JP2007191605A - Photocurable varnish - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable varnish which can inhibit the bleeding of photopolymerization initiators, photopolymerization initiator degradation products, sensitizers, and other compositions in printed articles, and can prevent the deterioration of low odor, cured coating film hardness and curability. <P>SOLUTION: This photocurable varnish comprises a resin, a monomer, and a specific oxime ester derived from a ketoxime in which one bonding hand of an acyl group is directly bonded to a benzene ring and the other is bonded to an oxime structure unit, as a photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photocurable varnish containing a photopolymerization initiator that is cured by light irradiation, and more specifically, a photopolymerization initiator, a photopolymerization initiator decomposition product, a sensitizer, and the like from the coating surface after varnish curing The present invention relates to a photo-curing varnish that can suppress oozing and leaching of the composition and odor.

Photocurable coating compositions, especially UV curable coating compositions are printing inks, clear varnishes, paints, photosensitive resins for printing plates, adhesives, adhesives, color filter resists, printed circuit board resists, semiconductor photoresists. Research has been actively conducted in the fields of hologram materials, molding resins, casting resins, optical modeling resins, sealants, various devices, and the like. These consist of photoinitiators, resins (including both resins having radical polymerizability and resins having no radical polymerizability), monomers having radical polymerizability, pigments (not included in clear varnish), additives, and the like. . Commonly used photoinitiators include benzophenone series such as methyl o-benzoylbenzoate, acetophenone series such as Darocur 1173, Darocur 2959, Irgacure 184, Irgacure 907 (Irgacure and Darocur are trademarks of Ciba Specialty Chemicals), Hydrogen donating systems such as benzoin, thioxanthone, EAB (made by Hodogaya Chemical Co., Ltd.), Seikol PAA (made by Seiko Chemical Co., Ltd.), Kayacure EPA (made by Nippon Kayaku Co., Ltd.) such as Irgacure 651 are used. It is also known that oxime compounds function as radical photopolymerization initiators. It is known that certain O, O′-diacylglyoximes function as photoradical polymerization initiators (see Non-Patent Documents 1 to 3). Furthermore, it is also known that certain oxime esters having a structure similar to O, O′-diacylglyoxime function as photoradical polymerization initiators (see Patent Documents 1 and 2). Further, α-ketoxime esters have been disclosed as photo radical polymerization initiators for positive or negative photosensitive polyimide precursor compositions (see Patent Document 3). Some benzophenone oxime ester compounds have been disclosed (see Patent Documents 4 and 5). In addition, certain α, α-diketooxime ester compounds are disclosed (see Patent Documents 6 to 10). Also, certain O-acyloxime ester compounds are disclosed (see Patent Documents 11 and 12). Also, certain O-sulfonyl oxime ester compounds and O-phosphoryl oxime ester compounds have been disclosed (see Patent Document 13). Furthermore, a photopolymerizable composition comprising an O-acyloxime ester compound and a carbazole derivative is disclosed (see Patent Document 14).
Journal of Polymer Science, Polymer Chemistry Edition, 1972, 10 (11), 3405-3419 Journal of Polymer Science, Polymer Chemistry Edition, 1974 12 (11), 2553-2566 Sumyu Konghakhoe Chi, 1972, 9 (2), 97-110 US Pat. No. 3,558,309 US Pat. No. 4,255,513 JP-A-7-140,658 US Pat. No. 4,590,145 JP-A-61-24,558 US Pat. No. 5,019,482 Japanese Patent Laid-Open No. 62-184,056 JP-A-62-273,259 JP 62-286,961 A JP-A-62-201,859 JP 2001-233842 A JP 2000-80,068 Special table 2002-538,241 gazette JP-A-2005-187,678

