched, with the result that no plastic lens was obtained.
With the exception that no MBP or DBP was employed and a fluorine mold releasing agent MS-443 (made by Daikin Industries (Ltd.)) was coated on the glass mold as an external mold releasing agent, the same process was conducted as in Embodiment 1 and plastic lease were obtained. The various physical properties of the plastic lens obtained are shown in Table 1. Table 1 reveals that although the plastic lenses of Comparative Example 2 had good impact resistance, they had poor mold releasing properties due to molding failures caused by mold separation during polymerization. Further, fogging was observed near the surface, resulting in poor transparency.
With the exception that the components shown in Table 1 were employed, plastic lenses were obtained by the same process as in Embodiment 1. The various physical properties of these plastic lenses are given in Table 1. Table 1 reveals that the plastic lenses of Comparative Example 3 had poor mold releasing properties, poor transparency, and poor impact resistance. Although the plastic lenses of Comparative Example 4 had good mold releasing properties, they exhibited little precipitation of opaque substances and had poor transparency and poor impact resistance. The plastic lens of Comparative Example 5, despite having good mold release properties and impact resistance, clearly exhibited fogging and had poor transparency. The plastic lens of Comparative Example 6, despite having good mold release properties, partly exhibited clouding and had poor transparency. Further, the lenses had poor impact resistance, with about 10 percent of the test samples exhibiting cracks in the 1 kg ball drop test. The plastic lenses of Comparative Example 7 had good mold releasing properties and impact resistance, but exhibited precipitation of opaque substances and had poor transparency.
1Molar ratio of isocyanate groups in component A relative to amino groups in component B.
The various physical properties of the plastic lenses (transparent molded articles) having cured coating films obtained in the present embodiment and comparative example were measured by the evaluation methods given below.
(4)-1 Scratch Resistance Test
The lens surface was rubbed with #0000 steel wools and the difficulty in imparting scratches was visually determined. The determination scale was as follows:
A. Almost no scratching even with vigorous rubbing.
B. Substantial scratching with vigorous rubbing.
C. Scratches equivalent to those on lens substrate.
(4)-2 Adhesion Test
100 cross cuts were made at 1 mm intervals, adhesive tape (tradename “Cellotape”, product of Nichiban (Ltd.)) was strongly adhered and quickly peeled off, and the presence or absence of cured coating film peeling was checked.
(4)-3 Appearance
Transparency and surface condition were visually examined indoors.
(4)-4 Impact resistance test
A steel ball drop test was conducted.
Specifically, 16 g or 1 kg steel balls were allowed to drop naturally onto the center of the lens from a height of 1.27 m. Lenses that did not crack passed.
A: passed, B: failed
While stirring 141 weight parts of water-dispersed colloidal silica (40 percent solid component, average particle size 15 millimicrons; component (F)) in a vessel made of glass and equipped with magnetic stirrer, 30 weight parts of acetic acid were added and the mixture was thoroughly mixed by stirring. Subsequently, 74 weight parts of γ-glycidoxypropyltrimethoxysilane (component (E)) were added dropwise and stirred for 24 hours at 5° C. Next, 100 weight parts of propylene glycol monomethylether, 150 weight parts of isopropyl alcohol, 0.2 part of silicone surfactant, and 7.5 weight parts of curing agent in the form of aluminum acetyl acetonate were added and the mixture was thoroughly stirred and filtered to prepare a coating composition solution.
The plastic lens (transparent molded article) produced in Embodiment 1 mentioned above was thoroughly cleaned by immersion for 5 min in a 10 percent sodium hydroxide aqueous solution at 55° C., after which a coating solution prepared by the above-described method was coated by dipping (lifting rate 20 cm/min) and heated for 2 hours at 120° C. to form a cured coating film Various evaluations were then conducted. As indicated in Table 2, the plastic lens (transparent molded article) having a cured coating film that was obtained had good scratch resistance, adhesion, appearance, and impact resistance.
