JP2013057049A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which gives a cured film which develops an excellent surface protection function without impairing high adhesion and high transparency of a coating film.SOLUTION: The active energy ray curable photosensitive composition includes at least one ester compound (A) selected from the group consisting of a phthalic acid ester, a trimellitic acid ester, and a pyromellitic acid ester, each ester having an ethylenic unsaturated bond-containing group (x); a polymerization initiator (C); and, optionally, at least one of a (meth)acrylate (B) having a urethane group and/or an urea group and an acid generator (D) which generates an acid by an active energy ray. The ethylenic unsaturated bond-containing group (x) is preferably at least one substituent selected from the group consisting of a (meth)acryloyl group, a vinyl group, a 1-propenyl group, and an allyl group.

Description

  The present invention provides a cured film having a high hardness when cured by irradiation with an active energy ray and applied to a substrate, and is particularly useful for a hard coat of a resin molded product or a hard coat of a display. The present invention relates to a sex composition.

  Conventionally, a photosensitive composition has been used as a hard coating agent, and the purpose of the hard coating agent is to prevent dust from adhering to the plastic surface and to prevent scratches due to friction. In particular, hard coat agents used for hard coats of resin molded products or for hard coats of displays [CRT (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (EL), touch panel, etc.] In addition, there are demands for materials having both high adhesion to the substrate surface, high gloss and high transparency for obtaining high image quality. Further, in other fields such as optical disks, optical fibers, and polarizers in LCDs, a hard coating agent having a surface protection function, high adhesion and high transparency is desired.

For the purpose of improving the surface protection function of the hard coat coating, it has been proposed to add an inorganic filler to the hard coat agent (for example, Patent Document 1).
However, in the inorganic filler addition system, if the content of the inorganic filler in the coating layer is small, sufficient surface protection function is not expressed, and if the content is large, the adhesion and transparency of the coating film are impaired, and the cost is very high. There was a problem of becoming high.

JP 2005-171216 A

  The objective of this invention is providing the photosensitive composition which gives the cured film which expresses the outstanding surface protection function, without impairing the high adhesiveness and high transparency of a coating film.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention relates to at least one ester compound (A) selected from the group consisting of phthalic acid ester, trimellitic acid ester and pyromellitic acid ester having an ethylenically unsaturated bond-containing group (x), a polymerization initiator ( C), and if necessary, an activity comprising at least one of a (meth) acrylate (B) having a urethane group and / or a urea group and an acid generator (D) that generates an acid by active energy rays. An energy ray-curable photosensitive composition; and a cured product obtained by curing the photosensitive composition with active energy rays.

The active energy ray-curable photosensitive composition of the present invention has the following effects.
(1) Since the cured product obtained by curing the photosensitive composition of the present invention exhibits high hardness, it has an excellent surface protection function.
(2) A cured product obtained by curing the photosensitive composition of the present invention exhibits high adhesion to various substrates.
(3) A cured product obtained by curing the photosensitive composition of the present invention exhibits high transparency.
(4) A cured product obtained by curing the photosensitive composition of the present invention is excellent in developability when used as a resist.
(5) The photosensitive composition of the present invention can be cured with a thick film at a high colorant-containing concentration even with a small amount of energy.

  The active energy ray-curable photosensitive composition of the present invention is at least one ester selected from the group consisting of phthalic acid esters, trimellitic acid esters and pyromellitic acid esters having an ethylenically unsaturated bond-containing group (x). At least one of the compound (A), the polymerization initiator (C), and, if necessary, a (meth) acrylate (B) having a urethane group and / or a urea group and an acid generator (D) that generates an acid by active energy rays. Containing.

  The ester compound (A) in the present invention is a group consisting of, for example, a compound having an ethylenically unsaturated bond-containing group (x) and a hydroxyl group, phthalic acid (including isophthalic acid and terephthalic acid), trimellitic acid and pyromellitic acid. It can obtain by making it react with the at least 1 sort (s) of acid chosen from these.

From the viewpoint of curability, the ethylenically unsaturated bond-containing group (x) of the ester compound (A) is preferably a (meth) acryloyl group, a vinyl group, a 1-propenyl group, and an allyl group, and more preferably An allyl group.
When the ester compound (A) has a plurality of (x), the plurality of (x) may be the same or different.

  Preferred examples of the ester compound (A) include compounds represented by any of the following general formulas (1) to (3). (A) may be used individually by 1 type, and may use 2 or more types together.

In the general formulas (1) to (3), R ^{1 to} R ⁹ are each independently a monovalent substituent represented by any one of the following general formulas (4) to (8).

In the general formulas (4) to (8), R ¹⁰ , R ¹² and R ¹⁴ are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and R ¹¹ , R ¹³ and R ¹⁵ are each Independently a hydrogen atom or a methyl group, * represents that the substituent is bonded to the oxygen atom of the oxycarbonyl group in the general formulas (1) to (3) by the bond to which it is attached.

Of the compounds represented by the general formulas (1) to (3), the compound represented by the general formula (2) or (3) is preferable from the viewpoint of surface hardness and adhesion, and more preferable is the general formula It is a compound represented by Formula (2). Of the substituents represented by the general formulas (4) to (8), the substituents represented by the general formula (4), (7) or (8) are preferable from the viewpoint of surface hardness and adhesion. Further preferred is a substituent represented by the general formula (8).
Among these, R ^{3 to} R ⁵ in the general formula (2) are particularly preferably represented by the general formula (4) in which R ¹⁰ is an ethylene group and R ¹¹ is a hydrogen atom in terms of surface hardness and adhesion. A compound that is a substituent, a compound in which R ^{3 to} R ⁵ in General Formula (2) are a substituent represented by General Formula (7) in which R ¹⁵ is a hydrogen atom, R in General Formula (2) ^A compound in which ^{3 to} R ⁵ are substituents represented by the general formula (8), R ^{6 to} R ⁹ in the general formula (3), R ¹⁰ is an ethylene group, and R ¹¹ is a hydrogen atom ( 4) a compound that is a substituent represented by formula (3), and R ^{6 to} R ⁹ in formula (3) are compounds that are a substituent represented by formula (7) in which R ¹⁵ is a hydrogen atom, A compound in which R ^{3 to} R ⁵ in the general formula (2) are substituents represented by the general formula (8) is preferable.

  The content of the ester compound (A) in the photosensitive composition of the present invention is preferably 1 to 80% by weight, more preferably 3 based on the weight of the photosensitive composition from the viewpoint of surface hardness and adhesion. -60% by weight, particularly preferably 5-40% by weight.

