JP6095964B2 - Photosensitive composition and cured product - Google Patents

Description

  The present invention relates to a photosensitive composition that forms a transparent cured product by light irradiation and a cured product obtained by curing the photosensitive composition.

  Demand for flat panel displays such as liquid crystal displays and organic EL displays continues to be strong. Materials used for flat panel displays include adhesion, surface hardness, transparency, light resistance, weather resistance, and heat resistance. There are various requirements such as flatness and surface hardness. In particular, in terms of adhesion, a material that can be applied to various substrates is required.

As a material used for these flat panel displays, polymerization using only a normal photo radical initiator is inhibited by curing due to oxygen, the curability near the surface is poor, and the hardness and scratch resistance are not sufficient. In order to solve this problem, it has been proposed to use specific inorganic particles (see, for example, Patent Document 1).
However, the invention described in Patent Document 1 uses inorganic particles having a specific structure in combination, and is improved in terms of satisfying hardness and scratch resistance, but the adhesion to the substrate becomes poor, And when obtaining hardened | cured materials, such as a transparent coating film, there exists a problem that transparency cannot be hold | maintained.

  Therefore, in the adhesiveness, since the dispersion | variation in adhesiveness by a base material is large and the compatible base material is restricted, development of the resin system which is excellent in the adhesiveness to various base materials is calculated | required strongly.

JP 2011-076002 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is excellent in adhesion to various substrates, hardness, scratch resistance, heat resistance, and a transparent cured product (coating film etc. Is to provide a photosensitive composition.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, this invention is a photosensitive composition containing the following (1)-(3), Comprising: All of a coloring agent, a metal oxide powder, and a metal powder are contained, and polymeric substance ( D) The photosensitive composition characterized in that the total content of the monofunctional radically polymerizable substance (D1) and / or the bifunctional radically polymerizable substance (D2) in 100% by weight is 10 to 70% by weight. And a cured product obtained by curing the photosensitive composition by irradiation with actinic rays.
(1) Photoradical initiator (A)
(2) A sulfonium salt derivative (B) that generates an acid by actinic rays and / or an iodonium salt derivative (C) that generates an acid by actinic rays
(3) Polymerizable substance (D)

  By using the photosensitive composition of the present invention, it is possible to produce a cured product that is excellent in adhesion to various substrates, hardness, scratch resistance, and heat resistance.

The photosensitive composition of the present invention contains the following (1) to (3);
(1) Photoradical initiator (A)
(2) A sulfonium salt derivative (B) that generates an acid by actinic rays and / or an iodonium salt derivative (C) that generates an acid by actinic rays
(3) Polymerizable substance (D)

  Below, (A)-(D) which is an essential structural component of the photosensitive composition of this invention is demonstrated in order.

In the present invention, the photoradical initiator (A) means a compound that generates radicals by actinic rays, and examples thereof include acylphosphine oxide derivative polymerization initiators (A1) and α-aminoacetophenone derivative polymerization initiators (A2). ), Benzyl ketal derivative polymerization initiator (A3), α-hydroxyacetophenone derivative polymerization initiator (A4), benzoin derivative polymerization initiator (A5), oxime ester derivative polymerization initiator (A6) and titanocene derivative It is a polymerization initiator (A7).
(A) may be used independently and may use 2 or more types together.

  As the acylphosphine oxide derivative polymerization initiator (A1), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF (LUCIRIN TPO)] and bis (2,4,6-trimethylbenzoyl) -phenyl And phosphine oxide [manufactured by BASF (IRGACURE 819)].

  As the α-aminoacetophenone derivative-based polymerization initiator (A2), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF (IRGACURE 907)], 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF (IRGACURE 379)] and the like.

  Examples of the benzyl ketal derivative polymerization initiator (A3) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (A4), 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1- ON [BASF (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [BASF (IRGACURE 2959)] And 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF (IRGACURE 127)] Can be mentioned.

  Examples of the benzoin derivative polymerization initiator (A5) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (A6), 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF (IRGACURE OXE 01)] and ethanone -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF (IRGACURE OXE 02)] and the like.

  As titanocene derivative polymerization initiator (A7), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [manufactured by BASF (IRGACURE 784)] and the like.

  The content of the photo radical initiator (A) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight with respect to 100% by weight of the polymerizable substance (D) from the viewpoint of photocurability. More preferably, it is 0.1 to 20% by weight.