To a glass vessel equipped with magnetic stirrer, 189 weight parts of isopropyl alcohol-dispersed colloidal silica (made by Nissan Kagaku Kogyo: 30 percent solid component, average particle size 15 millimicrons; component (F)) were added, and 74 weight parts of γ-glycidoxypropyltrimethoxysilane (component (E)) were then added with stirring. While stirring, 19 weight parts of 10−2 normal hydrochloric acid were added dropwise and stirring was conducted for 24 hours at 5° C. Next, 100 weight parts of propylene glycol monomethylether, 100 weight parts of isopropyl alcohol, 0.2 weight part of silicone surfactant, and 7.5 weight parts of curing agent in the form of aluminum acetyl acetonate were added and thoroughly mixed. The mixture was filtered to prepare a coating composition solution. Other than above-mentioned matter, the operation was conducted in the same manner as in Embodiment 8-1.
As shown in Table 2, the plastic lens (transparent molded article) having a cured coating film that was obtained exhibited the same good scratch resistance, adhesion, external appearance, and impact resistance as Embodiment 8-1.
To a glass vessel equipped with magnetic stirrer, while 94 weight parts of a compound sol (made by Nissan Kagaku Kogyo, tradename HIS-40MH: methanol dispersion, 30 percent solid component; component (F)) comprised chiefly of tin oxide, tungsten oxide, zirconia oxide, and silicon oxide, and 94 weight parts of n-propyl cellosolve-dispersed colloidal silica (made by Nissan Kagaku Kogyo: tradename NPC-ST30, solid component 30 percent; component (F)) were thoroughly mixed with stirring, 67.0 weight parts of an organic silicon compound in the form of γ-glycidoxypropyltrimethoxysilane (component (E)) were added dropwise with stirring. Following the dropwise addition, 16 weight parts of 10−2 normal hydrochloric acid, 230 weight parts of a solvent in the form of propylene glycol monomethylether, 0.2 weight part of silicone surfactant, and 3 weight parts of a curing promoter in the form of aluminum acetyl acetonate were added. The mixture was thoroughly stirred and filtered to obtain a coating composition.
Other than the above-mentioned matter, the operation was conducted in the same manner as in Embodiment 8-1.
As shown in Table 2, the plastic lens (transparent molded article) having a cured coating film that was obtained exhibited the same good scratch resistance, adhesion, external appearance, and impact resistance as Embodiment 8-1.
With the exception that a lens comprised of diethylene glycol bisallylcarbonate polymer was employed in place of the plastic lens (transparent molded article) employed in Embodiments 8-1 to 8-3, the same operation as in Embodiments 8-1 to 8-3 was conducted. As shown in Table 2, these lenses all had poor impact resistance relative to the plastic lenses (transparent molded articles) in the first aspect of the present invention.
The transparency and impact resistance of the plastic lenses obtained in the embodiments and comparative examples of the second aspect were evaluated by the same evaluation methods as in the first aspect above. The antiyellowing property was evaluated by the following method.
The 380-780 nm spectral spectrum of the lens was measured immediately following polymerization and the YI value was calculated from the results to evaluate the antiyellowing property for heat during polymerization. A YI values of less than 2.5 was ranked as A, 2.5 and above but less than 3.5 as B, and 3.5 and above as C.
[Antiyellowing property for light]
The 380-780 nm spectral spectrum of the lens obtained was respectively measured before and after 200 hours of irradiation with a xenon lamp and the respective YI values were calculated from the results. The value obtained by subtracting the YI value prior to irradiation from the NI value following irradiation was denoted as ΔYI and was adopted as an indicator of the antiyellowing property for light. A ΔYI value of less than 1 was ranked as A, 1 and above but less than 2 as B, and 2 and above as C.
Those lenses having an antiyellowing property ranking of C for either or both heat and light, or B for both heat and light, were unsuitable as lenses.
