Patent Grant
9574090
The disclosure relates to a resin composition and a resin film and electronic device which are obtained using this resin composition, more particularly relates to a resin cc position which can give a resin film which exhibits a high adhesion to a substrate and is excellent in transparency and chemical resistance and to a resin film and electronic device which are obtained using this resin composition.
A touch pallet or flexible organic EL display or other display device which is provided with a touch panel structure or an integrated circuit device, solid state imaging device, color filter, black matrix, or other electronic device is provided with a protective film for preventing deterioration or damage, a flattening film for flattening the device surface or interconnects, an electric insulating film for ensuring the electrical insulation property, etc. constituted by various types of resin films.
In the past, as the resin materials for forming such resin films, epoxy resins and other heat curable resin materials have been generally used. In recent years, along with the higher density of interconnects and devices, development of new resin materials excellent in low dielectric constant and other electrical characteristics has been sought for these resin materials as well.
To deal with such demands, for example, Patent Document 1 discloses a radiation-sensitive resin composition containing a cyclic olefin polymer which has a protonic polar group, unsaturated group-containing compound, silane-modified organic-inorganic hybrid compound, and radical-generating photopolymerization initiator.
Patent Document 1: Japanese Patent Publication No. 2012-211988A
However, according to the radiation-sensitive resin composition disclosed in Patent Document 1, a resin film which is excellent in transparency etc. can be given, but the adhesion to a soda glass substrate or other transparent substrate is not necessarily sufficient. For this reason, this was not suitable for use for applications in which resin materials excellent in adhesion to a soda glass substrate or other transparent substrate were sought, for example, an application of a protective film or an electrical insulating film of a display device provided with a touch panel structure.
Therefore, the present invention has as its object the provision of a resin composition which can give a resin film which exhibits high adhesion to a substrate and is excellent in transparency and chemical resistance. Further, the present invention has as its object the provision of a resin film which is obtained using such a resin composition and an electronic device which is provided with that resin film.
The present inventors engaged in intensive research for achieving the above objects and as a result discovered that the above objects can be achieved by mixing, into a binder resin, a photopolymerization initiator and an alkoxysilyl group-containing (meth)acrylate compound and tetrafunctional or higher functional (meth)acrylate compound in specific ratios and thereby completed the present invention.
That is, according to one aspect of the present invention, there are provided:
According to one aspect of the present invention, it is possible to provide a resin composition which can give a resin film which exhibits high adhesion to a substrate and is excellent in transparency and chemical resistance, a resin film which is obtained using such a resin composition, and an electronic device which is provided with that resin film.
The resin composition of one embodiment of the present invention contains a binder resin (A), alkoxysilyl group-containing (meth)acrylate compound (B), tetrafunctional or higher functional (meth)acrylate compound (C), and photopolymerization initiator (D), wherein a total content of the alkoxysilyl group-containing (meth)acrylate compound (B) and the tetrafunctional or higher functional (meth)acrylate compound (C) is 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin (A).
(Binder Resin (A))
The binder resin (A) used in one embodiment of the present invention is not particularly limited, but a cyclic olefin polymer which has a protonic polar group (A1), an acrylic resin (A2), Cardo resin (A3), polysiloxane (A4), or polyimide (A5) is preferable. Among these as well, from the viewpoint of being able to improve the adhesion to a substrate more, a cyclic olefin polymer which has a protonic polar group (A1) is particularly preferable. These binder resins (A) may respectively be used alone or as two types or more combined.
As the cyclic olefin polymer which has a protonic polar group (A1) (below, simply referred to as the “cyclic olefin polymer (A1)”), a polymer of one or more cyclic olefin monomers or a copolymer of one or more cyclic olefin monomers and a monomer which can copolymerize with them may be mentioned, but in one embodiment of the present invention, as the monomer for forming the cyclic olefin polymer (A1), it is preferable to use at least a cyclic olefin monomer which has a protonic polar group (a).
Here, the “protonic polar group” means a group which contains an atom belonging to Group XV or Group XVI of the Periodic Table to which a hydrogen atom directly bonds. Among the atoms belonging to Group XV or Group XVI of the Periodic Table, atoms belonging to Period 1 or Period 2 of Group XV or Group XVI of the Periodic Table are preferable, an oxygen atom, nitrogen atom, or sulfur atom is more preferable, and an oxygen atom is particularly preferable.
As specific examples of such a protonic polar group, a hydroxyl group, carboxy group (hydroxycarbonyl group), sulfonic acid group, phosphoric acid group, and other polar groups which have oxygen atoms; primary amino group, secondary amino group, primary amide group, secondary amide group (imide group), and other polar groups which have nitrogen atoms; a thiol group and other polar groups which have sulfur atoms; etc. may be mentioned. Among these as well, ones which have oxygen atoms are preferable, carboxy group is more preferable. In one embodiment of the present invention, the number of protonic polar groups which bond with the cyclic olefin resin which has protonic polar groups is not particularly limited. Further, different types of protonic polar groups may also be included.
As specific examples of the cyclic olefin monomer which has a protonic polar group (a) (below, suitably called the “monomer (a)”), 2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyltricyclo[5.2.1.02,6]deca-3,8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, N-(hydroxycarbonylmethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(dihydroxycarbonylpropyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylphenethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-(4-hydroxyphenyl)-1-(hydroxycarbonyl)ethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylphenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, and other carboxy group-containing cyclic olefins; 2-(4-hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(4-hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 4-(4-hydroxyphenyl)tetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-(4-hydroxyphenyl)tetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 2-hydroxybicyclo[2.2.1]hept-5-ene, 2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2-hydroxyethylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-(1-hydroxy-1-trifluormethyl-2,2,2-trifluoroethyl)bicyclo[2.2.1]hept-5-ene, 2-(2-hydroxy-2-trifluoromethyl-3, 3, 3-trifluoropropyl)bicyclo[2.2.1]hept-5-ene, 3-hydroxytricyclo[5.2.1.02,6]deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.02,6]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-hydroxymethyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.13,6.02,7]dodec-9-ene, N-(hydroxyethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(hydroxyphenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, and other hydroxyl group-containing cyclic olefins etc. may be mentioned. Among these as well, from the viewpoint of the adhesion of the obtained resin film becoming higher, carboxy group-containing cyclic olefins are preferable, while 4-hydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene is particularly preferable. These monomers (a) may respectively be used alone or may be used as two types or more combined.
In the cyclic olefin polymer (A1), the ratio of content of the units of the monomer (a) is preferably 10 to 90 mol % with respect to all monomer units. By the ratio of content of the units of the monomer (a) being in this range, heat resistance and solubility in a polar solvent can be further improved with a good balance.
Further, the cyclic olefin polymer (A1) used in one embodiment of the present invention may be a copolymer which is obtained by copolymerization of a cyclic olefin monomer which has a protonic polar group (a) and a monomer (b) which can copolymerize with this. As such a copolymerizable monomer (b), a cyclic olefin monomer which has a polar group other than a protonic polar group (b1), a cyclic olefin monomer which does not have a polar group (b2), and a monomer other than a cyclic olefin (b3) (below, suitably called the “monomer (b1)”, “monomer (b2)”, and “monomer (b3)”) may be mentioned.
As the cyclic olefin monomer which has a polar group other than a protonic polar group (b1), for example, a cyclic olefin which has an N-substituted imide group, ester group, cyano group, acid anhydride group, or halogen atom may be mentioned.
As a cyclic olefin which has an N-substituted imide group, for example, a monomer represented by the following formula (1) or a monomer represented by the following formula (2) may be mentioned.
(In the above formula (1), R1 indicates a hydrogen atom or C1 to C16 alkyl group or aryl group. “n” indicates an integer of 1 to 2.)
(In the above formula (2), R2 indicates a C1 to C3 bivalent alkylene group, while R3 indicates a C1 to C10 monovalent alkyl group or a C1 to C10 monovalent halogenated alkyl group.)
In the above formula (1), R1 is a C1 to C16 alkyl group or aryl group. As specific examples of the alkyl group, a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, and other straight chain alkyl groups; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, tricyclodecanyl group, adamantyl group, and other cyclic alkyl groups; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1-methyltetradecyl group, and other branched alkyl groups; etc. may be mentioned. Further, as specific examples of the aryl group, a benzyl group etc. may be mentioned. Among these as well, due to the more excellent heat resistance and solubility in a polar solvent, a C6 to C14 alkyl group and aryl group are preferable, while a C6 to C10 alkyl group and aryl group are more preferable. If the number of carbon atoms is 4 or less, the solubility in a polar solvent is inferior, while if the number of carbon atoms is 17 or more, the heat resistance is inferior. Further, when patterning the resin film, there is the problem that the resin film melts by heat and the patterns to end up disappearing.