  Examples of the sulfonium salt derivative (B) that generates an acid by actinic rays in the present invention include compounds represented by the following general formula (1) or the following general formula (2).

In General Formula (1) or (2), A ¹ is a divalent or trivalent group represented by any of the following General Formulas (3) to (10), and Ar ^{1 to} Ar ⁷ are each independently Having at least one benzene ring skeleton, halogen atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, carbon At least one atom or substitution selected from the group consisting of an alkylsilyl group, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group An aromatic hydrocarbon group or a heterocyclic group optionally substituted with a group, Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is a divalent group, and (X ^{1) -} and ( ^{2) -} represents an anion, a is an integer of 0 to 2, b is an integer from 1 to 3, and a + b is an integer equal the valence of ^{A 1} in 2 or 3.

R ^{1 to} R ⁷ in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R ¹ And R ² , R ⁴ and R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

As A ¹ in the general formula (2), groups represented by the general formula (5) and the general formulas (7) to (10) are preferable from the viewpoint of acid generation efficiency. The groups represented by 8) to (10) are more preferable.

Ar ^{1 to} Ar ⁷ in the general formula (1) and the general formula (2) are groups in which the compound represented by the general formula (1) or the general formula (2) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{1 to} Ar ⁷ is preferably 1 to 5, and more preferably 1 to 4.
As an example in the case of having one benzene ring skeleton, a residue obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline, coumarin, and the like can be given.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
As an example in the case of having three benzene ring skeletons, for example, one or two hydrogen atoms are removed from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
As an example in the case of having four benzene ring skeletons, for example, a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

As the atoms or substituents substituted by Ar ^{1 to} Ar ⁷ , preferred from the viewpoint of acid generation efficiency are halogen atoms, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, phenylthio groups, alkyl groups having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, They are an alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2, 4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group, m-chlorophenyl group and thioxanthyl group.

Ar ⁵ is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and 2- or 3-chloro, from the viewpoint of acid generation efficiency. A phenylene group.

Examples of the anion represented by (X ¹ ) ^— or (X ² ) ^— in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms. Dialkyldithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.) , An aliphatic or aromatic sulfoxy anion (such as trifluoromethanesulfonate anion) optionally substituted with halogen, hexafluoroantimonate anion (SbF ₆ ⁻ ), phosphorus anion [phosphorus hexafluoride anion (PF ₆ ⁻ ) And tris (perfluoroethyl) phosphorus trifluoride Anions _{(PF 3 (C 2 F 5} ) 3 -) , etc.] and borate anion (tetraphenyl borate and butyl triphenyl borate anion), and the like, from the viewpoint of acid generation efficiency, phosphorus anions, substituted by halogen Aliphatic sulfoxy anions and borate anions are preferred.

  As the sulfonium salt derivative (B) that generates an acid by actinic rays, triphenylsulfonium cation, tri-p-tolylsulfonium cation, or [p- (phenylmercapto) phenyl] diphenylsulfonium cation is preferable from the viewpoint of acid generation efficiency. Are compounds represented by the following general formulas (11) to (14), and compounds represented by the following general formulas (11) to (14) are more preferable.

(X ³ ) ⁻ to (X ⁶ ) ⁻ in the general formulas (11) to (14) represent anions, specifically, (X ¹ ) ⁻ or (X ^{2 in the} general formula (1) or (2). ) ^- it includes the same ones as exemplified as, preferable ones are also same.

  Examples of the iodonium salt derivative (C) that generates an acid by active light in the present invention include compounds represented by the following general formula (15) or the following general formula (16).

In the formula, A ² is a divalent or trivalent group represented by any one of the general formulas (3) to (10), and Ar ^{8 to} Ar ¹² each independently have at least one benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. , Aromatic group optionally substituted with at least one substituent selected from the group consisting of nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, phenoxy group and phenylthio group A hydrocarbon group or a heterocyclic group, wherein Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, Ar ¹¹ is a divalent group, and (X ⁷ ) ⁻ and (X ⁸ ) ⁻ are anions. C is 0 to Integer, d is an integer from 1 to 3, and c + d is an integer equal the valence of ^{A 2} in 2 or 3.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

As A ² in the general formula (16), a group represented by the general formula (5) and the general formulas (7) to (10) is preferable from the viewpoint of the efficiency of generating an acid. And groups represented by (8) to (10) are more preferable.