To 100 weight parts of isocyanate terminal prepolymer (denoted as ITP-1 in Table 3) having an isocyanate group content of 13 percent and comprised of polytetramethylene glycol with an average molecular weight of 400 and 4,4′-methylenebis(cyclohexyl isocyanate), 0.5 weight part of 4,4′-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite (denoted as PO-1 in Table 3), 1.5 weight parts of 2-(2′-hydroxy-5′-t-octylphenyl)benzotriazol, 1.25 weight parts of bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, 0.25 weight part of pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] were respectively added in advance. The mixture was uniformly mixed and defoamed. Next, 25.5 weight parts of a mixture (denoted as DETDA in Table 3) of 3,5-diethyl-2,4-toluene diamine and 3,5-diethyl-2,6-toluene diamine were uniformly admixed at 60-70° C. and stirred in short time at high speed. Immediately after stirring, the mixture was poured into a lens-forming glass mold and polymerized with heating for 15 hours at 120° C. to obtain a plastic lens (transparent molded article). The various physical properties of the plastic lens obtained are given in Table 3. Table 3 reveals that the obtained plastic lens exhibited excellent antiyellowing property for heat and light, and had excellent transparency without fogging caused, by cloud or scattering due to microcrystallization. The lens also had good impact resistance, remaining undamaged in ball drop tests employing not only 16 g balls, as FDA standard, but also 1 kg balls.
With the exception that the components shown in Table 3 were employed, plastic lenses (transparent molded articles) were obtained by the same operation as in Embodiment 9. The various physical properties of these plastic lenses are shown in Table 3. Table 3 shows that the plastic lenses obtained exhibited excellent antiyellowing properties for heat and light, and had excellent transparency without fogging caused by cloud or scattering due to microcrystallization. The lens also had good impact resistance, remaining undamaged in ball drop tests employing not only 16 g balls, as FDA standard, but also 1 kg balls.
With the exception that PO-1 was not employed, the same operation was conducted as in Embodiment 9. The various physical properties of the plastic lens obtained are given in Table 3. Table 3 reveals that the plastic lens had excellent transparency without fogging caused by cloud or scattering due to microcrystallization, remaining undamaged in ball drop tests employing not only 16 g balls, as FDA standard, but also 1 kg balls. However, it had poor antiyellowiing property for heat and light.
With the exception that a sulfur-based peroxide decomposing agent in the form of ditridecyl-3,3′-thiodipropionate (denoted as SO-1 in Table 3) was employed in place of PO-1, the same operation was conducted as in Embodiment 1. The various physical properties of the plastic lens obtained are given in Table 1. Table 1 reveals that the plastic lenses obtained had poor transparency due to slight fogging and poor antiyellowing properties for heat and light, becoming colored lenses. Although they did not break in the 16 g ball drop test, as FDA standard, impact resistance was poor as cracks were observed in about 20 percent of the test samples when tested with 1 kg balls.
The plastic lenses (transparent molded articles) having cured coating films obtained in the embodiments and comparative examples of the second aspect were subjected to the scratch resistance test, adhesion test, appearance (transparency, surface condition and the like), and impact resistance test measurements described in the first aspect above to measure the various physical properties thereof.
A coating composition solution was prepared by the same method as in Embodiment 8-1 of the first aspect above.
The plastic lens (transparent molded article) produced in Embodiment 9 described above was thoroughly cleaned by immersion for 5 min in a 10 percent sodium hydroxide aqueous solution at 55° C., after which a coating solution prepared by the above-described method was coated by dipping (lifting rate 20 cm/min) and heated for 2 hours at 120° C. to form a cured coating film Various evaluations were then conducted. The plastic lens (transparent molded article) having a cured coating film that was obtained had good scratch resistance, adhesion, appearance, and impact resistance.