As specific examples of the monomer represented by the above formula (1), bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-phenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-ethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-butylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-cyclohexylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-adamantylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylpenyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-ethylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-ethylbutyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-methylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-butylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-butylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-ethylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-propylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-propylpentyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-ethylheptyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-propylhexyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylnonyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-methylnonyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-methylnonyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-methylnonyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(5-methylnonyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(2-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(3-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(4-ethyloctyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyldecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyldodecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylundecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyldodecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyltridecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methyltetradecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(1-methylpentadecyl)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-phenyl-tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4, 5-dicarboxyimide, N-(2, 4-dimethoxyphenyl)-tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4, 5-dicarbox yimide, etc. may be mentioned. Note that, these may respectively be used alone or may be used as two types or more combined.
On the other hand, in the above formula (2), R2 is a C1 to C3 bivalent alkylene group. As the C1 to C3 bivalent alkylene group, a methylene group, ethylene group, propylene group, and isopropylene group may be mentioned. Among these as well, due to the excellent polymerization activity, a methylene group and ethylene group are preferable.
Further, in the above formula (2), R3 is a C1 to C10 monovalent alkyl group or C1 to C10 monovalent halogenated alkyl group. As the C1 to C10 monovalent alkyl group, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, hexyl group, cyclohexyl group, etc. may be mentioned. As the C1 to C10 monovalent halogenated alkyl group, for example, a fluoromethyl group, chloraethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, difluoroethyl group, trifluoromethyl group, trichloroethyl group, 2,2, 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, etc. may be mentioned. Among these as well, since the solubility in a polar solvent is excellent, as R3, a methyl group or ethyl group is preferable.
Note that, the monomer represented by the above formulas (1) and (2) can, for example, be obtained by an imidization reaction between a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. Further, the obtained monomer can be efficiently isolated by separating and refining the reaction solution of the imidization reaction by a known method.
As the cyclic olefin which has an ester group, for example, 2-acetoxybicyclo[2.2.1]hept-5-ene, 2-acetoxymethylbicyclo[2.2.1]hept-5-ene, 2-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-propoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-propoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-(2, 2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(2,2, 2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methoxycarbonyltricyclo[5.2.1.02,6]dec-8-ene, 2-ethoxycarbonyltricyclo[5.2.1.02,6]dec-8-ene, 2-propoxycarbonyltricyclo[5.2.1.02,6]dec-8-ene, 4-acetoxytetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-ethoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-propoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-butoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-methoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-propoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-butoxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.13,602,7]dodec-9-ene, etc. may be mentioned.
As the cyclic olefin which has a cyano group, for example, 4-cyanotetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-cyanotetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4,5-dicyanotetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 2-cyanobicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyanobicyclo[2.2.1]hept-5-ene, 2,3-dicyanobicyclo[2.2.1]hept-5-ene, etc. may be mentioned.
As the cyclic olefin which has an acid anhydride group, for example, tetracyclo[6.2.1.13,6.02,7]dodec-9-ene-4,5-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene anhydride, etc. may be mentioned.
As the cyclic olefin which has a halogen atom, for example, 2-chlorobicyclo[2.2.1]hept-5-ene, 2-chloromethylbicyclo[2.2.1]hept-5-ene, 2-(chlorophenyl)bicyclo[2.2.1]hept-5-ene, 4-chlorotetracyclo[6.2.1.13,6.02,7]dodec-9-ene, 4-methyl-4-chlorotetracyclo[6.2.1.13,6.02,7]dodec-9-ene, etc. may be mentioned.
These monomers (b1) may respectively be used alone or may be used as two types or more combined.
As the cyclic olefin monomer which does not have a polar group (b2), bicyclo[2.2.1]hept-2-ene (also called “norbornene”), 5-ethylbicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[5.2.1.02,6]deca-3,8-diene (common name: dicyclopentadiene), tetracyclo[10.2.1.02,11.04,9]pentadec-4,6,8,13-tetraene, tetracyclo[6.2.1.13,6.02,7]dodec-4-ene (also called “tetracyclododecene”), 9-methyl-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-ethyl-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-methylidene-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-ethylidene-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-vinyl-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-propenyl-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, pentacyclo[9.2.1.13,9.02,10.04,8]pentadeca-5,12-diene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, indene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, 9-phenyl-tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, tetracyclo[9.2.1.02,10.03,8]tetradec-3,5,7,12-tetraene, pentacyclo[9.2.1.13,9.02,10.04,8]pentadec-12-ene, etc. may be mentioned. These monomers (b2) may respectively be used alone or my be used as two types or more combined.
As specific examples of the monomer other than a cyclic olefin (b3), ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and other C2 to C20 α-olefins; 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, and other nonconjugated dienes and their derivatives; etc. may be mentioned. Among these as well, α-olefin is preferable. These monomers (b3) may respectively be used alone or may be used as two types or more combined.
Among these monomers (b1) to (b3) as well, from the viewpoint of the effect of one embodiment of the present invention becoming more remarkable, a cyclic olefin monomer which has a polar group other than a protonic polar group (b1) is preferable, while a cyclic olefin which has an N-substituted imide group is particularly preferable.
In the cyclic olefin polymer (A1), the ratio of content of units of the copolymerizable monomer (b) is preferably 10 to 90 mol % with respect to the total monomer units. If the ratio of content of the units of the copolymerizable monomer (b) is too small, the cyclic olefin polymer (A1) is liable to become insufficient in solubility in a polar solvent, while if too great, heat resistance is liable to become insufficient.
Note that, in one embodiment of the present invention, it is also possible to introduce a protonic group in a cyclic olefin-based polymer which does not have a protonic polar group utilizing a known modifying agent so as to obtain the cyclic olefin polymer (A1). The polymer which does not have a protonic polar group can be obtained by polymerizing at least one of the above-mentioned monomers (b1) and (b2) and, in accordance with need, a monomer (b3) in any combination.
Note that, the cyclic olefin polymer (A1) used in one embodiment of the present invention may be a ring-opened polymer obtained by ring-opening polymerization of the above-mentioned monomers or may be an addition polymer obtained by addition polymerization of the above-mentioned monomers, but from the viewpoint of the effect of one embodiment of the present invention becoming more remarkable, a ring-opened polymer is preferable.
A ring-opened polymer can be produced by ring-opening methathesis polymerization of a cyclic olefin monomer which has a protonic polar group (a) and a copolymerizable monomer (b) used according to need in the presence of a methathesis reaction catalyst. As the method of production, for example, the method described in International Publication No. 2010/110323A, [0039] to [0079], etc. can be used. On the other hand, an addition polymer can be obtained by causing polymerization of a cyclic olefin monomer which has a protonic polar group (a) and a copolymerizable monomer (b) used according to need using a known additional polymerization catalyst, for example, a catalyst comprised of a compound of titanium, zirconium, or vanadium and an organic aluminum compound.
Further, when the cyclic olefin polymer (A1) used in one embodiment of the present invention is a ring-opened polymer, it is preferable to further perform a hydrogenation reaction and obtain a hydrogenated product in which the carbon-carbon double bonds which are contained in the main chain are hydrogenated. When the cyclic olefin polymer (A1) is a hydrogenated product, the ratio of the hydrogenated carbon-carbon double bonds (hydrogenation rate) is usually 50% or more. From the viewpoint of the heat resistance, 70% or more is preferable, 90% or more is more preferable, and 95% or more is furthermore preferable.
Further, the acrylic resin (A2) used in one embodiment of the present invention is not particularly limited, but a homopolymer or copolymer having at least one of a carboxylic acid which has an acryl group, carboxylic anhydride which has an acryl group, epoxy group-containing acrylate compound and oxetane group-containing acrylate compound as an essential ingredient is preferable.
As specific examples of the carboxylic acid which has an acryl group, (meth)acrylic acid (meaning acrylic acid and/or methacrylic acid, below, same for methyl(meth)acrylate etc.), crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, phthalic acid mono-(2-((meth)acryloyloxy)ethyl), N-(carboxyphenyl)maleimide, N-(carboxyphenyl)(meth)acrylamide, etc. may be mentioned. As specific examples of the carboxylic anhydride which has an acryl group, maleic anhydride, citraconic anhydride, etc. may be mentioned.
As specific examples of the epoxy group-containing acrylate compound, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc. may be mentioned.
As specific examples of the oxetane group-containing acrylate compound, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (3-methyloxetan-3-yl)ethyl (meth)acrylate, (3-ethyloxetan-3-yl)ethyl (meth)acrylate, (3-chloromethyloxetan-3-yl)methyl (meth)acrylate, (oxetan-2-yl)methyl (meth)acrylate, (2-methyloxetan-2-yl)methyl (meth)acrylate, (2-ethyloxetan-2-yl)methyl (meth)acrylate, (1-methyl-1-oxetanyl-2-phenyl)-3-(meth)acrylate, (1-methyl-1-oxetanyl)-2-trifluoromethyl-3-(meth)acrylate, and (1-methyl-1-oxetanyl)-4-trifluormethyl-2-(meth)acrylate, etc. may be mentioned. Among these as well, (meth)acrylic acid, maleic anhydride, glycidyl (meth)acrylate, 6,7-epoxyheptyl methacrylate, etc. are preferable.