Ar ^{8 to} Ar ¹² in the general formula (15) or the general formula (16) are groups in which the compound represented by the general formula (15) or the general formula (16) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{8 to} Ar ¹² is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar ^{8 to} Ar ¹² include general formula (1) or general formula (2). The thing similar to what was illustrated as Ar < ¹ > -Ar < ⁷ > of these is mentioned, A preferable thing is also the same.

^(X 7) ^- and ^(X 8) ^- as is in the general formula (1) or (2) ^(X 1) ^- or ^(X 2) ^- the like can be mentioned and those exemplified as preferable ones also It is the same.

  As the iodonium salt derivative (C) that generates an acid by actinic rays, (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4- Compound having t-butylphenyl)] iodonium cation, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation and [bis (4-methoxyphenyl)] iodonium cation as cation skeleton Other than these, compounds represented by the following general formulas (17) to (20) are preferred, and compounds represented by the following general formulas (17) to (20) (including the exemplified compounds) are more preferable. .

In the general formulas (17) to (20), R ^{8 to} R ¹³ are a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An atom or substitution selected from the group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group And (X ⁹ ) ⁻ to (X ¹² ) ⁻ represents an anion.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

R ^{8 to} R ¹³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms. More preferred are a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, and particularly preferred are those having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

(X ⁹ ) ⁻ to (X ¹² ) ^{− in the} general formulas (17) to (20) are the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in the} general formula (1) or (2). The preferable thing is also the same.

  In general, a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) is colored by the initiator itself because it absorbs visible light, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (16), adverse effects on the hue of the cured film can be suppressed.

  Content of sulfonium salt derivative (B) that generates acid by active light and / or iodonium salt derivative (C) that generates acid by active light in the photosensitive composition of the present invention [of (B) and (C) Total] is preferably 0.05 to 30% by weight, more preferably 0.1 to 20% by weight, based on 100% by weight of the polymerizable substance (D), from the viewpoint of photocurability.

As the polymerizable substance (D) in the present invention, known compounds such as a monofunctional radical polymerizable substance (D1), a bifunctional radical polymerizable substance (D2), and a trifunctional or higher functional radical polymerizable substance (D3) are used. Can be used. From the viewpoint of substrate adhesion and curing speed, the polymerizable substance (D) is a monofunctional radically polymerizable substance (D1) and / or a bifunctional radically polymerizable substance (D2), and the polymerizable substance (D) is 100 weights. 10 to 70% by weight in total, preferably 15 to 65% by weight, more preferably 30 to 60% by weight.
From the viewpoint of adhesion to the substrate, the polymerizable substance (D) preferably contains the monofunctional radically polymerizable substance (D1), more preferably 1 to 20% by weight, and particularly preferably 3 -20% by weight, most preferably 5-10% by weight. Moreover, it is preferable to contain bifunctional radically polymerizable substance (D2) from a viewpoint of hardening rate, It is more preferable to contain 1-69 weight%, Especially preferably, it is 10-65 weight%, Most preferably, 30- 60% by weight. Therefore, the combined use of the monofunctional radically polymerizable substance (D1) and the bifunctional radically polymerizable substance (D2) is preferable from the viewpoints of substrate adhesion and curing speed.
The “monofunctional radically polymerizable substance (D1)” means a radically polymerizable substance having one polymerizable functional group, and the “bifunctional radically polymerizable substance (D2)” means a polymerization. Means a radically polymerizable substance having two functional groups, and “a radically polymerizable substance having three or more functions (D3)” means a radically polymerizable substance having three or more polymerizable functional groups. To do. Hereinafter, the same description method is used.

  Further, if necessary, a polymerization inhibitor such as hydroquinones may be used in combination.

Examples of the monofunctional radical polymerizable substance (D1) and the bifunctional radical polymerizable substance (D2) include a monofunctional (meth) acrylamide compound (D11) having 3 to 35 carbon atoms, and a monofunctional (meta) having 4 to 35 carbon atoms. ) Acrylate compound (D12), C6-C35 monofunctional aromatic vinyl compound (D13), C3-C20 monofunctional vinyl ether compound (D14), other monofunctional radical polymerizable compounds (D15), carbon Examples thereof include a bifunctional (meth) acrylate compound (D22) having 4 to 35 carbon atoms and a bifunctional vinyl ether compound (D24) having 3 to 20 carbon atoms.
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

  Examples of the monofunctional (meth) acrylamide compound (D11) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl Other than (meth) acryloylmorpholine such as (meth) acrylamide and N, N-diethyl (meth) acrylamide.