To a glass vessel equipped with magnetic stirrer, 189 weight parts of isopropyl alcohol-dispersed colloidal silica (made by Nissan Kagaku Kogyo: 30 percent solid component, average particle size 15 millimicrons; component (F)) were added, and 74 weight parts of γ-glycidoxypropyltrimethoxysilane (component (E)) were then added with stirring. While stirring, 19 weight parts of 10−2 normal hydrochloric acid were added dropwise and stirring was conducted for 24 hours at 5° C. Next, 100 weight parts of propylene glycol monomethylether, 100 weight parts of isopropyl alcohol, 0.2 weight part of silicone surfactant, and 7.5 weight parts of curing agent in the form of aluminum acetyl acetonate were added and thoroughly mixed. The mixture was filtered to prepare a coating composition solution. Other than above-mentioned matter, the operation was conducted in the same manner as in Embodiment 10-1.
As shown in Table 4, the plastic lens (transparent molded article) having a cured coating film that was obtained exhibited the same good scratch resistance, adhesion, external appearance, and impact resistance as Embodiment 18-1.
To a glass vessel equipped with magnetic stirrer, while 94 weight parts of a compound sol (made by Nissan Kagaku Kogyo, tradename HIS-40 MH: methanol dispersion, 30 percent solid component; component (F)) comprised chiefly of tin oxide, tungsten oxide, zirconia oxide, and silicon oxide, and 94 weight parts of n-propyl cellosolve-dispersed colloidal silica (made by Nissan Kagaku Kogyo: tradename NPC-ST30, solid component 30 percent; component (F)) were thoroughly mixed with stirring, 67.0 weight parts of γ-glycidoxypropyltrimethoxysilane (component (E)) were added dropwise with stirring. Following the dropwise addition, 16 weight parts of 10−2 normal hydrochloric acid, 230 weight parts of a solvent in the form of propylene glycol monomethylether, 0.2 weight part of silicone surfactant, and 3 weight parts of a curing promoter in the form of aluminum acetyl acetonate were added. The mixture was thoroughly stirred and filtered to obtain a coating composition.
Other than the above-mentioned matter, the operation was conducted in the same manner as in Embodiment 18-1.
As shown in Table 4, the plastic lens (transparent molded article) having a cured coating film that was obtained exhibited the same good scratch resistance, adhesion, external appearance, and impact resistance as Embodiment 10-1.
With the exception that a lens comprised of diethylene glycol bisallylcarbonate polymer was employed in place of the plastic lens (transparent molded article) employed in Embodiments 18-1 to 18-3, the same operation as in Embodiments 18-1 to 18-3 was conducted. As shown in Table 4, these lenses all had poor impact resistance relative to the plastic lenses (transparent molded articles) in the second aspect of the present invention.
The embodiments of the third aspect in which an antireflective film was applied to an optical member having a hard coat layer are described below. Although an antireflective film can be applied without an intermediate hard coat layer, an intermediate hard coat layer is preferred from the perspectives of strength, heat resistance, abrasion resistance, chemical resistance and the like.
Evaluation of the physical properties of the optical members having an antireflective film obtained in the embodiments of the third aspect was conducted by the following test methods.
The front surface side luminous reflectance Y of the plastic lenses was measured with a Hitachi U-3410 Spectrophotometer by coating the inside surface with a black magic marker, eliminating reflection, and measuring the luminous reflectance.
The back surface side luminous reflectance Y of the plastic lenses was measured with a Hitachi U-3410 Spectrophotometer by first measuring the luminous reflectance of a lens having an antireflective layer on the concave surface side, measuring the luminous reflectance (including the back surface side luminous reflectance) of the concave surface of the comparative product in which the same antireflective layer was provided, the convex surface was coated with a black magic marker, and reflection was eliminated. The back surface side luminous reflectance Y was calculated by subtracting the previously measured luminous reflectance from the concave surface luminous reflectance of the comparative product.
One hundred squares of 1 mm×1 mm were made with a razor on the surface of a plastic lens, cellophane tape was adhered on the squares, the tape was pulled off in one motion, and the evaluation was conducted from the number of remaining squares. In the table, this is given as the number of remaining over 100.