The acrylic resin (A2) may also be a copolymer of at least one compound which is selected from unsaturated carboxylic acids, unsaturated carboxylic anhydrides, and epoxy group-containing unsaturated compounds, and other acrylate-based monomers or copolymerizable monomers other than acrylates.
As other acrylate-based monomers, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, and other alkyl (meth)acrylates; hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and other phenoxyalkyl (meth)acrylates; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, and other alkoxyalkyl (meth)acrylates; polyethylene glycol mono(meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonyl phenoxypolyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and other polyalkylene glycol (meth)acrylates; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, tricyclo[5.2.1.02,6]decan-8-yl (meth)acrylate, tricyclo[5.2.1.02,6]-3-decen-8-yl (meth)acrylate, tricyclo[5.2.1.02,6]-3-decen-9-yl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, and other cycloalkyl (meth)acrylates; phenyl (meth)acrylate, naphthyl (meth)acrylate, biphenyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 5-tetrahydrofurfuryl oxycarbonylpentyl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-[tricyclo[5.2.1.02,6]decan-8-yloxy]ethyl (meth)acrylate, 2-[tricyclo[5.2.1.02,6]-3-decen-8-yloxy]ethyl (meth)acrylate, 2-[tricyclo[5.2.1.02,6]-3-decen-9-yloxy]ethyl (meth)acrylate, γ-butyrolactone (meth)acrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(2,6-diethylphenyl)maleimide, N-(4-acetylphenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(4-acetoxyphenyl)maleimide, N-(4-dimethylamino-3,5-dinitrophenyl)maleimide, N-(1-anilinonaphthyl-4)maleimide, N-[4-(2-benzooxazolyl)phenyl]maleimide, N-(9-acridinyl)maleimide, etc. may be mentioned. Among these as well, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, tricyclo[5.2.1.02,6]decan-8-yl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are preferable.
The copolymerizable monomer other than acrylate is not particularly limited so long as a compound which can copolymerize with the above carboxylic acid which has an acryl group, carboxylic anhydride which has an acryl group, epoxy group-containing acrylate compound, but, for example, vinylbenzylmethyl ether, vinylglycidyl ether, styrene, α-methylstyrene, vinyltoluene, indene, vinylnaphthalene, vinylbiphenyl, chlorostyrene, bromostyrene, chloromethylstyrene, p-tert-butoxystyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-acetoxystyrene, p-carboxystyrene, 4-hydroxyphenylvinylketone, acrylonitrile, methacrylonitrile, (meth)acrylamide, 1,2-epoxy-4-vinylcyclohexane, isobutene, norbornene, butadiene, isoprene, and other radical polymerizable compounds may be mentioned. These compounds may respectively be used alone or may be used as two types or more combined. The polymerization method of the above monomer may be an ordinary method. For example, the suspension polymerization method, the emulsion polymerization method, the solution polymerization method, etc. may be employed.
The Cardo resin (A3) used in one embodiment of the present invention is a resin which has a Cardo structure, that is, a skeletal structure with two cyclic structures bonded to a quaternary carbon atom which forms a cyclic structure. A general form of a Cardo structure is a structure in which benzene rings bond to a fluorene ring.
As specific examples of a skeletal structure where two cyclic structures are bonded to a quaternary carbon atom forming a cyclic structure, a fluorene skeleton, bisphenol fluorene skeleton, bisaminophenyl fluorene skeleton, fluorine skeleton having an epoxy group, fluorene skeleton having an acryl group, etc. may be mentioned.
The Cardo resin (A3) used in one embodiment of the present invention is formed by polymerization by reacting functional groups which bond to skeletons having Cardo structure each other. The Cardo resin (A3) has a structure where the main chain and bulky side chains are connected by a single element (Cardo structure) and has a cyclic structure in the direction substantially vertical to the main chain.
As one example of the Cardo structure, an example of a Cardo structure having an epoxyglycidyl ether structure is shown in the following formula (3).
(In the above formula (3), “n” is an integer of 0 to 10.)
The monomer which has a Cardo structure is, for example, a bis(glycidyloxyphenyl)fluorene-type epoxy resin; a condensate of a bisphenolfluorene-type epoxy resin and acrylic acid; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, or other Cardo structure-containing bisphenols; 9,9-bis(cyanomethyl)fluorene or other 9,9-bis(cyanoalkyl)fluorenes; 9,9-bis(3-aminopropyl)fluorene or other 9,9-bis(aminoalkyl)fluorenes; etc. may be mentioned.
The Cardo resin (A3) is a polymer which is obtained by polymerization of a monomer which has a Cardo structure, but may also be a copolymer with another copolymerizable monomer.
The polymerization method of the above monomers may be an ordinary method. For example, the ring-opening polymerization method or addition polymerization method etc. may be employed.
The polysiloxane (A4) used in one embodiment of the present invention is not particularly limited, but preferably a polymer which is obtained by mixing and reacting one or more types of organosilane represented by the following formula (4) may be mentioned.
(R4)m—Si—(OR5)4-m (4)
In the above formula (4), R4 is a hydrogen atom, C1 to C10 alkyl group, C2 to C10 alkenyl group, or C6 to C15 aryl group. The plurality of R4 may be the same or different. Note that, these alkyl groups, alkenyl groups, and aryl groups may all have substituents. Further, they may be nonsubstituted groups which do not have substituents and may be selected in accordance with the properties of the composition. As specific examples of the alkyl group, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2-(3,4-epoxy cyclohexyl)ethyl group, 3-aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatepropyl group may be mentioned. As specific examples of the alkenyl group, a vinyl group, 3-acryloxypropyl group, and 3-methacryloxypropyl group may be mentioned. As specific example of the aryl group, a phenyl group, tolyl group, p-hydroxyphenyl group, 1-(p-hydroxyphenyl)ethyl group, 2-(p-hydroxyphenyl)ethyl group, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group, and naphthyl group may be mentioned.
Further, in the above formula (4), R5 is a hydrogen atom, C1 to C6 alkyl group, C1 to C6 acyl group, or C6 to C15 aryl group, where the plurality of R5 may be the same or different. Note that, these alkyl groups and acyl groups may all have substituents. Further, they may be nonsubstituted groups which do not have substituents and may be selected in accordance with the properties of the composition. As specific examples of the alkyl group, a methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group may be mentioned. As a specific example of the acyl group, an acetyl group may be mentioned. As a specific example of an aryl group, a phenyl group may be mentioned.
Furthermore, in the above formula (4), “m” is an integer of 0 to 3. When m=0, the compound becomes tetrafunctional silane, when m=1, it becomes trifunctional silane, when m=2, it becomes bifunctional silane, and when m=3, it becomes monofunctional silane.
As specific examples of an organosilane represented by the above formula (4), tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, or other tetrafunctional silanes; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluorcnethyltrimethoxysilane, trifluoranethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or other trifunctional silanes; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, or other bifunctional silanes; trimethylmethoxysilane, tri-n-butylethoxysilane, or other monofunctional silanes; may be mentioned.
Among these organosilanes, from the viewpoint of the crack resistance or hardness of the obtained resin film, trifunctional silanes are preferably used. These organosilanes may be used alone or may be used as two types or more combined.
The polysiloxane (A4) used in one embodiment of the present invention is obtained by the hydrolysis or partial condensation of the above-mentioned organosilanes. For the hydrolysis and partial condensation, general methods can be used. For example, a solvent, water, and according to need a catalyst are added to the mixture and heated and stirred. During stirring, in accordance with need, distillation may be used to distill off the hydrolysis byproducts (methanol or other alcohol) or condensation byproduct (water).
The polyimide (A5) used in one embodiment of the present invention can be obtained by heat treating a polyimide precursor obtained by reacting a tetracarboxylic anhydride and diamine. As the precursor for obtaining the polyimide, a polyamic acid, polyamic acid ester, polyisoimide, polyamic acid sulfonamide, etc. may be mentioned.
The polyimide (A5) used in one embodiment of the present invention is synthesized by a known method. That is, it is synthesized by a known method such as selectively combining tetracarboxylic dianhydride and a diamine and reacting these in N-methyl-2-pyrrolidone, N,N-dimethylacetoamide, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, γ-butyrolactone, cyclopentanone, or other polar solvent.