  The ester compound (A) used in the present invention comprises, for example, an acid such as trimellitic acid in an organic solvent, a compound having an ethylenically unsaturated bond-containing group (x) and a hydroxyl group, if necessary, an acid catalyst (paratoluene). It can be obtained by reacting in the presence of sulfonic acid and the like, and then distilling off the organic solvent under reduced pressure.

Examples of the polymerization initiator (C) in the present invention include an acylphosphine oxide derivative polymerization initiator (C1), an α-aminoacetophenone derivative polymerization initiator (C2), a benzyl ketal derivative polymerization initiator (C3), and α. -Hydroxyacetophenone derivative polymerization initiator (C4), benzoin derivative polymerization initiator (C5), oxime ester derivative polymerization initiator (C6), titanocene derivative polymerization initiator (C7), organic peroxide polymerization start Examples thereof include an agent (C8), an azo compound-based polymerization initiator (C9), and other polymerization initiators (C10). (C) may be used individually by 1 type, and may use 2 or more types together.
Here, the acylphosphine oxide derivative polymerization initiator (C1) means a polymerization initiator which is a compound in which a part of the acylphosphine oxide is substituted with another group. The α-aminoacetophenone derivative polymerization initiator (C2) means a polymerization initiator that is a compound in which a part of α-aminoacetophenone is substituted with another group. The benzyl ketal derivative-based polymerization initiator (C3) means a polymerization initiator that is a compound in which a part of α-dihydroxyacetophenone is substituted with another group. The α-hydroxyacetophenone derivative polymerization initiator (C4) means a polymerization initiator that is a compound in which a part other than the hydroxyl group of α-monohydroxyacetophenone is substituted with another group. The benzoin derivative polymerization initiator (C5) means a polymerization initiator which is a compound in which a part of benzoin is substituted with another group. The oxime ester derivative polymerization initiator (C6) means a polymerization initiator which is a compound in which a part of N-acetyldimethyloxime is substituted with another group. The titanocene derivative polymerization initiator (C7) means a polymerization initiator that is a compound in which a part of titanocene is substituted with another group. The organic peroxide polymerization initiator (C8) means a polymerization initiator that is a compound having a peroxy group. The azo compound-based polymerization initiator (C9) means a polymerization initiator that is a compound having an azo group.

  As the acylphosphine oxide derivative polymerization initiator (C1), 2,4,6-trimethylbenzoyldiphenylphosphine oxide [manufactured by BASF (LUCIRIN TPO)] and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [ BASF (IRGACURE 819)] and the like.

  As the α-aminoacetophenone derivative-based polymerization initiator (C2), 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 (C3) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (C4), 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 (C5) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (C6), 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 (C7), 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.

  Examples of the organic peroxide polymerization initiator (C8) include benzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, and n-butyl. 4,4-di- (t-butylperoxy) valerate, di- (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5, -dimethyl-2 , 5, -di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide Oxide and t- butyl trimethylsilyl peroxide.

  As the azo compound polymerization initiator (C9), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of the other polymerization initiator (C10) include 2,3-dimethyl-2,3-diphenylbutane.

  Among these, acylphosphine oxide derivative polymerization initiators (C1), α-aminoacetophenone derivative polymerization initiators (C2), benzyl ketal derivative polymerization initiators (C3), are preferable from the viewpoint of photocurability. α-hydroxyacetophenone derivative polymerization initiator (C4), benzoin derivative polymerization initiator (C5), oxime ester derivative polymerization initiator (C6) and titanocene derivative polymerization initiator (C7), more preferred It is an acylphosphine oxide derivative polymerization initiator (C1).

  The content of the polymerization initiator (C) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight, more preferably, based on the weight of the photosensitive composition, from the viewpoint of photocurability. 0.1 to 20% by weight.

  The photosensitive composition of this invention can contain the (meth) acrylate (B) which has a urethane group and / or a urea group further as needed. By containing (B), the adhesion is further improved.

As the (meth) acrylate (B) having a urethane group and / or urea group, an active hydrogen component (h) containing a (meth) acrylate having a hydroxyl group and / or a (meth) acrylate having an amino group and an organic polyisocyanate Examples thereof include (meth) acrylate obtained by reacting component (i). (B) may be used individually by 1 type, and may use 2 or more types together.
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 (meth) acrylate having a hydroxyl group in the active hydrogen component (h) include a hydroxyalkyl (meth) acrylate having 5 to 8 carbon atoms [for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate], pentaerythritol di ( And (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

  Examples of the (meth) acrylate having an amino group include C5-C8 aminoalkyl (meth) acrylate [for example, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate] and the like.

  Among these, hydroxyethyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and aminoethyl (meth) are preferable from the viewpoint of curability. Acrylate.

  The total content of the hydroxyl group-containing (meth) acrylate and / or amino group-containing (meth) acrylate in the active hydrogen component (h) is preferably 1% by weight or more, more preferably 5% by weight or more.

  Examples of components other than the (meth) acrylate having a hydroxyl group and the (meth) acrylate having an amino group in the active hydrogen component (h) include a polyol and a chain extender.

  Examples of the polyol include a high molecular polyol having a hydroxyl group equivalent (average molecular weight per hydroxyl group calculated from a hydroxyl value) of 150 or more and a low molecular polyol having a hydroxyl group equivalent of less than 150.

  Examples of the polymer polyol having a hydroxyl group equivalent of 150 or more include polyether polyol and polyester polyol.

  Examples of polyether polyols include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include polyoxyethylene polyol (polyethylene glycol and the like), polyoxypropylene polyol (polypropylene glycol and the like), polyoxyethylene / propylene polyol and polytetramethylene ether glycol.

  As the aromatic polyether polyol, a polyol having a bisphenol skeleton, for example, an ethylene oxide (hereinafter abbreviated as EO) adduct of bisphenol A [EO2 mol adduct of bisphenol A, EO4 mol adduct of bisphenol A, EO6 of bisphenol A, Mole adduct, EO 8 mol adduct of bisphenol A, EO 10 mol adduct of bisphenol A and EO 20 mol adduct of bisphenol A] and propylene oxide (hereinafter abbreviated as PO) adduct of bisphenol A [PO2 mol of bisphenol A] Adduct, PO3 mol adduct of bisphenol A and PO5 mol adduct of bisphenol A, etc.] and EO or PO adduct of resorcin.