A 1 kgf/cm2 load was applied with steel wool to the surface of a plastic lens and the surface was scrubbed at 20 strokes. Evaluation was conducted from the surface condition according to the following criteria:
UA: Almost no scratching
A: Several light scratches
B: Numerous light scratches, several heavy scratches
C: Numerous light scratches, numerous heavy scratches
D: Nearly peeled
The plastic lens was heated in a dry oven for 1 hour and the temperature at which cracking occurred was measured.
The plastic lens was immersed for 1 hour in a 10 percent NaOH aqueous solution and evaluation was conducted from the surface condition according to the following criteria:
The plastic lenses were inserted into frames and an examination of the appearance of the antireflective film was conducted.
UA: No abnormality in darkroom, under fluorescent lamp and high-pressure mercury lamp.
A: No abnormality when inspected in darkroom and under fluorescent lamp.
B: Fogging present when inspected in darkroom and under fluorescent lamp.
C: Slight fogging present indoors and under fluorescent lamp.
D: Fogging present indoors and under fluorescent lamp
Plastic lenses having hard coat layers obtained by the method described in Reference Examples 1 and 2 further below were pretreated by an ion gun (acceleration voltage 250 V, current 160 mA, irradiation duration 60 sec) using Ar gas or oxygen gas. They were then heated to 85° C. and a first layer (refractive index 1.46, thickness 0.4233). (where is 500 nm; identical below)) comprised of SiO2 was formed as an undercoating by vacuum evaporation (vacuum degree of 2×10−5 Torr) on the above-described hard coat layer.
Next, formed was a ¼λ layer corresponding to a medium refractive index layer comprised of both a second layer (refractive index 2.21, film thickness 0.0374) formed by heating at an electron gun output current of 170 mA a three-component evaporation composition A (weight ratio: Nb2O5:ZrO2:Y2O3=90:5:5) obtained by admixing Nb2O5 powder, ZrO2 powder, and Y2O3 powder, pressing the mixture at a pressure of 300 kg/cm2, and sintering it at a temperature of 1,300° C., and a third layer (refractive index 1.46, film thickness 0.0962λ) comprised of SiO2.
A ½λ layer corresponding to a high refractive index layer comprised of a fourth layer (refractive index 2.21, film thickness 0.1396λ) formed from the above-mentioned evaporation composition A, a fifth layer (refractive index 1.46, film thickness 0.0674λ) comprised of SiO2, and a sixth layer (refractive index 2.21, film thickness 0.1584λ) formed from the above-mentioned evaporation substance A was formed on the ¼λ layer corresponding to a medium refractive index layer.
A ¼λ low refractive index layer comprised of SiO2 was formed as the seventh layer on the ½λ layer corresponding to a high refractive index layer to obtain a plastic lens having an antireflective film
This operation was also conducted on the back surface of the plastic lens to obtain a plastic lens having antireflective films on both surfaces.
Each of the above-described second through seventh layers was formed by vacuum evaporation in the same manner as the first layer.
Table 5 gives various conditions such as the evaporation composition and thickness of the above-described antireflective films
Table 5 also gives the results of evaluation of (1)-(6) above for the plastic lenses obtained as set forth above.
The antireflective film of the present embodiment comprises, from the substrate side, a ¼λ layer (corresponding to a medium refractive index layer), a ½λ layer (corresponding to a high refractive index layer), and ¼ λ layer (corresponding to a low refractive index layer). A layer of SiO2, which is a substance of low refractive index, was inserted between the two high refractive index layers formed from the evaporation composition A in the ½λ layer (this applies to the fourth, fifth and sixth layers of the embodiment).
By such a combination, the film thickness of the high refractive index layer, normally requiring a film thickness of about 0.5λ can be reduced to about 0.3λ by combining the fourth and sixth layers.