When excessively using a diamine for polymerization, it is possible to make a carboxylic anhydride react with the end amino group of the produced polyimide (A5) so as to protect the end amino group. Further, when excessively using tetracarboxylic anhydride for polymerization, it is possible to make an amine compound react with the end acid anhydride group of the produced polyimide (A5) so as to protect the end acid anhydride group.
As examples of such carboxylic anhydrides, phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic acid anhydride, etc. may be mentioned, while as examples of amine compounds, aniline, 2-hydroxyaniline, 3-hydroxyaniline, 4-hydroxyaniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, etc. may be mentioned.
The binder resin (A) used in the present invention has a weight average molecular weight (Mw) of usually 1,000 to 1,000,000, preferably 1,500 to 100,000, more preferably 2,000 to 10,000 in range.
Further, the binder resin (A) has a molecular weight distribution of a weight average molecular weight/number average molecular weight (Mw/Mn) ratio of usually 4 or less, preferably 3 or less, more preferably 2.5 or less.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the binder resin (A) are values which are found by gel permeation chromatography (GPC) using tetrahydrofuran and other solvents as eluents and as values converted to polystyrene.
(Alkoxysilyl Group-Containing (Meth)Acrylate Compound (B))
The alkoxysilyl group-containing (meth)acrylate compound (B) used in one embodiment of the present invention is a (meth)acrylic acid (acrylic acid and/or methacrylic acid (same below)) ester is a (meth)acrylic acid (acrylic acid and/or methacrylic acid (same below)) ester which has an alkoxysilyl group. In one embodiment of the present invention, by jointly using such an alkoxysilyl group-containing (meth)acrylate compound (B), later explained tetrafunctional or higher functional (meth)acrylate compound (C), and photopolymerization initiator (D) and making the total ratio of content of the alkoxysilyl group-containing (meth)acrylate compound (B) and the tetrafunctional or higher functional (meth)acrylate compound (C) a specific range, the resin film which is obtained using the resin composition of one embodiment of the present invention can be made excellent in adhesion to a substrate.
As specific examples of the alkoxysilyl group-containing (meth)acrylate compound (B), 2-acryloxyethyl trimethoxysilane, 2-acryloxyethyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropylmethyl dimethoxysilane, 3-acryloxypropyl triethoxysilane, 4-acryloxybutyl trimethoxysilane, 4-acryloxybutyl triethoxysilane, 2-methacryloxyethyl trimethoxysilane, 2-methacryloxyethyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropylmethyl dimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxymethyl diethoxysilane, 4-methacryloxybutyl trimethoxysilane, 4-methacryloxybutyl triethoxysilane, etc. may be mentioned. Among these as well, an alkoxysilyl group-containing acrylate compound is preferable, 2-acryloxyethyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropylmethyl dimethoxysilane, and 4-acryloxybutyl trimethoxysilane are more preferable, and 3-acryloxypropyl trimethoxysilane is particularly preferable. These may be used as single type alone or as two types or more combined.
In the resin composition of one embodiment of the present invention, the content of the alkoxysilyl group-containing (meth)acrylate compound (B) is, as a total with the later explained tetrafunctional or higher functional (meth)acrylate compound (C), preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 0.8 to 8 parts by weight, furthermore preferably 1.1 to 6 parts by weight, most preferably 3 to 5 parts by weight. By making the total content of these the above range, the adhesion to a substrate can be further improved.
Note that, in the resin cc position of one embodiment of the present invention, the content of the alkoxysilyl group-containing (meth)acrylate compound (B) may be made an amount whereby the content of the total with the tetrafunctional or higher functional (meth)acrylate compound (C) becomes the above range, but the content of the alkoxysilyl group-containing (meth)acrylate compound (B) alone is preferably 0.25 to 4 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 0.5 to 4 parts by weight, furthermore preferably 0.5 to 2.5 parts by weight, particularly preferably 0.8 to 2 parts by weight. By making the content of the alkoxysilyl group-containing (meth)acrylate compound (B) alone with respect to 100 parts by weight of the binder resin (A) the above range, the adhesion to a substrate can be further improved.
(Tetrafunctional or Higher Functional (Meth)acrylate Compound (C))
The tetrafunctional or higher functional (meth)acrylate compound (C) used in one embodiment of the present invention is a (meth)acrylic acid ester which has four or more (meth)acryloyl groups.
As specific examples of the tetrafunctional or higher functional (meth)acrylate compound (C), dipentaerythritol hexaacrylate (hexafunctional) (for example, product name “DPHA”, made by Daicel Cytec, or product name “Light Acrylate DPE-6A”, made by Kyoei Kagaku Kogyo, or product name “A-DPH”, made by Shin-Nakamura Chemical), pentaerythritol ethoxy tetracrylate (tetrafunctional) (for example, product name “EBECRYL40”, made by Daicel Cytec), ditrimethylolpropane tetracrylate (tetrafunctional) (for example, product name “AD-TMP”, made by Shin-Nakamura Chemical), ethoxylated pentaerythritol tetracrylate (tetrafunctional) (for example, product name “ATM-35E”, made by Shin-Nakamura Chemical), pentaerythritol tetracrylate (tetrafunctional) (for example, product name “A-TMMT”, made by Shin-Nakamura Chemical), dipentaerythritol polyacrylate (for example, product name “A-9550”, made by Shin-Nakamura Chemical), pentaerythritol tri/tetracrylate (trifunctional and tetrafunctional mixture) (for example, product name “Aronix M-303 Tri 40-60%”, or product name “Aronix M-305 Tri 55-63%”, or product name “Aronix M-306 Tri 65-70%”, all made by Toagosei), dipentaerythritol penta/hexaacrylate (pentafunctional and hexafunctional mixture) (for example, product name “Aronix M-402 Penta 30-40%”, or product name “Aronix M-406 Penta 25-35%”, all made by Toagosei), ditrimethylolpropane tetracrylate (tetrafunctional) (for example, product name “Aronix M-408”, made by Toagosei), polybasic acid-modified acrylic oligomer (for example, product name “Aronix M-510”, made by Toagosei), etc. may be mentioned. These may be used as single type alone or as two types or more combined. As the tetrafunctional or higher functional (meth)acrylate compound (C), from the viewpoint of improving more the adhesion to a substrate, use of tetrafunctional or higher functional (meth)acrylate compounds with different numbers of functional groups in combination is preferable (including the case of use of a mixture of (meth)acrylate compounds with different numbers of functional groups), while use of a pentafunctional (meth)acrylate compound and a hexafunctional (meth)acrylate compound in combination is preferable.
In the resin composition of one embodiment of the present invention, the content of the tetrafunctional or higher functional (meth)acrylate compound (C) may be made an amount whereby the total content with the above-mentioned alkoxysilyl group-containing (meth)acrylate compound (B) becomes the above range, but the content of the tetrafunctional or higher functional (meth)acrylate compound (C) alone is preferably 0.25 to 7 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 0.5 to 7 parts by weight, furthermore preferably 0.5 to 5 parts by weight, particularly preferably 1 to 4 parts by weight, most preferably 2 to 4 parts by weight. By making the content of the tetrafunctional or higher functional (meth)acrylate compound (C) with respect to 100 parts by weight of the binder resin (A) the above range, the adhesion to a substrate can be further improved.
(Photopolymerization Initiator (D))
The photopolymerization initiator (D) used in one embodiment of the present invention is not particularly limited so long as a compound which causes a chemical reaction by light, but a radical generating type photopolymerization initiator which generates radicals due to light and thereby causes a chemical reaction is preferable. In particular, among radical generating type photopolymerization initiators, a compound which has a sensitivity with respect to 400 nm or less wavelength light and generates radicals and which causes a chemical reaction when being irradiated by 400 nm or less wavelength light, specifically ultraviolet light or electron beams and other radiation, is preferable.
As specific examples of such a radical generating type photopolymerization initiator, benzophenone, methyl o-benzoyl benzoate, 4,4-bis(dimethylamine) benzophenone, 4,4-bis(diethylamine)benzophenone, α-amino-acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenylketone, dibenzylketone, fluorene, 2,2-diethoxyaoetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroaoetophenone, thioxantone, 2-methylthioxantone, 2-chlorothioxantone, 2-isopropylthioxantone, diethylthioxantone, benzyldimethylketal, benzylmethoxyethylacetal, benzoinmethyl ether, benzoinbutyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylbutylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methylene anthrone, 4-acidabenzylacetophenone, 2,6-bis(p-azidebenzylidene)cyclohexane, 2,6-bis(p-azidebenzylidene)-4-methylcyclohexanone, 2-phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1-phenyl-propanedion-2-(o-ethoxycarbonyl)oxime, 1,3-diphenyl-propanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxy-propanetrione-2-(o-benzoyl)oxime, Michler's ketone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacrylidone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, N,N-octamethylenebisacridine, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (product name “Irgacure 379EG”, made by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (product name “IRGACURE 184”, made by BASF), 2-hydroxy-1-(4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl)-2-methyl propan-1-one (product name “IRGACURE 127”, made by BASF), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name “IRGACURE 907”, made by BASF), 1,7-bis(9-acridyl)-heptane (made by ADEKA, N1717), 1,2-octanedion, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)](made by BASF, OXE-01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (made by BASF, OXE-02), carbon tetrachloride, tribromophenylsulfone, benzoin peroxide, eosin, methylene blue, and other photoreducing dyes and ascorbic acid or triethanolamine and other reducing agents in combination etc. may be mentioned. These may be used as single type alone or as two types or more combined.