  Polyether polyol is obtained by subjecting an aliphatic or aromatic low molecular weight active hydrogen atom-containing compound to ring-opening addition reaction of EO or PO in the presence of an addition catalyst (a known catalyst such as alkali metal hydroxide and Lewis acid). It is obtained by.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyether polyol is usually 300 or more, preferably 300 to 10,000, and more preferably 300 to 6,000. In the present invention, the Mn of the polyol is measured by the method described later. However, Mn of the low molecular polyol is a calculated value from the chemical formula.

  Examples of the polyester polyol include condensed polyester, polylactone polyol, polycarbonate polyol, and castor oil-based polyol.

Condensation type polyesters are low molecular weight (Mn 300 or less) polyhydric alcohol and polyvalent carboxylic acid or ester-forming derivatives thereof [acid anhydride, acid halide, or low molecular weight alkyl (alkyl group having 1 to 4 carbon atoms) ester] And polyester.
Examples of the low molecular weight polyhydric alcohol include dihydric to octavalent or higher aliphatic polyhydric alcohol having a hydroxyl group equivalent of 30 to less than 150 and dihydric to octavalent or higher phenol having a hydroxyl group equivalent of 30 to less than 150. Alkylene oxide low molar adducts can be used.
Among the low molecular weight polyhydric alcohols that can be used in the condensed polyester, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, bisphenol A EO or PO low molar addition Products and combinations thereof.

  Examples of polyvalent carboxylic acids or ester-forming derivatives thereof that can be used in the condensed polyester include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.) and trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), and their anhydrides (succinic anhydride, Maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl (1 to 4 carbon atoms) esters (such as dimethyl succinate and dimethyl phthalate) And combinations thereof.

  Examples of the condensed polyester include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate Diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and Examples include polyneopentyl terephthalate diol.

The polylactone polyol is a polyadduct of lactone to the low molecular weight polyhydric alcohol. As the lactone, a lactone having 4 to 12 carbon atoms can be used, for example, γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc. Is mentioned.
Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

The polycarbonate polyol is a polyaddition product of an alkylene carbonate to a low molecular weight polyhydric alcohol. As the alkylene carbonate, an alkylene carbonate having 2 to 8 carbon atoms can be used, and examples thereof include ethylene carbonate and propylene carbonate.
Examples of the polycarbonate polyol include polyhexamethylene carbonate diol.
Examples of commercially available polycarbonate polyols include NIPPOLAN 980R [Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.], T5652 [Mn = 2,000, manufactured by Asahi Kasei Co., Ltd.], and T4672 [Mn = 2,000, Asahi Kasei. Made by Co., Ltd.].

  The castor oil-based polyol includes castor oil and castor oil modified with polyol or alkylene oxide. Modified castor oil can be produced by transesterification of castor oil and polyol and / or addition of alkylene oxide. Castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

Low molecular polyols having a hydroxyl equivalent weight of less than 150 include aliphatic dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, etc.) and aliphatic trihydric alcohols (triglycerides). Methylolpropane and glycerin).
A polyol may be used individually by 1 type and may use 2 or more types together.

Examples of chain extenders include water, diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine and piperazine), polyalkylenepolyamines (for example, diethylenetriamine and triethylenetetramine), and hydrazine. Or derivatives thereof (acid hydrazide and the like) (for example, dibasic acid dihydrazide such as adipic acid dihydrazide) and amino alcohols having 2 to 10 carbon atoms (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol and triethanolamine) ) And the like.
A chain extender may be used individually by 1 type, and may use 2 or more types together.

  The organic polyisocyanate component (i) is an aromatic polyisocyanate having 2 to 3 or more isocyanate groups and having 6 to 20 carbon atoms (excluding carbon in the isocyanate group, the same shall apply hereinafter), and 2 to 18 carbon atoms. Aliphatic polyisocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, and araliphatic polyisocyanates having 8 to 15 carbon atoms.

  Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4′- or 2,4′-diphenylmethane diisocyanate, 1,5. Naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2,6-diisocyanate. Hexanoate is mentioned.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate is mentioned.

  Examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Among the polyisocyanates, preferred are isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, from the viewpoint of surface hardness and adhesion. 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate, more preferably isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
The organic polyisocyanate component (i) may be used alone or in combination of two or more.

  The (meth) acrylate (B) having a urethane group and / or urea group in the present invention can be produced by a usual method, for example, a (meth) acrylate having a hydroxyl group and / or an amino group (meth). The active hydrogen component (h) containing acrylate as an essential component and the organic polyisocyanate component (i) may be reacted together, or a (meth) acrylate having a hydroxyl group and a (meth) acrylate having an amino group. A prepolymer having an isocyanate group at the terminal obtained by reacting an active hydrogen component (h) not containing and the organic polyisocyanate component (i), a (meth) acrylate and / or an amino group having a hydroxyl group (meth) An acrylate may be reacted.

The ratio of the active hydrogen equivalent of the active hydrogen component (h) to the equivalent of the isocyanate group in the organic polyisocyanate component (i) (equivalent of active hydrogen / equivalent of isocyanate group) is preferably from 0.1 to 10, -1.2 is particularly preferred. The reaction temperature is preferably 30 to 150 ° C, more preferably 50 to 100 ° C. The end point of the reaction can be confirmed by, for example, disappearance of the isocyanate group absorption (2250 cm ⁻¹ ) in the infrared absorption spectrum or determining the isocyanate group content by the method described in JIS K 7301-1995.

  Mn (molecular weight in the case of a single product) of (meth) acrylate (B) having a urethane group and / or a urea group is preferably 300 to 10,000, more preferably 350, from the viewpoint of heat resistance and adhesion of the cured product. -8000, particularly preferably 400-5000, most preferably 450-2000.

The number average molecular weight (Mn) in the present invention is measured under the following conditions.
Apparatus: High-temperature gel permeation chromatography Solvent: Tetrahydrofuran Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 40 ° C

  The content of the (meth) acrylate (B) having a urethane group and / or urea group in the photosensitive composition of the present invention is preferably based on the weight of the photosensitive composition from the viewpoint of surface hardness and adhesion. Is 0 to 90% by weight, more preferably 1 to 85% by weight, and particularly preferably 5 to 80% by weight.

  The active energy ray-curable photosensitive composition of the present invention can further contain an acid generator (D) that generates an acid by active energy rays, if necessary. By containing (D), curability is improved.

  Examples of the acid generator (D) that generates an acid by active energy rays include a sulfonium salt (D1) and an iodonium salt (D2). (D) may be used individually by 1 type, and may use 2 or more types together.