Since general photopolymerization initiators may be low molecular weight compounds, various disadvantages are caused when they are used. For example, the photopolymerization initiator, photopolymerization initiator decomposition product, sensitizer, and other compositions may bleed out from the cured curable coating composition. It is not preferable. In addition, bleeding of the photoinitiator causes odors of printing, coating sites or printed materials, and coated materials, and further causes problems such as deterioration of film hardness of printed materials. An object of the present invention is to prevent photopolymerization initiators, photopolymerization initiator decomposition products, sensitizers, and other compositions from suppressing bleeding, low odor, cured film hardness, and curability deterioration in printed materials.
Moreover, it is often performed to print a photocurable varnish on the printed ink with an offset printer, and such a photocurable varnish is also called an overprint varnish (OP varnish). The OP varnish is offset printed in the same manner as the ink, but depending on the type of the photopolymerization initiator, there may be a non-image residue that is called a piling phenomenon. In offset printing, when ink or varnish (hereinafter referred to as ink) is supplied from the ink fountain to the plate surface via a plurality of rollers, and dampening water is supplied from the water boat to the plate surface via a plurality of rollers. Since the image area on the printing plate is oleophilic, ink or the like is accepted, and since the non-image area on the printing plate is hydrophilic, an image is formed on the paper surface by coating with dampening water. If there is an imbalance between the amount of ink supplied and the amount of dampening water supplied, printing troubles may occur. Among them, the piling phenomenon often occurs due to insufficient dampening water during printing. .
It is a further object of the present invention to provide a photocurable varnish suitable for offset varnished OP varnish applications that does not cause a piling phenomenon.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, this invention relates to the photocurable varnish which consists of resin, a monomer, and the photoinitiator represented by following General formula (1).

General formula (1)

(However, in the formula, R _{1 to} R ₅ each independently represents a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₅ may be an alkoxy group which may have a substituent, or In addition, R _{1 to} R ₅ may be a cyclic structure in which adjacent substituents are bonded to each other in an integrated manner.
R ₆ represents a monovalent organic residue. )

  Furthermore, the present invention relates to a printed matter obtained by printing the photocurable varnish on a substrate and curing it by light irradiation.

  Furthermore, this invention relates to the manufacturing method of the printed matter which prints the said photocurable varnish on a base material, and hardens | cures by light irradiation.

Since the photocurable varnish of the present invention has excellent curability compared to the conventional photocurable varnish containing a general-purpose photoinitiator composition, the photopolymerization initiator and photopolymerization start from the coating surface after varnish curing. The amount of exudation such as volatilization and elution of the agent decomposition product, sensitizer and other compositions can be suppressed. Further, as a result, the odor derived from the photopolymerization initiator, the photopolymerization initiator decomposition product, the sensitizer, and other compositions can be reduced. Prints using this varnish are not only excellent for food packaging materials, but also lead to environmental improvements in the printing process.
Further, the structure of the photopolymerization initiator also has an effect of suppressing the pyring phenomenon.

  The photocurable varnish of the present invention comprises a resin, a monomer, and a photopolymerization initiator represented by the general formula (1). Various additives (for example, other polymerization initiators and photosensitizers) can be used in combination.

  First, the photopolymerization initiator will be described. As the photopolymerization initiator, an oxime ester derivative represented by the general formula (1) is used.

R _{1 to} R ₅ in the general formula (1) represent a hydrogen atom or a monovalent organic residue. However, one or more of R _{1 to} R ₅ are an alkoxy group which may have a substituent or an aryloxy group which may have a substituent. Further, two of R ₁ to R ₅ may be a cyclic structure bound to each other together.

Examples of the monovalent organic residue represented by R _{1 to} R ₅ include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An aryloxy group which may have a substituent, an acyloxy group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or a substituent Good alkylsulfanyl group, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkyl which may have a substituent Sulfonyl group, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, carbamoyl group which may have a substituent, substituted May have a group Rufamoiru group, an amino group which may have a substituent, a substituent having optionally phosphinoyl group, substituent a heterocyclic group which may have, a halogen group.

  Here, the alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, Dodecyl, okdadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl, 1-naphtho Irmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methyl Phenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-ni A trofenacyl group etc. are mentioned.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms,
Phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-
Phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-,
And p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoran Tenenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, biantracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, Naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group , Heptaphenyl group, heptacenyl group, pyrantrenyl group,
And an ovalenyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2- Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbo group Rumechiruokishi group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group,
2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3 A nitrophenyloxy group,
Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N, N-dialkylamino group. N, N-diarylamino group, N-alkyl-N-arylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkoxy group which may have a substituent, the aryloxy group which may have a substituent, substitution An acyloxy group which may have a group, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent An arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, Amino group which may have a group which may have a substituent phosphinoyl group, optionally the heterocyclic group may have a substituent may be further substituted with other substituents.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexylamino Groups such as alkylamino groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups, etc., arylamino groups such as phenylamino groups, p-tolylamino groups, methyl groups, ethyl groups, tert-butyl groups, In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups Group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumumyl group, dimethylsulfoniumumyl group, tri Such as phenylphenacylphosphoniumyl group It is.