In the resin composition of one embodiment of the present invention, the content of the photopolymerization initiator (D) is preferably 0.3 to 8 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 0.5 to 6 parts by weight, furthermore preferably 0.7 to 4 parts by weight. By making the content of the photopolymerization initiator (D) this range, the adhesion to a substrate can be made more excellent.
(Epoxy Group-Containing (Meth)acrylate Compound (E))
The resin composition of one embodiment of the present invention preferably contains, in addition to the above-mentioned binder resin (A), alkoxysilyl group-containing (meth)acrylate compound (B), tetrafunctional or higher functional (meth)acrylate compound (C), and photopolymerization initiator (D), an epoxy group-containing (meth)acrylate compound (E). By further containing an epoxy group-containing (meth)acrylate compound (E), the obtained resin film can be further raised in adhesion to a substrate.
As specific examples of the epoxy group-containing (meth)acrylate compound (E), glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethylacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate (for example, product name “Cyclomer M100”, made by Daicel), 4-glycidyloxy-3,5-dimethylbenzyl acrylate, 4-glycidyloxy-3,5-dimethylbenzyl methacrylate, etc. may be mentioned. These may be used as single type alone or as two types or more combined. Among these as well, epoxy group-containing (meth)acrylate compounds which have alicyclic structures are preferable, while 3,4-epoxy cyclohexylmethyl methacrylate is particularly preferable. By using, as the epoxy group-containing (meth)acrylate compound, an epoxy group-containing (meth)acrylate compound which has an alicyclic structure, the adhesion to a substrate can be further improved.
In the resin composition of one embodiment of the present invention, the content of the epoxy group-containing (meth)acrylate compound (E) is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 0.8 to 3 parts by weight. By making the content of the epoxy group-containing (meth)acrylate compound (E) this range, the effect of addition, that is, the effect of improvement of the adhesion to a substrate, can made more remarkable.
(Cross-Linking Agent (F))
Further, the resin composition of one embodiment of the present invention preferably further contains, in addition to the above-mentioned ingredients, a cross-linking agent (F). As the cross-linking agent (F), one which forms a cross-linked structure between cross-linking agent molecules due to heating or one which reacts with the binder resin (A) to form a cross-linked structure between resin molecules may be mentioned, specifically, a compound which has two or more reactive groups may be mentioned. As such a reactive group, for example, an amino group, carboxy group, hydroxyl group, epoxy group, or isocyanate group may be mentioned. More preferably, it is an amino group, epoxy group, or isocyanate group. An amino group or epoxy group is particularly preferable.
The molecular weight of the cross-linking agent (F) is not particularly limited, but is usually 100 to 100,000, preferably 300 to 50,000, more preferably 500 to 10,000. The cross-linking agent (F) may be used as single type alone or as two types or more combined.
As specific examples of the cross-linking agent (E), hexamethylenediamine and other aliphatic polyamines; 4,4′-diaminodiphenyl ether, diaminodiphenyl sulfone, and other aromatic polyamines; 2,6-bis(4′-azidobenzal)cyclohexanone, 4,4′-diazidodiphenyl sulfone, and other azides; nylon, polyhexamethylenediamine terephthalamide, polyhexamethyleneisophthalamide, and other polyamides; N,N,N′,N′,N″,N″-(hexaalkoxyalkyl) melamine, and other melamines which may have a methylol group, imino group, etc. (product name “Cymel 303, Cymel 325, Cymel 370, Cymel 232, Cymel 235, Cymel 272, Cymel 212, Mycoat 506” (above, made by Cytec Industries) and other Cymel series and Mycoat series products); N,N′,N″,N″′-(tetraalkoxyalkyl)glycoluryl, and other glycolurils which may have a methylol group, imino group etc. (product name “Cymel 1170” (above, made by Cytec Industries) and other Cymel series products); ethylene glycol di(meth)acrylate and other acrylate compounds; hexamethylene diisocyanate-based polyisocyanate, isophorone diisocyanate-based polyisocyanate, tolylene diisocyanate-based polyisocyanate, hydrated diphenylmethane diisocyanate, and other isocyanate-based compounds; 1,4-di-(hydroxymethyl)cyclohexane, 1,4-di-(hydroxymethyl) norbornane; 1,3,4-trihydroxycyclohexane; bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, polyphenol-type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, and other epoxy compounds; may be mentioned.
Further, as specific examples of the epoxy compound, a trifunctional epoxy compound which has a dicyclopentadiene structure (product name “XD-1000”, made by Nippon Kayaku), a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl) 1-butanol (pentadecafunctional alicyclic epoxy resin having a cyclohexane structure and end epoxy groups, product name “EHPE3150”, made by Daicel Chemical Industry), epoxylated 3-cyclohexene-1,2-dicarboxylic acid bis(3-cyclohexenylmethyl) modified e-caprolactone (aliphatic cyclic trifunctional epoxy resin, product name “Epolide GT301”, made by Daicel Chemical Industry), epoxylated butanetetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified e-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, product name “Epolide GT401”, made by Daicel Chemical Industry), and other epoxy compounds having alicyclic structures;
aromatic amine-type polyfunctional epoxy compound (product name “H-434”, made by Tohto Chemical Industry), cresol novolac-type polyfunctional epoxy compound (product name “EOCN-1020”, made by Nippon Kayaku), phenol novolac-type polyfunctional epoxy compound (Epicoat 152, 154, made by Japan Epoxy Resin), polyfunctional epoxy compound having a naphthalene structure (product name EXA-4700, made by DIC), chain alkylpolyfunctional epoxy compound (product name “SR-TMP”, made by Sakamoto Yakuhin Kogyo Co., Ltd.), polyfunctional epoxy polybutadiene (product name “Epolide PB3600”, made by Daicel Chemical Industry), glycidyl polyether compound of glycerin (product name “SR-GLG”, made by Sakamoto Yakuhin Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound (product name “SR-DGE”, made by Sakamoto Yakuhin Kogyo Co., Ltd.), polyglycerin polyglycidyl ether compound (product name “SR-4GL”, made by Sakamoto Yakuhin Kogyo Co., Ltd.), and other epoxy compounds not having an alicyclic structure; may be mentioned.
In the resin composition of one embodiment of the present invention, the content of the cross-linking agent (F) is not particularly limited and may be freely set considering the extent of heat resistance which is sought to the resin film which is obtained by using the resin composition of one embodiment of the present invention, but is preferably 3 to 70 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 4 to 45 parts by weight, furthermore preferably 5 to 25 parts by weight. Whether the cross-linking agent (F) is too great or too small, the heat resistance tends to fall.
(Other Compounding Agents)
The resin composition of one embodiment of the present invention may further contain a solvent. The solvent is not particularly limited, but one known as a solvent of a resin composition, for example, acetone, methylethylketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, or other straight chain ketones; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, or other alcohols; ethyleneglycol dimethyl ether, ethyleneglycol diethyl ether, dioxane, or other ethers; ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, or other alcohol ethers; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, or other esters; cellosolve acetate, methylcellosolve acetate, ethylcellosolve acetate, propylcellosolve acetate, butylcellosolve acetate, or other cellosolve esters; propyleneglycol, propyleneglycol monaethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, or other propylene glycols; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, or other diethylene glycols; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-caprylolactone, or other saturated γ-lactones; trichloroethylene or other halogenated hydrocarbons; toluene, xylene, or other aromatic hydrocarbons; dimethylacetoamide, dimethylformamide, N-methylacetoamide, or other polar solvents; etc. may be mentioned. These solvents may be used alone or as two types or more combined. The content of the solvent is preferably 10 to 10000 parts by weight with respect to 100 parts by weight of the binder resin (A), more preferably 50 to 5000 parts by weight, furthermore preferably 100 to 1000 parts by weight in range. Note that, when the resin composition is made to include a solvent, the solvent is normally removed after forming the resin film.
Further, the resin composition of one embodiment of the present invention may be one which contains, in addition to the above ingredients, a radiation-sensitive compound. A radiation-sensitive compound is a compound which can cause a chemical reaction by irradiation by ultraviolet rays or an electron beam or other radiation. In one embodiment of the present invention, the radiation-sensitive compound is preferably one which can control the alkali solubility of a resin film which is comprised of the resin composition, particularly a photoacid generator is preferable.