  As the sulfonium salt (D1), triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate [manufactured by Wako Pure Chemical Industries, Ltd., “WPAG- 281H], tri-p-tolylsulfonium trifluoromethanesulfonate, [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate [“CPI-100P” and [p- (phenylmercapto) phenyl] manufactured by San Apro Co., Ltd. And diphenylsulfonium [tri (perfluoroethyl)] trifluorophosphate.

  Examples of the iodonium salt (D2) include iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate [manufactured by BASF (IRGACURE 250)], iodonium [bis (4-t-butyl). Phenyl)] hexafluorophosphate, iodonium [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] trifluoro [tris (perfluoro Ethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] [tetrakis (perfulphenyl)] borate, and a compound represented by the following chemical formula (9).

  Among these, iodonium salt (D2) is preferable from the viewpoint of photocurability, and a compound represented by chemical formula (9) is more preferable.

  The content of the acid generator (D) in the photosensitive composition of the present invention is preferably 0 to 30% by weight, more preferably 0.8%, based on the weight of the photosensitive composition, from the viewpoint of photocurability. It is 05 to 25% by weight, particularly preferably 0.1 to 20% by weight. When the photosensitive composition does not contain the (meth) acrylate (B) having the urethane group and / or urea group, it is preferable to contain (D) in the photosensitive composition.

  The photosensitive composition of the present invention can further contain an active energy ray-curable compound (E) other than (A) and (B) as required, as long as the effects of the present invention are not impaired. Examples of (E) include an acrylamide compound (E1) having 3 to 35 carbon atoms, a (meth) acrylate compound (E2) having 4 to 35 carbon atoms, an aromatic vinyl compound (E3) having 6 to 35 carbon atoms, and a carbon number. Examples of the vinyl ether compound (E4) of 3 to 35 and the other active energy ray-curable compound (E5) that do not correspond to any of (A) and (B) are mentioned.

  Examples of the (meth) acrylamide compound (E1) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- n-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, N, N-diethyl (meth) acrylamide and (meth) acryloylmorpholine.

Examples of the (meth) acrylate compound (E2) having 4 to 35 carbon atoms include (meth) acrylates that do not have any of the following monofunctional to hexafunctional urethane groups and urea groups.
The “monofunctional to hexafunctional (meth) acrylate” means a (meth) acrylate having 1 to 6 (meth) acryloyl groups, and the same description method is used hereinafter.
Monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, 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 Relate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-ethylhexyl 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) Chryrate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, diethylene glycol Monovinyl ether mono (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, diethylamino Ethyl (meth) 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 Id 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, EO-modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, Examples thereof include PO-modified nonylphenol (meth) acrylate and EO-modified-2-ethylhexyl (meth) acrylate.

  Examples of the bifunctional (meth) acrylate 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 (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-butyl Diol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (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-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) ) Acrylate and tricyclodecane di (meth) acrylate.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate And ethoxylated glycerin tri (meth) acrylate.

  Tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate and pentaerythritol EO addition. And tetra (meth) acrylate of the product.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate. It is done.

  Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (E3) include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro. Styrene, dichlorostyrene, bromostyrene, 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, Propenyl styrene, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

As a C3-C35 vinyl ether compound (E4), the following monofunctional or polyfunctional vinyl ether is mentioned, for example.
The “monofunctional vinyl ether” means a vinyl ether compound having one vinyl group, and the “polyfunctional vinyl ether” means two or more vinyl groups.
Examples of the monofunctional vinyl ether 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-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene 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, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

  Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, EO-added trimethylolpropane trivinyl ether, PO-added trimethylolpropane trivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, EO-added Examples thereof include dipentaerythritol hexavinyl ether and PO-added dipentaerythritol hexavinyl ether.

  Other active energy ray-curable compounds (E5) include acrylonitrile, vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), allyl ester compounds (such as allyl acetate), and halogen-containing monomers (vinylidene chloride). And vinyl chloride) and olefin compounds (ethylene, propylene, etc.).

  The content of the active energy ray-curable compound (E) other than (A) and (B) in the photosensitive composition of the present invention is 0 to 60% by weight based on the weight of the photosensitive composition. More preferably, it is 0 to 50% by weight, and particularly preferably 1 to 30% by weight.

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

Organic solvents include glycol ethers (ethylene glycol monoalkyl ether and 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 the like). Propylene glycol alkyl ether acetate, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran and 1,8- Cineol and the like). These may be used alone or in combination of two or more.
The content of the organic solvent is preferably 0 to 96% by weight based on the weight of the photosensitive composition, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight.

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

  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 based on the weight of the photosensitive composition, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight.

  Examples of the leveling agent include fluorine-based leveling agents (perfluoroalkylethylene oxide adducts and the like) and silicone-based leveling agents (amino polyether-modified silicone, methoxy-modified silicone, polyether-modified silicone, and the like). The content of the leveling agent is preferably 0 to 2% by weight, more preferably 0.05 to 2% by weight, and particularly preferably 0.1% from the viewpoint of the addition effect and transparency based on the weight of the photosensitive composition. ˜1% by weight.

  Examples of the polymerization inhibitor include hydroquinone and methyl ether hydroquinone. The content of the polymerization inhibitor is preferably 0 to 1% by weight, more preferably 0 to 0.1% by weight, based on the weight of the photosensitive composition.

  The photosensitive composition of the present invention further includes inorganic fine particles, a dispersant, an antifoaming 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. Can be contained.

  The photosensitive composition of the present invention comprises at least one ester compound (A) selected from the group consisting of a phthalic acid ester having an ethylenically unsaturated bond-containing group (x), trimellitic acid ester and pyromellitic acid ester, A polymerization initiator (C), and if necessary, a (meth) acrylate (B) having a urethane group and / or a urea group, an acid generator (D) that generates an acid by active energy rays, an organic solvent, and other components. It can be obtained by mixing and stirring with a disperser or the like. The mixing and stirring temperature is usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C.

  The photosensitive composition of this invention can be used for formation of a negative resist pattern by containing the polymer which has a carboxyl group further in addition to said each component.

  As the polymer having a carboxyl group in the present invention, a known compound such as a cresol novolac-type acid-modified epoxy acrylate resin can be used. For example, CCR-1218H, CCR-1159H, CCR-1222H, CCR-1314H, PCR- 1191H, TCR-1335H, ZAR-2001H, and ZCR-1569H [all are all manufactured by Nippon Kayaku Co., Ltd.]. The content of the polymer having a carboxyl group is preferably 0 to 50% by weight, more preferably 1 to 30% by weight from the viewpoint of developability, based on the weight of the photosensitive composition.