Further, R _{1 to} R ₅ may be a cyclic structure in which adjacent substituents are integrally bonded to each other.

These substituents R _{1 to} R ₅ preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An aryloxy group that may be substituted, an acyl group that may have a substituent, a heterocyclic group that may have a substituent, and the like are exemplified, but the present invention is not limited to these examples.

At least one of the substituents R _{1 to} R ₅ is an alkoxy group which may have a substituent or an aryloxy group, but preferably R ₂ , R ₃ and R ₄ have a substituent. An alkoxy group that may be substituted, or an aryloxy group that may have a substituent, and more preferably, R ₂ and R ₃ have an alkoxy group that may have a substituent or a substituent. It may be an aryloxy group.

R ₆ in the general formula (1) represents a monovalent organic residue.

  The monovalent organic residue of R6 includes an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkoxy group that may have a substituent, and a substituent. An aryloxy group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a heterocyclic group which may have a substituent Etc.

Here, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a substituent As the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent, the aforementioned R _{1 to} R _This is synonymous with that described in ₅ .

In the substituent R ₆ , an alkyl group which may have a substituent and an aryl group which may have a substituent are preferable, and an alkyl group which may have a substituent is more preferable.

  Particularly preferable specific examples of the photopolymerization initiator described above include the following compounds (where Me is a methyl group, Et is an ethyl group, n-Pr is a normal propyl group, and iso-Pr is an isopropyl group). N-Bu is a normal butyl group, tert-Bu is a tertiary butyl group, n-Pe is a normal pentyl group, n-Hex is a normal hexyl group, OMe is a methoxy group, OEt is an ethoxy group, and Ac is an acetyl group. To express.)

Specific examples of compounds that can be represented by the general formula (1) are shown in Table 1. Table 2 shows specific examples in the case where R _{1 to} R ₅ have a cyclic structure in which adjacent substituents are integrally bonded to each other.

  As the resin of the photocurable varnish used in the present invention, there are a resin having radical polymerization and a resin having no radical polymerization. As the resin having radical polymerizability, alkyd (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or the like is used.

  Resins having no radical polymerizability include resins having a softening point of 70 to 120 ° C., and more specifically polyesters, epoxy esters, urethanes, diallyl phthalate resins, and the like, but the present invention is limited to these. It is not a thing.

  The monomer in the photocurable varnish of the present invention is a monomer having an ethylenically unsaturated bond capable of radical polymerization, and the monomer having an ethylenically unsaturated bond capable of radical polymerization is capable of radical polymerization in the molecule. Any monomer having at least one ethylenically unsaturated bond may be used. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

Examples of monomers having such an ethylenically unsaturated bond capable of radical polymerization include
Examples include acrylic acid derivatives, methacrylic acid derivatives, itaconic acid derivatives, crotonic acid derivatives, isocrotonic acid derivatives, unsaturated carboxylic acid derivatives such as maleic acid derivatives, and radically polymerizable monomers such as styrene derivatives. Is not to be done.

  Specific radical polymerizable monomers include (hydrogenated) bisphenol (A or F) alkylene oxide adduct diacrylate, (alkyl) phenol or polyhydric phenol alkylene oxide adduct acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl. Acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) butane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, Acrylic acid derivatives such as N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, (hydrogenated) bisphenol (A or F) alkylene oxide adduct dimethacrylate, (alkyl) phenol or polyhydric phenol alkylene oxide adduct methacrylate, Methyl methacrylate, N-butyl methacrylate Rate, 2-hexyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol ethanetri Methacrylic acid derivatives such as methacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of aryl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. More specifically, edited by Shinzo Yamashita et al., “Crosslinking agent handbook” (1981, Taiseisha) and Kato Seikatsu, “UV / EB Curing Handbook (raw material)” (1985, Polymer Publications), Radtech Research Group, “Application and Market of UV / EB Curing Technology”, 79, (1989, CMC), edited by Kiyoshi Akamatsu, “New / Sensitive Resin Technology” (1987, CMC), Shinichiro Takiyama, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun) Examples include radically polymerizable or crosslinkable monomers, oligomers and polymers known in the art or in the industry, but the present invention is not limited thereto.