As such a radiation-sensitive compound, for example, an acetophenone compound, triaryl sulfonium salt, quinone diazide compound, and other azide compounds etc. may be mentioned, but it is preferably an azide compound, particularly preferably a quinone diazide compound.
As the quinone diazide compound, for example, an ester compound of a quinone diazide sulfonic acid halide and a compound which has a phenolic hydroxyl group can be used. As specific examples of the quinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, etc. may be mentioned. As typical examples of a compound which has a phenolic hydroxyl group, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, etc. may be mentioned. As other compounds which have a phenolic hydroxyl group, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, oligomers of novolac resins, oligomers obtained by copolymerization of a compound which has one or more phenolic hydroxyl groups and dicyclopentadiene, etc. may be mentioned.
Among these as well, a condensate of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and a compound which has a phenolic hydroxyl group is preferable, while a condensate of 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane (1 mole) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (1.9 mole) is more preferable.
Further, as the photoacid generator, in addition to the quinone diazide compound, an osmium salt, halogenated organic compound, α,α′-bis(sulfonyl)diazomethane-based compound, α-carbonyl-α′-sulfonyldiazomethane-based compound, sulfone compound, organic acid ester compound, organic acid amide compound, organic acid imide compound, or other known one can be used. These radiation-sensitive compounds may be used as single type alone or as two types or more combined.
Further, the resin composition of one embodiment of the present invention may contain, to an extent where the effects of one embodiment of the present invention are not inhibited, as desired a surfactant, acidic compound, coupling agent or its derivative, sensitizer, latent acid generator, antioxidant, photostabilizer, defoamer, pigment, dye, filler, and other compounding agents etc.
The surfactant is used to prevent striation, improve the development property, and for other purposes. As specific examples of the surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octylphenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene aryl ethers; polyoxyethylene dilaurate, polyoxyethylene distearate, and other polyoxyethylene dialkyl esters, and other nonion-based surfactants; fluorine-based surfactants; silicone-based surfactants; methacrylic acid copolymer-based surfactants; acrylic acid copolymer-based surfactants; etc. may be mentioned.
The coupling agent or its derivative has the effect of further raising the adhesion of a resin film comprised of the resin composition and the layers, including the semiconductor layer, which forms the semiconductor device substrate. As the coupling agent or its derivative, a compound which has one atom selected from a silicon atom, titanium atom, aluminum atom, and zirconium atom and has a hydrocarbyloxy group or hydroxyl group which bonds with that atom can be used.
As the coupling agent or its derivative, for example, tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, alkoxysilanes, silicon atom-containing compounds, titanium atom-containing compounds, zirconium atom-containing compounds, etc. may be mentioned, but among these, trialkoxysilanes are preferable. As specific examples of the trialkoxysilanes, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. may be mentioned.
As specific examples of the sensitizer, 2H-pyrido-(3,2-b)-1,4-oxazin-3 (4H)-ones, 10H-pyrido (3,2-b)-1,4-benzothiadines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides, etc. may be mentioned.
As antioxidants, a phenol-based antioxidant, phosphorus-based antioxidant, sulfur-based antioxidant, lactone-based antioxidant, etc. used for a usual polymer can be used. For example, as phenols, 2,6-di-t-butyl-4-methylphenol, p-methoxyphenol, styrenated phenol, n-octadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl) propionate, 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2-t-butyl-6-(3′-t-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenylacrylate, 4,4′-butylidene-bis-(3-methyl-6-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], alkylated bisphenol, etc. may be mentioned. As the phosphorus-based antioxidants, triphenyl phosphite and tris(nonylphenyl) phosphite may be mentioned, while as the sulfur-based ones, dilauryl thiodipropionate etc. may be mentioned.
As light stabilizers, benzophenone-based, salicyclic acid ester-based, benzotriazole-based, cyanoacrylate-based, metal complex-based, and other ultraviolet ray absorbers, hindered amine-based light stabilizers (HALS) and other stabilizers which trap radicals generated due to light may be used. Among these as well, a HALS is a compound which has a piperidine structure and is preferable since it causes little coloring with respect to a radiation-sensitive resin composition and is good in stability. As specific compounds, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl/tridecyl-1,2,3,4-butanetetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, etc. may be mentioned.
The method of preparation of the resin composition of one embodiment of the present invention is not particularly limited, but the ingredients forming the resin composition may be mixed by a known method.
The method of mixing is not particularly limited, but it is preferable to dissolve or disperse the components which form the resin composition in solvents and mix the solutions or dispersions. Due to this, the resin composition is obtained in the form of a solution or dispersion.
The method of dissolving or dispersing the components which form the resin composition in solvents may be an ordinary method. Specifically, this may be performed by stirring using a stirring bar and magnetic stirrer, high speed homogenizer, disperser, planetary stirrer, twin-screw stirrer, ball mill, triple roll, etc. Further, the ingredients may also be dissolved or dispersed in a solvent, then for example filtered using a filter with a pore size of 0.5 μm or so etc.
The solid content concentration of the resin composition of one embodiment of the present invention is usually 1 to 70 wt %, preferably 5 to 60 wt %, more preferably 10 to 50 wt %. If the solid content concentration is in this range, stability of dissolution, coatability, uniformity of thickness and flatness of the resin film which is formed, etc. are obtained in a high balance.
Further, in the resin composition of one embodiment of the present invention, the ratios of content of Na, Mg, Al, K, Ca, Cr, Mn, Fe, and Ni is preferably a weight ratio with respect to the total radiation-sensitive resin composition of preferably less than 500 ppb, more preferably less than 200 ppb, particularly preferably less than 100 ppb.
(Resin Film)
The resin film of one embodiment of the present invention can be obtained using the above-mentioned resin composition of one embodiment of the present invention. The resin film of one embodiment of the present invention is preferably obtained by the above-mentioned resin composition of one embodiment of the present invention being formed on the substrate.
As the substrate, for example, a printed circuit board, silicon wafer substrate, soda glass or other glass substrate, polyethylene naphthalate or other plastic substrate, etc. may be used. Among these as well, a soda glass substrate used for a display device provided with a touch panel structure or a polyethylene naphthalate substrate is preferably used.
The method of forming the resin film is not particularly limited, but for example the coating method, film lamination method, or other method can be used.
The coating method is, for example, the method of coating a resin composition, then drying by heating to remove the solvent. As the method of coating the resin composition, for example, the spray method, spin coat method, roll coat method, die coat method, doctor blade method, spin coat method, bar coat method, screen print method, and other various methods can be employed. The heating and drying conditions differ according to the type and ratio of the ingredients, but are usually 30 to 150° C., preferably 60 to 120° C. usually for 0.5 to 90 minutes, preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
The film lamination method is a method comprising coating a resin composition on a resin film, metal film or other substrate for forming B-stage film, then heating and drying it to remove the solvent to obtain the B-stage film, then laminating this B-stage film. The heating and drying conditions may be suitably selected in accordance with the types and ratios of content of the ingredients, but the heating temperature is usually 30 to 150° C. and the heating time is usually 0.5 to 90 minutes. The film lamination may be performed by using a press laminator, press, vacuum laminator, vacuum press, roll laminator, and other press bonding machines.
The thickness of the resin film is not particularly limited, but may be suitably set in accordance with the application, but when the resin film is a protective film or insulating film of, for example, a touch panel structure of a display device provided with a touch panel structure, the thickness of the resin film is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, furthermore preferably 0.5 to 30 μm.
Further, when the resin composition of one embodiment of the present invention includes a cross-linking agent (F), the resin film which is formed by the above-mentioned coating method or film lamination method can be cross-linked. This cross-linking may be performed by selecting a suitable method in accordance with the type of the cross-linking agent (F), but usually is performed by heating. The heating method, for example, may be one using a hot plate, oven, etc. The heating temperature is usually 180 to 250° C. The heating time is suitably selected in accordance with the area or thickness of the resin film, the equipment which is used, etc. For example, when using a hot plate, it is normally 5 to 60 minutes, while when using an oven, it is normally 30 to 90 minutes. The heating may be performed in accordance with need in an inert gas atmosphere. The inert gas may be one which does not contain oxygen and which does not oxidize a resin film. For example, nitrogen, argon, helium, neon, xenon, krypton, etc. may be mentioned. Among these as well, nitrogen and argon are preferable. In particular, nitrogen is preferable. In particular, inert gas with an oxygen content of 0.1 vol % or less, preferably 0.01 vol % or less, in particular nitrogen, is suitable. These inert gases may be respectively used alone or as two types or more combined.