This is because the combined refractive index of the fourth, fifth and sixth layer, inserted the SiO2 layer between them, can be made 2.02-2.08. In the present configuration, it was about 2.04.
The use of the present configuration is undesirable when the refractive index in the high refractive index substance is not greater than 2.1 because the antireflective property decreases.
Since the high refractive index substance layer has poorer structural strength and heat resistance than the SiO2 layer, the insertion of SiO2 with high structural strength and heat resistance could increase the strength and heat resistance of the antireflective film
Since the evaporation substance A had a high refractive index of not less than 2.2 when evaporated only with an electron gun (an ion assist method must be employed to achieve the same refractive index in a TiO2 layer, which is commonly employed as the high refractive index substance), even when a thin layer of SiO2 of a low refractive index substance was intermediately inserted, there was little influence of decrease in refractive index and it was possible to form a low reflectance antireflective film
Plastic lens having hard coat layers obtained by the methods shown in Reference Examples 1 and 2, described further below, was pretreated (acceleration voltage 250 V, current 160 mA, irradiation duration 60 sec) with an ion gun using Ar gas or oxygen gas and then heated to 85° C. A first layer comprised of SiO2 (refractive index 1.46, film thickness 0.4230λ (where λ was 500 nm; identical below)) was formed as an undercoating layer by vacuum evaporation (vacuum of 2×10−5 Torr) on the above-mentioned hard coat layers.
Formed was a ¼λ layer corresponding to a medium refractive index layer comprised of a second layer (refractive index 2.27, film thickness 0.0416λ, ion assist output 350 V, 150 mA, O2 gas and Ar gas) formed from three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O3=90:5:5) at an electron gun output current of 170 mA jointly using an ion assist, and a third layer (refractive index 1.46, film thickness 0.0969λ) comprised of SiO2.
On the ¼λ layer corresponding to a medium refractive index layer, formed was a ½λ layer corresponding to a high refractive index layer, comprised of a fourth layer (refractive index 2.27, film thickness 0.1370λ) formed from the above-mentioned evaporation composition A (jointly employing ion assist), a fifth layer (refractive index 1.46, film thickness 0.0696λ) comprised of SiO2, and a sixth layer (refractive index 2.27, film thickness 0.1461λ) formed from the above-mentioned evaporation substance A (jointly employing ion assist).
On the ½λ layer corresponding to a high refractive index layer, a ¼ λ low refractive index layer comprised of SiO2 was then formed as the seventh layer to obtain a plastic lens having an antireflective film. This operation was also conducted on the back surface of the plastic lens, yielding a plastic lens having antireflective layers on both surfaces.
A mixture gas of oxygen and argon was employed as the ionized gas in the ion assist.
The results are given in Table 6.
A plastic lens having a hard coat layer obtained by the manner described in Reference Examples 1 and 2 further below was pretreated (acceleration voltage 250 V, current 160 mA, irradiation duration 60 sec) with an ion gun using Ar gas or oxygen gas and then heated to 85° C. A first layer (refractive index 1.46, film thickness 0.4670λ (where λ was 500 nm; identical below)) comprised of SiO2 was formed as an undercoating layer by vacuum evaporation (vacuum degree of 2×10−5 Torr) on the hard coat layer mentioned above.
Formed was a ¼λ layer A corresponding to a medium refractive index layer comprised of a second layer (refractive index 2.21, film thickness 0.014λ) formed by heating a three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O3=90:5:5) at an electron gun output current of 170 mA and a third layer (refractive index 1.46, film thickness 0.2001λ) comprised of SiO2.
Next, formed was a ¼λ layer B corresponding to a medium refractive index layer, comprised of a fourth layer (refractive index 2.21, film thickness 0.0390λ) formed by heating a three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O3=90:5:5) at an electron gun output current of 170 mA and a fifth layer (refractive index 1.46, film thickness 0.1420λ) comprised of SiO2.