  Examples of the monofunctional (meth) acrylate compound (D12) having 4 to 35 carbon atoms include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, and isoamyl. (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl ( (Meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) Acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (meth) acrylate, 2-ethyl Hexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2- Tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (Meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, Glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate , Oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (Meth) acrylate, polypropylene oxide monoalkyl Ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate Perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (hereinafter referred to as EO) modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (Meth) acrylate, propylene oxide (hereinafter referred to as PO) -modified nonylphenol (meth) acrylate and EO-modified-2-ethylhexyl (meth) acrylate And the like which does not have vinyl ether groups and / or allyl ether groups and the like.

  C6-C35 monofunctional aromatic vinyl compound (D13) [The vinyl ether compound (D14) mentioned later is not included. ], For example, vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl Benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, isopropenylstyrene, butenyls Ren, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

  Examples of the monofunctional vinyl ether compound (D14) having 3 to 20 carbon atoms include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, Cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxy Ethoxyethyl vinyl ether, methoxy Ethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether Chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

  Other monofunctional radically polymerizable compounds (D15) include, for example, acrylonitrile, aliphatic vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatic acid), aliphatic allyl ester compounds (such as allyl acetate), and halogen-containing compounds. Examples include monomers other than aromatic ester compounds such as monomers (vinylidene chloride, vinyl chloride, etc.) and olefin compounds (ethylene, propylene, etc.).

  Examples of the bifunctional (meth) acrylate compound (D22) having 4 to 35 carbon atoms include 1,4-butanedi (meth) acrylate, 1,6-hexanedi (meth) acrylate, polypropylene di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (Meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) Acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, Polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonane (Meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, and the like.

  Examples of the bifunctional vinyl ether compound (D24) having 3 to 20 carbon atoms include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, and alkylene oxide modified. Examples thereof include bisphenol A divinyl ether and alkylene oxide-modified bisphenol F divinyl ether.

  Among these, from the viewpoints of curing speed and adhesion, monofunctional (meth) acrylamide compound (D11) having 3 to 35 carbon atoms, monofunctional (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and It is a C4-C35 bifunctional (meth) acrylate compound (D22).

  Examples of the tri- or higher functional radical polymerizable substance (D3) include a 3-6 functional (meth) acrylate compound (D31) of a 3-6 valent alcohol, and a 3-6 functional vinyl ether compound (D32) of a 3-6 valent alcohol. And other trifunctional or higher functional radical polymerizable compounds (D33).

  Examples of the 3-6 functional (meth) acrylate compound (D31) of 3-6 valent alcohols include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and trimethylolpropane alkylene oxide-modified tris. Carbon number of (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate of 2 to 4 alkylene oxide 1-30 mol adduct, ethoxylated glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate Carbon number of pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, pentaerythritol Tetraalkyl (1) to 30 mol adduct tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, Examples include caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Examples of the 3-6 functional vinyl ether compound (D32) of 3-6 valent alcohol include, for example, trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, glycerin trivinyl ether EO-added trimethylol propane trivinyl ether, PO-added trimethylol propane tri Vinyl ether, ditrimethylolpropane tetravinyl ether, pentaerythritol tetravinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, di Pentaerythritol hexavinyl ester Ether, EO adduct of dipentaerythritol hexa ether include PO adduct of dipentaerythritol hexa vinyl ether.

  Examples of other tri- or higher functional radical polymerizable compounds (D33) include isocyanuric acid alkylene oxide modified tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri. (Meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and the like.

  A tri- or higher functional radical polymerizable substance (D3) is preferably a tri- to hexa-valent alcohol 3-6 functional (meth) acrylate compound (D31), more preferably pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  The photosensitive composition of the present invention includes a coloring material (a pigment such as an inorganic pigment and an organic pigment, a dye), a metal oxide, and a metal powder, from the viewpoint of transparency of the resulting cured product. It is necessary to not contain substantially. Here, the phrase “not substantially contained” means that the content in the photosensitive composition is less than 1% by weight.