  The photosensitive composition of the present invention can be used for UV curable inks by containing pigments conventionally used in paints and inks. The content of the pigment is preferably 0 to 80% by weight and more preferably 0 to 50% by weight from the viewpoint of concealability and curability based on the weight of the photosensitive composition.

  Examples of the pigment include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

The photosensitive composition of the present invention can contain a pigment dispersant in order to improve the dispersibility and the storage stability of the photosensitive composition when a pigment is used.
Examples of the pigment dispersant include pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184 and 2020). Etc.), Ajinomoto Fine Techno Co., Ltd. pigment dispersants (Ajisper PB711, PB821, PB814, PN411, PA111, etc.), Lubrizol Corporation pigment dispersants (Solspers 5000, 12000, 32000, 33000, 39000, etc.). These pigment dispersants may be used alone or in combination of two or more. The content of the pigment dispersant is preferably 0 to 10% by weight, more preferably 0 to 5% by weight from the viewpoint of concealability and curability, based on the weight of the photosensitive composition.

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 planographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing. A known printing method can be applied. In addition, ink-jet coating that continuously discharges fine droplets can also be applied.
A coating film thickness is 0.5-300 micrometers normally as a film thickness after hardening drying. A preferable upper limit is 250 μm from the viewpoints of drying properties and curability, and a preferable lower limit is 1 μm from the viewpoints of wear resistance, solvent resistance, and stain resistance.

  When the photosensitive composition of the present invention is used after being diluted with an organic solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.

Examples of active energy rays in the present invention include actinic rays and electron beams.
In the present invention, active light means light having a wavelength of 360 nm to 830 nm.
As an energy source for curing the photosensitive composition of the present invention by irradiation with actinic rays, 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. (UV / EB curing) The latest trends in technology, edited by Radtech Institute, CM Publishing, 138 pages, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently.

As an energy source for curing the photosensitive composition of the present invention by electron beam irradiation, a commonly used electron beam irradiation apparatus can be used.
The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20, and preferably 1 to 15 from the viewpoint of curability of the photosensitive composition, flexibility of the cured product, and prevention of damage to the cured film and the substrate. is there.

  Heating may be performed for the purpose of diffusing the acid generated from the acid generator (D) during and / or after irradiation with actinic rays or electron beams. The heating temperature is usually 30 ° C to 200 ° C, preferably 35 ° C to 150 ° C, more preferably 40 ° C to 120 ° C.

  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 Example 1
<Synthesis of ester compound (A-1)>
In a flask equipped with a thermometer, an air / nitrogen mixed gas introduction tube, a stirrer, a water separator, and a reflux condenser, 210 parts of trimellitic acid, 365.4 parts of 2-hydroxyethyl acrylate, 70 parts of toluene, p- Charge 5 parts of toluenesulfonic acid and 2 parts of p-methoxyphenol, raise the temperature to 120 ° C while stirring under an air / nitrogen mixed gas stream, and continuously remove the generated water from the system using a water separator. The reaction was continued until the acid value of the reaction solution was 5 or less. After completion of the reaction, toluene was distilled off under reduced pressure to obtain trimellitic acid ester (A-1) having an acryloyl group.

Production Example 2
<Synthesis of ester compound (A-2)>
A flask equipped with a thermometer, air / nitrogen mixed gas introduction tube, stirrer, water separator and reflux condenser was charged with 254 parts pyromellitic acid, 344 parts vinyl acetate, 5 parts calcium hydroxide and 70 parts toluene. The mixture was allowed to react for 12 hours under reflux in an oil bath at 120 ° C. while stirring under an air / nitrogen mixed gas stream. After cooling, it was washed three times with water, and toluene was distilled off under reduced pressure to obtain a pyromellitic acid ester (A-2) having a vinyl group.

Production Example 3
<Synthesis of ester compound (A-3)>
A flask equipped with a thermometer, an air / nitrogen mixed gas introduction tube, a stirrer, a water separator, and a reflux condenser was charged with 210 parts of trimellitic acid, 76.5 parts of allyl chloride, 70 parts of toluene and 101 parts of triethylamine. The mixture was stirred at 25 ° C. for 20 hours under an air / nitrogen mixed gas stream. After completion of the reaction, the precipitate was removed by filtration, and toluene was distilled off under reduced pressure to obtain trimellitic acid ester (A-3) having an allyl group.

Production Example 4
<Synthesis of acrylate (B-1) having urethane group>
In a flask equipped with a stirrer, an air / nitrogen mixed gas inlet tube, a condenser tube and a thermometer, 568 parts of butyl acetate, 168 parts of hexamethylene diisocyanate, 1.2 parts of p-methoxyphenol and 1.2 parts of dibutyltin diacetate The temperature was raised to 70 ° C. under a stream of air / nitrogen mixed gas, and while maintaining the temperature at 70 ± 10 ° C., “light acrylate PE3A” [manufactured by Kyoeisha Chemical Co., Ltd .: pentaerythritol diacrylate and pentane 795 parts of a mixture of erythritol triacrylate and pentaerythritol tetraacrylate (weight ratio is about 5:60:35)] was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was allowed to proceed at 70 ° C. for 3 hours under a stream of air / nitrogen mixed gas, and butyl acetate was distilled off under reduced pressure to obtain an acrylate (B-1) having a urethane group. Mn of (B-1) was 1200.

Production Example 5
<Synthesis of acrylate (B-2) having urethane group>
An acrylate (B-2) having a urethane group was obtained in the same manner as in Production Example 4, except that “795 parts of“ light acrylate PE3A ”” was changed to “243.6 parts of 2-hydroxyethyl acrylate”. Mn of (B-2) was 450.

Production Example 6
<Synthesis of acrylate (B-3) having urethane group>
“Hexamethylene diisocyanate 168 parts” is changed to “4,4′-dicyclohexylmethane diisocyanate 262 parts”, “Light acrylate PE3A” 795 parts is changed to “Neomer DA-600” (manufactured by Sanyo Chemical Industries, Ltd .: Dipenta A mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate) 831 parts ”was used in the same manner as in Production Example 4 to obtain an acrylate (B-3) having a urethane group. Mn of (B-3) was 1500.

Production Example 7
<Synthesis of acrylate (B-4) having urethane group>
Except for changing “light acrylate PE3A” 795 parts to “2-hydroxyethyl acrylate 243.6 parts” and “hexamethylene diisocyanate 168 parts” to “isophorone diisocyanate 222 parts”, the same as in Production Example 4, An acrylate (B-4) having a urethane group was obtained. Mn of (B-4) was 550.