Further, when the above-mentioned resin composition contains the radiation-sensitive compound, the resin film which is formed using the resin composition may be patterned if necessary. As the method of patterning a resin film, for example, the method of forming a resin film before patterning, irradiating active radiation at the resin film before patterning to form latent patterns, then bringing the resin film which has the latent patterns into contact with the developing solution to bring out the patterns etc. may be mentioned.
The active radiation is not particularly limited so long as able to activate radiation-sensitive compound contained in the resin composition and change the alkali solubility of the resin composition containing the radiation-sensitive compound. Specifically, ultraviolet light, g-rays or i-rays and other single wavelength ultraviolet light, KrF excimer laser light, ArF excimer laser light, and other light beams; electron beams and other particle beams; etc. may be used. As the method of selectively radiating active radiation in a pattern manner to form latent patterns, an ordinary method may be used. For example, the method of using a reduced projection exposure apparatus etc. to irradiate ultraviolet light, g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, and other light beams through a desired mask pattern or the method of using an electron beam or other particle beam for lithography etc. may be used. When using light beams as active radiation, single wavelength light or mixed wavelength light may be used. The irradiation conditions may be suitably selected in accordance with the active radiation used, but, for example, when using wavelength 200 to 450 nm light beams, the amount of irradiation is normally 10 to 1,000 mJ/cm2, preferably 50 to 500 mJ/cm2 in range and is determined in accordance with the irradiation time and illuminance. After irradiating the active radiation in this way, in accordance with need, the resin film is heat treated at 60 to 130° C. or so in temperature for 1 to 2 minutes or so.
Next, the latent patterns which are formed in the resin film before patterning are developed to bring them out. As the developing solution, normally aqueous solutions of alkali compounds may be used. As alkali compounds, for example, alkali metal salts, amines, and ammonium salts may be used. The alkaline compounds may be inorganic compounds or organic cc pounds. As specific examples of these compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, metasodium silicate, and other alkali metal salts; ammonia water; ethylamine, n-propylamine, and other primary amines; diethylamine, di-n-propylamine, and other secondary amines; triethylamine, methyldiethylamine, and other tertiary amines; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline, and other quaternary ammonium salts; dimethylethanolamine, triethanolamine, and other alcohol amines; pyrrol, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, N-methylpyrrolidone, and other cyclic amines; etc. may be mentioned. These alkali compounds may be respectively used alone or as two types or more combined.
As the aqueous medium which is used as the aqueous solution of an alkali compound, water; methanol, ethanol, and other water soluble organic solvents may be used. The alkali aqueous solution may have a surfactant etc. added in a suitable amount.
As the method for bringing the developing solution in contact with the resin film which has the latent patterns, for example, the puddle method, spray method, dipping method, and other methods may be used. The development conditions are suitably selected as normally 0 to 100° C., preferably 5 to 55° C., more preferably 10 to 30° C. and normally 30 to 180 seconds.
The resin film which is formed with the targeted patterns in this way may be rinsed by a rinse solution in accordance with need so as to remove development residue. After the rinse treatment, the remaining rinse solution is removed by compressed air or compressed nitrogen.
In one embodiment of the present invention, the resin film may be cross-linked after patterning. The cross-linking can be performed by the above-mentioned method.
(Electronic Device)
The electronic device of one embodiment of the present invention comprises the above-mentioned resin film of one embodiment of the present invention. The electronic device of one embodiment of the present invention is not particularly limited, but various electronic devices may be mentioned. Specifically, a touch pallet or flexible organic EL display or other display device provided with a touch panel structure etc. may be mentioned.
A display device provided with a touch panel structure of one example of an electronic device of one embodiment of the present invention is not particularly limited, but one comprised of a soda glass substrate or polyethylene naphthalate film on which an electrode layer comprised of a pair of ITO electrodes sandwiching an insulating film is arranged etc. may be mentioned. In this case, the above-mentioned resin film of one embodiment of the present invention can be used as an insulating film sandwiched between the electrode layers or a protective film for protecting the touch panel structure.
The resin composition of one embodiment of the present invention contains the binder resin (A), alkoxysilyl group-containing (meth)acrylate compound (B), tetrafunctional or higher functional (meth)acrylate compound (C), and photopolymerization initiator (D), where the total content of the alkoxysilyl group-containing (meth)acrylate compound (B) and the tetrafunctional or higher functional (meth)acrylate compound (C) is made the above specific range, so the resin film which is obtained using the resin composition of one embodiment of the present invention exhibits a high adhesion to a substrate and is excellent in transparency and chemical resistance. In particular, the resin film which is obtained using the resin composition of one embodiment of the present invention exhibits excellent adhesion to a soda glass substrate or polyethylene naphthalate film or other substrate which is used for a display provided with a touch panel structure. For this reason, the resin film which is obtained using the resin composition of one embodiment of the present invention can be suitably used as an insulating film or protective film of a display device provided with a touch panel structure.
Below, examples and comparative examples will be given to more specifically explain one embodiment of the present invention. In the examples, “parts” are based on weight unless otherwise indicated.
Note that, the definitions and methods of evaluation of the properties were as follows.
<Adhesion>
A soda glass substrate was coated with a resin composition by the spin coat method and prebaked using a hot plate at 110° C. for 2 minutes. Next, a 2.38 wt % tetramethylammonium hydroxide aqueous solution was used to develop the composition at 25° C. for 30 seconds, then ultrapure water was used for rinsing for 30 seconds. Next, ultraviolet light of a light intensity at 365 nm of 50 mJ/cm2 was irradiated for 300 seconds in the air. Next, an oven was used to heat the film in a nitrogen atmosphere at 230° C. for 30 minutes as post-baking to thereby obtain a resin film-coated substrate comprised of a resin film and a soda glass substrate. Note that, when forming the resin film, the speed at the time of spin coating was controlled so that the film thickness after post-baking becomes about 2.0 μm. The obtained resin film-coated substrate was stored in an environment of a temperature of 80° C. and a humidity of 85% for 24 hours, then the surface and interfacial cutting analysis method (SAICAS method) was used to test for the adhesion (peeling strength).
Specifically, the resin film part of the above obtained resin film-coated substrate was formed with a cut of 1 mm width by a cutter. A blade (made by 1.0 mm width, rake angle 20°, relief angle 10° noncrystalline diamond) was used to cut the sample at a horizontal speed of 0.2 μm/sec and a vertical speed of 0.02 μm/sec, and measured the adhesion using a measuring device constituted by a Saicas DN-20 model made by Daipla Wintes. When the blade cut to the interface between the resin film and the soda glass surface, the vertical speed was reduced to 0 μm/sec and the blade was made to move parallel to the substrate to measure the horizontal force FH [N]. Further, from the width w [m] of the blade, the peeling strength P was found from the calculation formula “P[N/m]=FH[N]/w[m]”. The peeling strength P was made the value of adhesion between the resin film and the soda glass substrate. In the examples, 50 N/m or more was deemed as “good”.
<Transparency>
A resin film-coated substrate which was prepared using an alkali-free glass substrate by a method similar to the evaluation of the above adhesion was used to measure transmittance in the range of wavelength 400 nm to 700 nm at 1 nm intervals using a spectrophotometer (made by JAS(OX, “Ultraviolet Visible Spectrophotaneter V-560 (product name)”). The average of the total transmittance in the range of 400 nm to 700 nm which was obtained was measured as the transparency. Note that the transparency was evaluated by the following criteria.
Good: total transmittance of 95% or more
Poor: total transmittance of less than 95%
<Chemical Resistance>
The resin film-coated substrate which was used for the above evaluation of adhesion was dipped in a solvent constituted by a mixture of monoethanolamine and N-methylpyrrolidone in a weight ratio of 7:3 at 65° C. for 5 minutes. The rate of change of thickness of the resin film before and after dipping was measured to evaluate the chemical resistance. Note that, the rate of change of thickness of resin film before and after dipping was calculated in accordance with “rate of change of thickness of resin film before and after dipping (%)=(I thickness of resin film after dipping-thickness of resin film before dipping l/thickness of resin film before dipping)×100”. Further, the chemical resistance was evaluated by the following criteria.
Good: rate of change of thickness of resin film before and after dipping of less than 3.0%
Fair: rate of change of thickness of resin film before and after dipping of 3.0% to less than 5.0%
Poor: rate of change of thickness of resin film before and after dipping of 5.0% or more
<Preparation of Cyclic Olefin Polymer (A-1)>
100 parts of monomer mixture comprised of 40 mol % of N-phenyl-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide (NBPI) and 60 mol % of 4-hydroxycarbonyltetracyclo[6.2.1.13,6.02,7]dodec-9-ene (TCDC), 2.0 parts of 1,5-hexadiene, 0.02 part of (1,3-dimesitylimidazolin-2-ylidene) (tricyclohexylphosphine)benzylidene ruthenium dichloride (synthesized by method described in Org. Lett., vol. 1, pp. 953, 1999), and 200 parts of diethyleneglycolethylmethyl ether were charged into a nitrogen-substituted glass pressure-resistant reactor and stirred while making them react at 80° C. for 4 hours to obtain a polymerization reaction solution.