  The photosensitive composition of the present invention can contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent) and the like, if necessary.

Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran) And 1,8-cineole etc.). These may be used alone or in combination of two or more.
The content of the solvent in the photosensitive composition is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight.

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight with respect to the photosensitive composition.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight with respect to the photosensitive composition.

  The photosensitive composition of the present invention further includes a dispersant, an antifoaming agent, a leveling agent, a thixotropy imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, an ultraviolet absorber, etc. according to the purpose of use. In addition to (meth) acrylic resin, it can contain.

  The photosensitive composition of the present invention comprises a photo radical initiator (A), a polymerizable substance (D), a sulfonium salt derivative (B) that generates an acid by actinic rays and / or an iodonium that generates an acid by actinic rays. It can be obtained by kneading the salt derivative (C) and, if necessary, a solvent or other components with a ball mill or a three-roll mill. The kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.

Examples of the active light used for curing the photosensitive composition of the present invention include visible light and ultraviolet light.
Since the photosensitive composition of the present invention can be photocured by irradiation with an actinic ray of 360 nm to 830 nm, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, etc. The latest trends in EB curing technology, edited by Radtech Research Association, CMC Publishing, 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Furthermore, sunlight, a low-pressure mercury lamp, a semiconductor laser, etc. can be used. Heating may be performed for the purpose of diffusing the acid generated from the acid generator during and / or after irradiation with actinic rays. The heating temperature is preferably 30 ° C to 200 ° C, more preferably 35 ° C to 150 ° C, and particularly preferably 40 ° C to 120 ° C.

  Examples of the method for applying the photosensitive composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and nanoimprint processes, lithographic printing, carton printing, metal printing, offset printing, screen printing, and the like. Printing methods such as gravure printing can be applied. In addition, the present invention can also be applied to ink jet type coating in which fine droplets are continuously discharged.

  The nanoimprint process uses a mold with a desired pattern resolution drawn on the nano order, presses the film with the photosensitive composition on it, presses it, and then cures from the film side. Therefore, it refers to a process of obtaining a nano-shaped film by exposing to light and peeling the cured resin film from the mold.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

[Production of sulfonium salt derivative (B)]
Production Example 1
[Synthesis of Sulfonium Salt Derivative (B-1) {Compound Represented by Chemical Formula (21)} that Generates Acid by Actinic Light]

(1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (B-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) yielded 3.1 parts of intermediate (B-1-1) (yellow solid).

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (B-1-2)]:
While stirring 11.2 parts of intermediate (B-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide was gradually added dropwise to the mixture. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (B-1-2) (yellow solid).

(3) Synthesis of sulfonium salt derivative (B-1):
While stirring 4.3 parts of intermediate (B-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise to After reacting at 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. did. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, charged into 65 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing with water three times, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of a sulfonium salt derivative (B-1) (yellow solid).

Production Example 2
[Synthesis of Iodonium Salt Derivative (C-1) {Compound Represented by Chemical Formula (22)} that Generates Acid by Active Light]

  6.5 parts of toluene [manufactured by Tokyo Chemical Industry Co., Ltd.], 8.1 parts of isopropylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 5.35 parts of potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] and acetic anhydride 20 parts were dissolved in 70 parts of acetic acid, cooled to 10 ° C., and a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour while maintaining the temperature at 10 ± 2 ° C. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium tris (pentafluoroethyl) trifluorophosphate was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed three times with water, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target iodonium salt derivative (C-1) (light yellow liquid). It was.

Examples 1-22
Monofunctional radical polymerizable substance (D1), bifunctional radical polymerizable substance (D2), trifunctional or higher functional radical polymerizable substance (D3), photo radical initiator (A) shown in Table 1, and an active light beam Using the generated sulfonium salt derivative (B) and / or the iodonium salt derivative (C) that generates an acid by actinic rays, the number of parts (D1) to (D3) shown in Table 1 and “photo radical initiator” (A) 5 parts, sulfonium salt derivative (B) that generates acid by actinic rays or 0.5 part of iodonium salt derivative (C) that generates acids by actinic light [However, in Example 9, (B) and (C) 2.5 parts each] ”was kneaded at 25 ° C. for 3 hours using a ball mill to produce photosensitive compositions (Q-1) to (Q-22) of the present invention.