Production Example 8
<Synthesis of acrylate (B-5) having a urea group>
An acrylate (B-5) having a urea group was obtained in the same manner as in Production Example 4 except that “795 parts of“ light acrylate PE3A ”” was changed to “243.6 parts of 2-aminoethyl acrylate”. Mn of (B-5) was 500.

Production Example 9
<Synthesis of acrylate (B-6) having urethane group>
An acrylate (B-6) having a urethane group was obtained in the same manner as in Production Example 4 except that “168 parts of hexamethylene diisocyanate” was changed to “250 parts of 4,4′-diphenylmethane diisocyanate”. Mn of (B-6) was 1300.

Production Example 10
[Synthesis of Acid Generator (D2-1) {Compound Represented by Chemical Formula (9)}]

  6.5 parts of toluene, 8.1 parts of isopropylbenzene, 5.35 parts of potassium iodide and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid, cooled to 10 ° C., and kept at a temperature of 10 ± 2 ° C. A mixed solution of 12 parts of sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour. 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 [trifluoro {tris (perfluoroethyl)} phosphate] 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 ethyl acetate was distilled off under reduced pressure to obtain 5.0 parts of a light yellow solid acid generator (D2-1).

Example 1 [Photosensitive composition for hard coat]
Ester compound (A-1) 16 parts, urethane group-containing acrylate (B-1) 67 parts, urethane group-containing acrylate (B-2) 17 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide [BASF Corp. "LUCIRIN TPO"] (C-1), 0.5 part of acid generator (D2-1) and aminopolyether-modified silicone as a leveling agent ["KF-889" manufactured by Shin-Etsu Chemical Co., Ltd.] 1 Parts were mixed at once, and mixed and stirred uniformly with a disperser to obtain a photosensitive composition (Q-1) of the present invention.

Example 2 [Photosensitive composition for hard coat]
The same procedure as in Example 1 was conducted except that the acid generator (D2-1) was not used and the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C-1) was changed to 5.5 parts. The photosensitive composition (Q-2) of this invention was obtained.

Example 3 [Photosensitive composition for hard coat]
“Acrylate having a urethane group (B-1)” is changed to “Acrylate having a urethane group (B-3)”, and “Acrylate having a urethane group (B-2)” is changed to “Acrylate having a urethane group (B-4)”. The photosensitive composition (Q-3) of the present invention was obtained in the same manner as in Example 1 except that it was changed to “)”.

Example 4 [Photosensitive composition for hard coat]
“67 parts of acrylate having urethane group (B-1)” is changed to “5 parts of acrylate having urea group (B-5)” and “17 parts of acrylate having urethane group (B-2)” is changed to “urethane group. A photosensitive composition (Q-4) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to “5 parts of acrylate (B-6)”.

Example 5 [Photosensitive composition for hard coat]
A photosensitive composition (Q-5) of the present invention was obtained in the same manner as in Example 1 except that “ester compound (A-1)” was changed to “ester compound (A-2)”.

Example 6 [Photosensitive composition for hard coat]
A photosensitive composition (Q-6) of the present invention was obtained in the same manner as in Example 1 except that “ester compound (A-1)” was changed to “ester compound (A-3)”.

Example 67 [Photosensitive composition for hard coat]
Add “neomer EA-300 [Sanyo Chemical Industries, Ltd .: pentaerythritol tetraacrylate] (E-1) 60 parts” without using urethane group-containing acrylates (B-1) and (B-2). And the photosensitive composition (Q-7) of this invention was obtained like Example 1 except changing the preparation amount of an ester compound (A-1) into 40 parts.

Example 8 [Photosensitive composition for hard coat]
Other than changing the acid generator (D2-1) to iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate [“IRGACURE 250” manufactured by BASF] (D2-2) In the same manner as in Example 1, a photosensitive composition (Q-8) of the present invention was obtained.

Example 9 [Photosensitive composition for hard coat]
Except for changing the acid generator (D2-1) to [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate ["CPI-100P" manufactured by San Apro Co., Ltd.] (D1-1), Examples In the same manner as in No. 1, a photosensitive composition (Q-9) of the present invention was obtained.

Example 10 [Photosensitive composition for hard coat]
Except for changing the acid generator (D2-1) to triphenylsulfonium trifluoromethanesulfonate [“WPAG-281H” manufactured by Wako Pure Chemical Industries, Ltd.] (D1-2), the same as in Example 1, The photosensitive composition (Q-10) of this invention was obtained.

Comparative Example 1
Except that the ester compound (A-1) was not used and the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C-1) was changed to 5.5 parts, the same as in Example 1, A comparative photosensitive composition (Q′-1) was obtained.
Comparative Example 2
Except for adding 10 parts of silica sol [Nissan Chemical Industries "Snowtex UP"] and changing the amount of urethane group-containing acrylate (B-1) to 57 parts in the same manner as in Comparative Example 1. A comparative photosensitive composition (Q′-2) was obtained.

[Performance evaluation of coating after curing]
Each of the photosensitive compositions for hard coat obtained in Examples 1 to 10 and Comparative Examples 1 and 2 was subjected to surface treatment and a 100 μm thick PET (polyethylene terephthalate) film [“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd. ] Was applied using an applicator so as to have a film thickness of 20 μm, and was exposed using a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”). The exposure dose at 365 nm was 150 mJ / cm ² .

[Performance evaluation method]
(1) Pencil hardness Pencil hardness is measured according to JIS K-5400.

(2) Adhesiveness In accordance with JIS K-5400, the adhesiveness is evaluated by a grid cellophane tape peeling test.

(3) Transmittance and haze (transparency)
Based on JIS-K7105, a transmittance and haze are measured using a total light transmittance measuring device [trade name “haze-garddual” manufactured by BYK Gardner Co., Ltd.]. In both cases, the unit is%.

Example 11 [Photosensitive composition for negative resist]
5 parts of ester compound (A-1), 33 parts of acrylate having urethane group (B-1), 6 parts of acrylate having urethane group (B-2), “Neomer DA-600” [manufactured by Sanyo Chemical Industries, Ltd. : Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate] (E-2) 5 parts, ethanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- 1- (0-acetyloxime) ["IRGACURE OXE 02" manufactured by BASF] (C-2) 4.5 parts, 2-hydroxy-2-methyl-1-phenyl-propan-1-one [manufactured by BASF " DAROCUR 1173 "] (C-3) 2 parts, acid generator (D2-1) 0.5 parts, diethylthioxanthone as a sensitizer [Nippon Kayaku Co., Ltd. “Kayacure DETX-S”] 5 parts, CCR-1314H as a polymer having a carboxyl group [manufactured by Nippon Kayaku Co., Ltd.] 24 parts, ethylene glycol monomethyl ether as an organic solvent [manufactured by Tokyo Chemical Industry Co., Ltd.] 15 Parts were kneaded at 25 ° C. for 3 hours using a ball mill to produce a photosensitive composition (Q-11) of the present invention.