A ½λ layer corresponding to a high refractive index layer comprised of a sixth layer (refractive index 2.21, film thickness 0.1381λ) formed from an evaporation composition A, a seventh layer (refractive index 1.46, film thickness 0.0805λ) comprised of SiO2, and an eighth layer (refractive index 2.21, film thickness 0.1524λ) formed from the above-mentioned evaporation substance A was formed on the ¼λ layers A and B.
A ¼λ low refractive index layer comprised of SiO2 was then formed as the ninth layer on the ½λ layer corresponding to a high refractive index layer to obtain a plastic lens having an antireflective film. This operation was also conducted on the back surface of the plastic lens, yielding a plastic lens having antireflective layers on both surfaces.
The results are given in Table 7.
A plastic lens having a hard coat layer obtained by the manner described in Reference Examples 1 and 2 further below was pretreated (acceleration voltage 250 V, current 160 mA, irradiation duration 60 sec) with an ion gun using Ar gas or oxygen gas and then heated to 85° C. A first layer (refractive index 1.46, film thickness 0.4670λ (where λ was 500 nm; identical below)) comprised of SiO2 was formed as an undercoating layer by vacuum evaporation (vacuum degree of 2×10−5 Torr) on the hard coat layer.
Formed was a ¼λ layer A corresponding to a medium refractive index layer, comprised of a second layer (refractive index 2.27, film thickness 0.0136λ) formed from a three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O3=90:5:5) at an electron gun output current of 170 mA jointly using ion assist, and a third layer (refractive index 1.46, film thickness 0.2044λ) comprised of SiO2.
Next, formed was a ¼λ layer B corresponding to a medium refractive index layer, comprised of a fourth layer (refractive index 2.27, film thickness 0.0445λ) formed from a three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O=90:5:5) at an electron gun output current of 170 mA jointly using ion assist, and a fifth layer (refractive index 1.46, film thickness 0.1505λ) comprised of SiO2.
A ½λ layer corresponding to a high refractive index layer comprised of a sixth layer (refractive index 2.27, film thickness 0.1367λ) formed from the above-mentioned evaporation composition A (jointly using ion assist), a seventh layer (refractive index 1.46, film thickness 0.0892λ) comprised of SiO2, and an eighth layer (refractive index 2.27, film thickness 0.1592λ) formed from the above-mentioned evaporation substance A was formed on the ¼λ layers A and B corresponding to a medium refractive index layers.
A ¼λ low refractive index layer comprised of SiO2 was then formed as the ninth layer on the high refractive index layer to obtain a plastic lens having an antireflective film. This operation was also conducted on the back surface of the plastic lens, yielding a plastic lens having antireflective layers on both surfaces.
The results are given in Table 8.
The above-mentioned plastic lens having a hard coat layer obtained by the manner described in Reference Examples 1 and 2 further below was pretreated (acceleration voltage 250 V, current 160 mA, irradiation duration 60 sec) with an ion gun using Ar gas or oxygen gas and then heated to 85° C. A first layer (refractive index 1.46, film thickness 0.4222λ (where 2 was 500 nm; identical below)) comprised of SiO2 was formed as an undercoating layer by vacuum evaporation (vacuum degree of 2×10−5 Torr) on the hard coat layer.
Formed was a ¼λ layer corresponding to a medium refractive index layer, comprised of a second layer (refractive index 2.21, film thickness 0.0458λ) formed by heating a three-component evaporation composition A (weight ratio Nb2O5:ZrO2:Y2O3=90:5:5) at an electron gun output current of 170 mA, and a third layer (refractive index 1.46, film thickness 0.0814λ) comprised of SiO2.
Next, on the ¼λ layer corresponding a medium refractive index layer, formed was a ½λ layer corresponding to a high refractive index layer, comprised of a fourth layer (refractive index 2.21, film thickness 0.1172λ) formed from the above-mentioned evaporation composition A, a fifth layer (refractive index 1.46, film thickness 0.0280λ) comprised of SiO2, a sixth layer (refractive index 2.21, film thickness 0.1143λ) formed from the above-mentioned evaporation substance A, a seventh layer (refractive index 1.46, film thickness 0.0246λ) comprised of SiO2, and an eighth layer (refractive index 2.21, film thickness 0.1280λ) formed from the above-mentioned evaporation substance A.