Comparative Examples 1-19
Use 5 parts of the monofunctional radical polymerizable substance (D1), the bifunctional radical polymerizable substance (D2), the trifunctional or higher functional radical polymerizable substance (D3) and the photo radical initiator (A) in the number of parts shown in Table 2. In the same manner as in Example 1, except that 0.5 part of a sulfonium salt derivative (B) that generates an acid by active light or an iodonium salt derivative (C) that generates an acid by active light is used, if necessary. Photosensitive compositions (Q′-1) to (Q′-19) were prepared.

  Regarding the compounds described in Tables 1 and 2, LUCIRIN TPO as (A) was a product manufactured by BASF.

[Adhesion]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was subjected to surface treatment and a 100 μm thick PET (polyethylene terephthalate) film [Toyobo Cosmo Shine A4300, the same for the following evaluations. A thing was used. ] TAC (triacetylcellulose) film (TF-80UL manufactured by Fuji Film Holding Co., Ltd.), 125 μm thick PMMA (polymethylmethacrylate) film [Acryprene HBS010P manufactured by Mitsubishi Rayon Co., Ltd.], thickness A 25 μm thick PP (polypropylene) film [Nippon Polypro Wintech WFX4TA] and a 100 μm thick COP (cycloolefin polymer) film [Nippon ZEON ZEONOR Film ZF14] are made to have a film thickness of 20 μm using an applicator. Then, exposure was performed using a belt conveyor type UV irradiation device (“ECS-151U” manufactured by Eye Graphics Co., Ltd., the same device was also used for the following evaluation). The exposure amount was 150 mJ / cm ² at 365 nm.
About the coating film after hardening apply | coated to PET, TAC, PMMA, PP, and a COP film, adhesiveness was evaluated by the cross-cut cellophane tape peeling test based on JISK-5600-5-6.

[Transparency (transmittance and haze)]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
Based on JIS-K7105, the cured coating film was measured for transmittance and haze using a total light transmittance measuring device [trade name “haze-garddual” manufactured by BYK Gardner Co., Ltd.] (PET film of substrate) Was subtracted as a blank). In both cases, the unit is%.
In addition, if the transmittance is 90% or more and the haze is 0.5% or less, the transparency is satisfactory for industrial use.

[Pencil hardness]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
About the coating film after hardening, pencil hardness was measured based on JISK-5400.

[Abrasion resistance]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
The cured coating film was subjected to 30 reciprocal scratches by applying a load of 250 g per 1 cm ² using steel wool # 0000, and the appearance was evaluated visually according to the following criteria.
A: Not scratched at all.
○: Some scratches are recognized.
X: Many scratches are recognized and the surface becomes cloudy.

[Heat-resistant]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was performed using the belt conveyor type UV irradiation apparatus. The exposure amount was 150 mJ / cm ² at 365 nm.
The cured coating film was placed in a blast constant-temperature thermostatic chamber (DKN302: manufactured by Yamato Scientific Co., Ltd.) at 85 ° C. and temperature-controlled for 100 hours or 300 hours. The temperature-controlled resin film was visually observed and observed at 50 times using a shape measurement microscope (ultra-deep shape measurement microscope VK-8550, manufactured by Keyence Corporation), and evaluated according to the following criteria.
A: No change in appearance and no color change before temperature control and no discoloration.
○: Appearance change is not recognized at all before temperature adjustment, but there is discoloration.
Δ: There is no change visually, but a change is observed with a microscope before temperature adjustment.
X: Visual change before temperature control is recognized

[Curing property]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. About the exposure, it implemented using the following 2 types of irradiation apparatuses.
(1) It exposed using the said belt conveyor type | mold UV irradiation apparatus. The exposure amount was 150 mJ / cm ² at 365 nm.
(2) Exposure was performed using a spot type LED irradiation device (“RX FireFlex” manufactured by Foseon Technology). The exposure amount was 150 mJ / cm ² at 395 nm.
The curability immediately after light irradiation of the coated film after curing was evaluated by the following evaluation criteria by scratching with a finger and nails.
A: There is no tack on the surface and it is not damaged by the nail.
○: There is no tack on the surface, but the nail is damaged.
Δ: There is tack on the surface and it is damaged by the nail.
X: Uncured.