Example 12 [Photosensitive composition for negative resist]
Without using an acid generator (D2-1), ethanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) (C The photosensitive composition (Q-12) of the present invention was obtained in the same manner as in Example 11 except that the charge amount of -2) was changed to 5.5 parts.

Example 13 [Photosensitive composition for negative resist]
“Acrylate having a urethane group (B-1)” is changed to “Acrylate having a urethane group (B-3)”, and “Acrylate having a urethane group (B-2)” is changed to “Acrylate having a urethane group (B-4)”. The photosensitive composition (Q-13) of the present invention was obtained in the same manner as in Example 11 except for changing to ")".

Example 14 [Photosensitive composition for negative resist]
"33 parts of acrylate having urethane group (B-1)" is replaced with "5 parts of acrylate having urea group (B-5)" and "6 parts of acrylate having urethane group (B-2)" is replaced with "urethane group. A photosensitive composition (Q-14) of the present invention was obtained in the same manner as in Example 11 except for changing to "1 part of acrylate (B-6) having".

Example 15 [Photosensitive composition for negative resist]
A photosensitive composition (Q-15) of the present invention was obtained in the same manner as in Example 11 except that “ester compound (A-1)” was changed to “ester compound (A-2)”.

Example 16 [Photosensitive composition for negative resist]
A photosensitive composition (Q-16) of the present invention was obtained in the same manner as in Example 11 except that “ester compound (A-1)” was changed to “ester compound (A-3)”.

Example 17 [Photosensitive composition for negative resist]
Except not using acrylate (B-1) and (B-2) which have a urethane group, it carried out similarly to Example 11, and obtained the photosensitive composition (Q-17) of this invention.

Example 18 [Photosensitive composition for negative resist]
Except for changing the acid generator (D2-1) to iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate (D2-2), the same procedure as in Example 11 was performed. Thus, a photosensitive composition (Q-18) of the present invention was obtained.

Example 19 [Photosensitive composition for negative resist]
The photosensitive composition of the present invention was the same as in Example 11 except that the acid generator (D2-1) was changed to [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate (D1-1). A product (Q-19) was obtained.

Example 20 [Photosensitive composition for negative resist]
A photosensitive composition (Q-20) of the present invention was obtained in the same manner as in Example 11 except that the acid generator (D2-1) was changed to triphenylsulfonium trifluoromethanesulfonate (D1-2). .

Comparative Example 3
A photosensitive composition for comparison (Example 1) except that the ester compound (A-1) was not used and the amount of the acrylate (B-1) having a urethane group was changed to 38 parts. Q′-3) was obtained.

[Evaluation of coating film developability]
Each negative resist photosensitive composition obtained in Examples 11 to 20 and Comparative Example 3 was subjected to surface treatment and a 100 μm thick PET (polyethylene terephthalate) film [“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.] Then, it was applied using an applicator to a film thickness of 20 μm. Subsequently, pre-baking was performed at 80 ° C. for 3 minutes under reduced pressure (4 kPa) to dry the solvent. Next, a linear mask having a width of 15 μm was set and then exposed. For the exposure, a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”) was used. The exposure dose was 75 mJ / cm ² and 150 mJ / cm ² at 365 nm.
The test specimen after exposure was immersed in a 1% NaCO ₂ aqueous solution for 100 seconds, and then alkali development was performed by spraying ion exchange water. Subsequently, post-baking was performed at 80 ° C. for 3 minutes under reduced pressure (4 kPa).
Table 2 shows the results of visually observing the developability of the coating film after development with an optical microscope and evaluating the area (%) on which patterning can be performed according to the following evaluation criteria.
(Double-circle): It has patterned without missing 98% or more.
○ to ◎: Patterning can be performed without chipping in a range of 95% or more and less than 98%.
○: Patterning can be performed without chipping in the range of 92% or more and less than 95%.
(Triangle | delta): It has patterned without missing in the range of 90% or more and less than 92%.
X: The area | region which is not missing is less than 90%, and it has not patterned.

Example 21 [Photosensitive composition for UV curable ink]
[Preparation of ink composition]
<Preparation of high concentration pigment dispersion>
42 parts of titanium oxide [Ishihara Sangyo "Typaque R-930"], pigment dispersant [Lubrisol "Solspers 32000"] 5 parts, N, N-diethylacrylamide [Kojin Co., Ltd. "DEAA"] A mixture of 31 parts of (E-3) and 22 parts of the ester compound (A-1) was kneaded for 3 hours using a ball mill to prepare a pigment dispersion having a pigment concentration of 42%.
<Preparation of ink composition containing pigment>
43 parts of the pigment dispersion, 32 parts of acrylate (B-1) having a urethane group, 14 parts of acrylate (B-2) having a urethane group, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C-1) 4 .5 parts, 4,4′-bis (dimethylamino) benzophenone as a sensitizer [“SpeedCure EMK” manufactured by Nippon Sebel Hegner] and diethylthioxanthone [“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.] Two parts and 0.5 part of an acid generator (D2-1) were kneaded at 25 ° C. for 3 hours using a ball mill to obtain a photosensitive composition (Q-21) of the present invention.

Example 22 [Photosensitive composition for UV curable ink]
The same procedure as in Example 21 was conducted except that the acid generator (D2-1) was not used and the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (C-1) was changed to 5.5 parts. The photosensitive composition (Q-22) of this invention was obtained.

Example 23 [Photosensitive composition for UV curable ink]
“Acrylate having a urethane group (B-1)” is changed to “Acrylate having a urethane group (B-3)”, and “Acrylate having a urethane group (B-2)” is changed to “Acrylate having a urethane group (B-4)”. The photosensitive composition (Q-23) of the present invention was obtained in the same manner as in Example 21, except for changing to ")".

Example 24 [Photosensitive composition for UV curable ink]
"32 parts of acrylate having urethane group (B-1)" is replaced with "10 parts of acrylate having urea group (B-5)" and "14 parts of acrylate having urethane group (B-2)" is replaced with "urethane group. A photosensitive composition (Q-24) of the present invention was obtained in the same manner as in Example 21 except that the content was changed to "10 parts of acrylate (B-6) having".