A ¼λ low refractive index layer comprised of SiO2 was then formed as the ninth layer on the ½λ layer corresponding to a high refractive index layer to obtain a plastic lens having an antireflective film. This operation was also conducted on the back surface of the plastic lens, yielding a plastic lens having antireflective layers on both surfaces.
To 100 weight parts of isocyanate terminal prepolymer having an isocyanate group content of 13 percent and comprised of polytetramethylene glycol with an average molecular weight of 400 and 4,4′-methylenebis(cyclohexyl isocyanate), 0.024 weight part of monobutoxyethyl acid phosphate and 0.036 weight parts of di(butoxyethyl) acid phosphate were added in advance. The mixture was uniformly mixed and defoamed. Next, 25.5 weight parts of a mixture of 3,5-diethyl-2,4-toluene diamine and 3,5-diethyl-2,6-toluene diamine were uniformly admixed at 60-70° C. and stirred in short time at high speed. Immediately after stirring, the mixture was poured into a lens-forming glass mold and polymerized with heating for 15 hours at 120° C. to obtain a plastic lens.
A coating composition solution was prepared by the same method as in Embodiment 8-1 of the first aspect above.
The plastic lens comprised of the polyurethane urea polymer of Reference Example 1 was thoroughly cleaned by immersion for 5 min in a 10 percent sodium hydroxide aqueous solution at 55° C., after which a coating solution prepared by the above-described method was coated by dipping (lifting rate 20 cm/rain) and heated for 2 hours at 120° C. to form a hard coat layer.
According to the first aspect of the present invention, a molded article having excellent transparency and mold releasing property from a forming mold that is suited to optical applications, and a method of manufacturing the same can be provided. In particular, a molded article provided with good mold releasing property that is suited to optical applications without loss of transparency of polyurethane urea material as disclosed in U.S. Pat. No. 6,127,505 mentioned above, and a method of manufacturing the same can be provided.
According to the second aspect of the present invention, a molded article suited to optical applications, which tends not to yellow for light and heat, and a method of manufacturing the same can be provided. In particular, a molded article provided with antiyellowing property for light and heat, that is suited to optical applications, without loss of transparency of materials which are obtained by cast polymerization of an aromatic diamine and an isocyanate terminal prepolymer having an intramolecular urethane bond as disclosed in U.S. Pat. No. 6,127,505 mentioned above, and a method of manufacturing the same can be provided.
According to the third aspect of the present invention, an optical member comprising a substrate in the form of a material comprised of polyurethane urea polymer and having an antireflective layer that is suited to the substrate and has a good heat resistance and high film strength as well as that is undergone little reduction of heat resistance over time can be provided.
Number | Date | Country | Kind |
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2001-081518 | Mar 2001 | JP | national |
2001-081720 | Mar 2001 | JP | national |
2002-025923 | Feb 2002 | JP | national |
2002-025934 | Feb 2002 | JP | national |
2002-025953 | Feb 2002 | JP | national |
This application is a Division of U.S. application Ser. No. 10/471,287, filed Sep. 22, 2003; which is a 371 of PCT/JP02/02666, filed Mar. 20, 2002. Priority to Japanese patent application Nos. 2001-081518, filed Mar. 21, 2001; 2001-081720, filed Mar. 21, 2001; 2002-025923, filed Feb. 1, 2002; 2002-025934, filed Feb. 1, 2002; and 2002-025953, filed Feb. 1, 2002, are claimed. All of the above applications are incorporated herein by reference.
Number | Date | Country | |
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Parent | 10471287 | Mar 2004 | US |
Child | 14713181 | US |