Further, the obtained polymerization reaction solution was placed in an autoclave and stirred at 150° C. at a hydrogen pressure 4 MPa for 5 hours for a hydrogenation reaction to obtain a polymer solution which contains a cyclic olefin polymer (A-1). The polymerization conversion rate of the obtained cyclic olefin polymer (A-1) was 99.7%, the weight average molecular weight converted to polystyrene was 7,150, the number average molecular weight was 4,690, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.7%. Further, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4 wt %.
<Preparation of Acrylic Resin (A-2)>
20 parts of styrene, 25 parts of butyl methacrylate, 25 parts of 2-ethylhexylacrylate, 30 parts of methacrylate, 0.5 part of 2,2-azobisisobutyronitrile, and 300 parts of propyleneglycolmonomethyl ether acetate were stirred in a nitrogen stream while heating at 80° C. for 5 hours. The obtained resin solution was concentrated by a rotary evaporator to obtain a solid content concentration 35 wt % acrylic resin (A-2) polymer solution.
291 parts of the polymer solution of the cyclic olefin polymer (A-1) obtained in Synthesis Example 1 (as cyclic olefin polymer (A-1), 100 parts) as a binder resin (A), 1 part of 3-acryloxypropyl trimethoxysilane (product name “KBM-5103”, made by Shin-Etsu Chemical) as an alkoxysilyl group-containing (meth)acrylate compound (B), 3 parts of dipentaerythritol penta/hexaacrylate (product name “Aronix M-406 Penta 25-35%”, made by Toagosei) as a tetrafunctional or higher functional (meth)acrylate compound (C), 1 part of 2-hydroxy-1-(4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl-2-methylpropan-1-one (product name “Irgacure 127”, made by BASF) as a photopolymerization initiator (D), 15 parts of epoxylated butanetetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic tetrafunctional epoxy resin, product name “Epolide GT401”, made by Daicel Chemical Industry) as a cross-linking agent (F), 0.03 part of a silicone-based surfactant (product name “KP-341”, made by Shin-Etsu Chemical), and 270 parts of ethyleneglycolethylmethyl ether as a solvent were mixed and made to dissolve, then the mixture was filtered by a pore size 0.45 μm polytetrafluoroethylene filter to prepare a solid content concentration 20.7 wt % resin composition.
Further, the above obtained resin composition was used in accordance with the above method to evaluate the adhesion and transparency. The results are shown in Table 1.
Except for changing the amount of the 3-acryloxypropyltrimethoxysilane from 1 part to 0.5 part and changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 0.5 part, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.2 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for changing the amount of 3-acryloxypropyltrimethoxysilane from 1 part to 3 parts and changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 1 part, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 7 parts, the same procedure was followed as in Example 1 to prepare a solid content concentration 21.2 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for using, as the tetrafunctional or higher functional (meth)acrylate compound (C), instead of 3 parts of dipentaerythritol penta/hexaacrylate, 3 parts of pentaerythritol tri/tetracrylate (product name “Aronix M-303 Tri 40-60%”, made by Toagosei), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for further mixing 1 part of 3,4-epoxy cyclohexylmethyl methacrylate (product name “Cyclomer M100”, made by Daicel) as an epoxy group-containing (meth)acrylate compound (E), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.8 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for using, as the binder resin (A), instead of 291 parts of the polymer solution of the cyclic olefin polymer (A-1), 285 parts of the polymer solution of the acrylic resin (A-2) which was obtained in Synthesis Example 2 (as acrylic resin (A-2), 100 parts), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.9 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for further mixing 0.5 part of 3,4-epoxy cyclohexylmethyl methacrylate (product name “Cyclomer M100”, made by Daicel) as an epoxy group-containing (meth)acrylate compound (E), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for further mixing 4 parts of 3,4-epoxy cyclohexylmethyl methacrylate (product name “Cyclomer M100”, made by Daicel) as an epoxy group-containing (meth)acrylate compound (E), the same procedure was followed as in Example 1 to prepare a solid content concentration 21.2 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for further mixing 1 part of glycidyl methacrylate (made by Mitsubishi Gas Chemical) as an epoxy group-containing (meth)acrylate compound (E), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.8 wt % resin composition and the sane procedure was followed to evaluate it. The results are shown in Table 1.
Except for changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 14 parts, the same procedure was followed as in Example 1 to prepare a solid content concentration 22.1 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for further mixing 1 part of 3,4-epoxy cyclohexylmethyl methacrylate (product name “Cyclomer M100”, made by Daicel) as an epoxy group-containing (meth)acrylate compound (E), the same procedure was followed as in Comparative Example 1 to prepare a solid content concentration 22.3 wt % resin composition and the sane procedure was followed to evaluate it. The results are shown in Table 1.
Except for changing the amount of 3-acryloxypropyltrimethoxysilane from 1 part to 5 parts and changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 9 parts, the same procedure was followed as in Example 1 to prepare a solid content concentration 22.0 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for changing the amount of 3-acryloxypropyltrimethoxysilane from 1 part to 0.2 part and changing the amount of dipentaerythritol penta/hexaacrylate from 3 parts to 0.2 part, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.2 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for not mixing dipentaerythritol penta/hexaacrylate, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.2 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for not mixing 3-acryloxypropyltrimethoxysilane, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.5 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for using, instead of 3 parts of dipentaerythritol penta/hexaacrylate, 3 parts of trimethylolpropane triacrylate (product name “Aronix M-309”, made by Toagosei), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for using, instead of 3 parts of dipentaerythritol penta/hexaacrylate, 3 parts of ethylene glycol dimethacrylate (product name “NK Ester 1G”, made by Shin-Nakamura Chemical), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for using, instead of 3 parts of dipentaerythritol penta/hexaacrylate, 3 parts of benzylacrylate (product name “Fancryl FA-BZA”, made by Hitachi Chemical), the same procedure was followed as in Example 1 to prepare a solid content concentration 20.7 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
Except for not mixing 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, the same procedure was followed as in Example 1 to prepare a solid content concentration 20.5 wt % resin composition and the same procedure was followed to evaluate it. The results are shown in Table 1.
As shown in Table 1, a resin film which is obtained using a resin composition which contains a binder resin (A), alkoxysilyl group-containing (meth)acrylate compound (B), tetrafunctional or higher functional (meth)acrylate compound (C), and photopolymerization initiator (D), where a total content of the alkoxysilyl group-containing (meth)acrylate compound (B) and the tetrafunctional or higher (meth)acrylate compound (C) with respect to 100 parts by weight of the binder resin (A) is made 0.5 to 10 parts by weight, was high in adhesion to a substrate and excellent in transparency and chemical resistance (Examples 1 to 9). Among these as well, Examples 6, 8, and 9 further containing the epoxy group-containing (meth)acrylate compound (E) are excellent in adhesion to a substrate and are particularly excellent in results.
On the other hand, when making the total content of the alkoxysilyl group-containing (meth)acrylate compound (B) constituted by 3-acryloxypropyl trimethoxysilane and the tetrafunctional or higher functional (meth)acrylate compound (C) constituted by dipentaerythritol penta/hexaacrylate less than 0.5 part by weight or over 10 parts by weight, the obtained resin film became inferior in adhesion to a substrate (Comparative Examples 1 to 4).
Further, when not mixing the alkoxysilyl group-containing (meth)acrylate compound (B) constituted by 3-acryloxypropyltrimethoxysilane, the tetrafunctional or higher functional (meth)acrylate compound (C) constituted by dipentaerythritol penta/hexaacrylate, or the photopolymerization initiator (D) constituted by 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, the obtained resin film became inferior in adhesion to a substrate (Comparative Examples 5 to 10).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-175463 | Aug 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/072111 | 8/25/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/029931 | 3/5/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20120156448 | Sunaga et al. | Jun 2012 | A1 |
| 20120175790 | Han | Jul 2012 | A1 |
| 20130237629 | Doi | Sep 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 103210008 | Jul 2013 | CN |
| 2001-354896 | Dec 2001 | JP |
| 2010-31162 | Feb 2010 | JP |
| 2012-48185 | Mar 2012 | JP |
| 2012-211988 | Nov 2012 | JP |
| 2011024421 | Mar 2011 | WO |
| 2012-070382 | May 2012 | WO |
| Entry |
|---|
| International Search Report dated Nov. 11, 2014, issued in counterpart Application No. PCT/JP2014/072111 (2 pages). |
| Number | Date | Country | |
|---|---|---|---|
| 20160200914 A1 | Jul 2016 | US |