Example 25 [Photosensitive composition for UV curable ink]
A photosensitive composition (Q-25) of the present invention was obtained in the same manner as in Example 21, except that “ester compound (A-1)” was changed to “ester compound (A-2)”.

Example 26 [Photosensitive composition for UV curable ink]
A photosensitive composition (Q-26) of the present invention was obtained in the same manner as in Example 21, except that "ester compound (A-1)" was changed to "ester compound (A-3)".

Example 27 [Photosensitive composition for UV curable ink]
Except not using acrylate (B-1) and (B-2) which have a urethane group, it carried out similarly to Example 21, and obtained the photosensitive composition (Q-27) of this invention.

Example 28 [Photosensitive composition for UV curable ink]
Except for changing the acid generator (D2-1) to iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate (D2-2), the same procedure as in Example 21 was performed. Thus, a photosensitive composition (Q-28) of the present invention was obtained.

Example 29 [Photosensitive composition for UV curable ink]
The photosensitive composition of the present invention was the same as in Example 21, except that the acid generator (D2-1) was changed to [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate (D1-1). Thing (Q-29) was obtained.

Example 30 [Photosensitive composition for UV curable ink]
A photosensitive composition (Q-30) of the present invention was obtained in the same manner as in Example 21, except that the acid generator (D2-1) was changed to triphenylsulfonium trifluoromethanesulfonate (D1-2). .

Comparative Example 4
A comparative photosensitive composition (Q′-4) was prepared in the same manner as in Example 21 except that “ester compound (A-1)” was changed to “urethane group-containing acrylate (B-3)”. Obtained.

[Curability evaluation]
A 100 μm thick PET (polyethylene terephthalate) film [“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.] obtained by subjecting each of the photosensitive compositions for UV curable inks obtained in Examples 21 to 30 and Comparative Example 4 to surface treatment. Then, it was applied using an applicator to a film thickness of 20 μm. For the exposure, a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”) was used. The exposure dose was 75 mJ / cm ² and 150 mJ / cm ² at 365 nm.
Table 3 shows the results of evaluating the curability immediately after light irradiation of the coated film after curing with the following evaluation criteria by scratching with finger touch and nails.
A: There is no tack on the surface, and it is not damaged by the nails.
○ to ◎: There is no tack on the surface and the nail is not scratched, but a mark remains.
○: There is no tack on the surface, but the nail is damaged.
X: There is tack on the surface, and the nail is damaged.

  Since the cured film after curing of the active energy ray-curable photosensitive composition of the present invention is excellent in hardness, adhesion and high transparency, it is used for resin molded product hard coat and display hard coat (CRT, liquid crystal display). , For plasma display, electroluminescence display or touch panel). The cured film obtained by curing the active energy ray-curable photosensitive composition of the present invention is also useful as a protective film for a polarizing plate. In addition, because it has excellent developability of the resist pattern of the cured film, it is also useful as a resist film and can be cured with a thick film at a high colorant concentration even with a small amount of energy. It is also useful for printing inks and the like.

Claims (12)

  At least one ester compound (A) selected from the group consisting of phthalic acid ester, trimellitic acid ester and pyromellitic acid ester having ethylenically unsaturated bond-containing group (x), polymerization initiator (C), and necessary An active energy ray-curable photosensitive material comprising at least one of (meth) acrylate (B) having a urethane group and / or urea group and an acid generator (D) that generates an acid by active energy rays. Sex composition.   The photosensitive property according to claim 1, wherein the ethylenically unsaturated bond-containing group (x) is at least one substituent selected from the group consisting of a (meth) acryloyl group, a vinyl group, a 1-propenyl group, and an allyl group. Composition. The photosensitive composition according to claim 1 or 2, wherein the ester compound (A) is a compound represented by any one of the following general formulas (1) to (3).

[Wherein, R ^{1 to} R ⁹ are each independently a substituent represented by any one of the following general formulas (4) to (8). ]

[Wherein R ¹⁰ , R ¹² and R ¹⁴ are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and R ¹¹ , R ¹³ and R ¹⁵ are each independently a hydrogen atom or a methyl group. * Represents that the substituent is bonded to the oxygen atom of the oxycarbonyl group in the general formulas (1) to (3) by the bond to which it is attached. ]   Active hydrogen component (h) and organic polyisocyanate containing (meth) acrylate (B) having urethane group and / or urea group, (meth) acrylate having hydroxyl group and / or (meth) acrylate having amino group The photosensitive composition according to claim 1, which is a compound obtained by reacting component (i).   The organic polyisocyanate component (i) is isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, The photosensitive composition of Claim 4 containing the at least 1 sort (s) of isocyanate chosen from the group which consists of 4,4'- diphenylmethane diisocyanate and 1, 5- naphthalene diisocyanate.   The polymerization initiator (C) is an acylphosphine oxide derivative polymerization initiator (C1), an α-aminoacetophenone derivative polymerization initiator (C2), a benzyl ketal derivative polymerization initiator (C3), or an α-hydroxyacetophenone derivative. At least one radical polymerization selected from the group consisting of a systemic polymerization initiator (C4), a benzoin derivative polymerization initiator (C5), an oxime ester derivative polymerization initiator (C6) and a titanocene derivative polymerization initiator (C7). It is an initiator, The photosensitive composition in any one of Claims 1-5.   The photosensitive composition according to any one of claims 1 to 6, wherein the acid generator (D) that generates an acid by active energy rays is a sulfonium salt (D1) and / or an iodonium salt (D2). The photosensitive composition according to claim 7, wherein the iodonium salt (D2) is a compound represented by the following chemical formula (9).

  (Meth) acrylate having a content of the ester compound (A) of 1 to 80% by weight, a content of the polymerization initiator (C) of 0.05 to 30% by weight, and having a urethane group and / or a urea group ( The photosensitivity according to any one of claims 1 to 8, wherein the content of B) is 0 to 90 wt%, and the content of the acid generator (D) that generates an acid by the active energy ray is 0 to 30 wt%. Composition.   The photosensitive composition according to any one of claims 1 to 9, which is used for hard coating (for hard coating of resin molded products or for hard coating of displays), for resist, or for UV curable ink.   Hardened | cured material formed by hardening | curing the photosensitive composition in any one of Claims 1-10 with an active energy ray.   The cured product according to claim 11, which is a hard coat coating film or a resist film.