[Yellowing resistance]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was performed using the belt conveyor type UV irradiation apparatus. The exposure amount was 10,000 mJ / cm ² at 365 nm. The appearance was visually observed and evaluated according to the following criteria.
A: No yellowing.
○: Slightly yellowed when observed on white paper.
Δ: Yellowing is observed under fluorescent light.
X: Severe yellowing is observed.

[Pattern reproducibility]
Each photosensitive composition obtained in Examples 1 to 22 and Comparative Examples 1 to 19 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. A film applied to a mold having a line pattern with a line width of 10 nm and a depth of 10 nm was pressed with a roller, and exposure was performed from the film surface using the belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm. 2 mL of methyl ethyl ketone was applied so as to cover the coating film, and then dried at 80 ° C. for 2 minutes using a circulating air dryer. The coating film in which methyl ethyl ketone was completely dried was evaluated by AFM (Atomic Force Microscope) based on the following criteria to reproduce the pattern of the mold.
A: Line width 10 nm ± 0.5 nm and pattern height 10 nm ± 0.5 nm.
○: Line width 10 nm ± 2 nm and pattern height 10 nm ± 2 nm.
Δ: Line width 10 nm ± 5 nm and pattern height 10 nm ± 5 nm.
X: The line pattern cannot be confirmed.

  These evaluation results are shown in Tables 3 and 4.

  The photosensitive composition of the present invention is extremely useful for flat panel displays because it has excellent adhesion to various substrates, hardness, scratch resistance, and heat resistance and can form a transparent cured product.

Claims (6)

A photosensitive composition containing the following (1) to (3), which contains substantially no colorant, metal oxide powder and metal powder, and is contained in 100% by weight of the polymerizable substance (D). 33-70 wt% der content is the sum of the monofunctional radically polymerizable substance (D1) and bifunctional radically polymerizable substance (D2) of is,
The content of the monofunctional radical polymerizable substance (D1) in 100% by weight of the polymerizable substance (D) is 3 to 20% by weight, and the content of the bifunctional radical polymerizable substance (D2) is 30 to 30%. the photosensitive composition according to claim 60 wt% der Rukoto.
(1) Acylphosphine oxide derivative polymerization initiator (A1), α-aminoacetophenone derivative polymerization initiator (A2), benzyl ketal derivative polymerization initiator (A3), α-hydroxyacetophenone derivative polymerization initiator (A4) ), Benzoin derivative polymerization initiator (A5), oxime ester derivative polymerization initiator (A6) and at least one photoradical initiator (A) selected from the group consisting of titanocene derivative polymerization initiators (A7 )
(2) A sulfonium salt derivative (B) that generates an acid by actinic rays and / or an iodonium salt derivative (C) that generates an acid by actinic rays
(3) Polymerizable substance (D) The monofunctional radical polymerizable substance (D1) is a monofunctional (meth) acrylamide compound (D11) having 3 to 35 carbon atoms, a monofunctional (meth) acrylate compound (D12) having 4 to 35 carbon atoms, or 6 to 6 carbon atoms. monofunctional aromatic vinyl compound (D13) and a photosensitive composition according to claim 1, wherein at least one polymerizable material selected from the group consisting of monofunctional vinyl compound (D14) of 3 to 20 carbon atoms 35. The bifunctional radically polymerizable substance (D2) is selected from the group consisting of a bifunctional (meth) acrylate compound (D22) having 4 to 35 carbon atoms and a bifunctional vinyl ether compound (D24) having 3 to 20 carbon atoms. claim 1 or 2 photosensitive composition wherein the species of the polymerizable material. A content of the photo radical initiator (A) is 0.05 to 30% by weight with respect to 100% by weight of the polymerizable substance (D), and an acid is generated by the active light with respect to 100% by weight of the polymerizable substance (D). The content of the sulfonium salt derivative (B) and / or the iodonium salt derivative (C) that generates an acid by actinic rays [the sum of (B) and (C)] is 0.05 to 30% by weight. The photosensitive composition in any one of -3 . The photosensitive composition according to any one of claims 1-4 is for a flat panel display using nanoimprint process. Hardened | cured material formed by hardening the photosensitive composition in any one of Claims 1-5 by irradiation of actinic light.