  The photocurable varnish of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.

  Other polymerization initiators that can be used in combination with the photocurable varnish of the present invention include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP No. 3567453, diazonium compound gazette, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, JP-B 36-22062, JP-B 37-13109 Disclosed in Japanese Patent Publication No. SHO 38-18015 and SHO 45-9610. Luto-quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977) Various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science” (J.IMAG.SCI.), Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY REVIEW 84), 85-277 (1988) and JP-A-2- Transition metal complexes containing transition metals such as ruthenium described in 82701, Aluminate complexes described in JP-A-3-209477, Borate compounds described in JP-A-2-157760, JP-A-55-127550 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, JP-A-5-255347. Sulfonium complex or oxosulfonium complex described in JP-A No. 2001-264530, JP-A No. 2001-261761, JP-A No. 2000-80068, JP-A No. 2001-233842, US Pat. No. 3,558,309 (1971). ), USP4202697 (1980) and special Examples include oxime ester compounds described in JP-A 61-24558, but the present invention is not limited thereto.

  In addition, by combining with a sensitizer that absorbs ultraviolet to near-infrared light to increase the activity for light from the ultraviolet to the near-infrared region, it is an extremely sensitive photopolymerizable composition. Is possible.

  In the case of using such a photosensitizer, any one of known photosensitizers can be selected and used. Specific examples thereof include chalcone derivatives and dibenzalacetone. Unsaturated ketones, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, Polymethine dyes such as ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives , Tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium Derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, etc. Other specific examples include Ogahara Nobu et al., “Dye Handbook” (1986, Kodansha), Nobu Okawara et al., "Chemicals of Functional Pigments" (1981, CMC), Ed. Tadaburo Ikemori et al., "Special Functional Materials" (1986, Shibuya) The dyes and sensitizers described in (MC) are included, but are not limited thereto, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region. You may use 2 or more types by arbitrary ratios as needed. Among the sensitizers described above, a thioxanthone derivative may be mentioned as a sensitizer that can particularly preferably sensitize the photopolymerization initiator of the present invention. More specific examples include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. However, it is not limited to these.

  The photopolymerization initiator used in the present invention is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to the monomer.

  The resin / monomer composition ratio is 0.01 to 60% by weight for the resin and 10 to 95% by weight for the monomer.

  In addition, a polymerization inhibitor can be added to the photocurable varnish of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added to the photocurable varnish of the present invention include hydroquinone, p-methoxyphenol, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, and phenothiazine. The addition amount of the polymerization inhibitor is not particularly limited, but it is preferably used in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  The material used for the conventional photocurable varnish can be appropriately used for the photocurable varnish of the present invention. For example, viscosity adjusting agents, surfactants for adjusting printing properties of varnish, phosphoric acid additives for preventing sensitization of plates, and auxiliary agents for adjusting the surface of a cured film such as wax.

  In the polymerization reaction, the photocurable varnish of the present invention can be polymerized by applying energy by ultraviolet rays, visible rays, near infrared rays, electron beams or the like to obtain a desired polymer. The definitions of ultraviolet rays, visible rays, near-infrared rays and the like in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the photocurable varnish of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser, etc. Polymer or cured product can be obtained.

  As a method for applying the photocurable varnish of the present invention, for example, known means such as a roll coater, a gravure coater, a flexo coater, an offset printing machine, a screen printing machine can be appropriately employed, but the application is not limited thereto. Absent.

  The photocurable varnish is printed on a substrate to form a printed material. The substrate that can be used in the present invention is not particularly limited as long as it is a substrate that is usually used for printing, such as paper, synthetic paper, plastic, metal stay, and wood. These substrates may be printed with a primer, a picture, or characters before the varnish is printed. Further, the substrate may be subjected to a treatment such as a corona treatment.

  The photocurable varnish obtained in the present invention can be printed and cured using the same technique as in the prior art. The varnish of the present invention provides excellent curability compared to a photocurable varnish containing a conventional general-purpose photoinitiator composition, so that the photopolymerization initiator volatilizes and dissolves from the surface of the film after varnish curing. The amount of exudation can be suppressed. Furthermore, as a result, the odor derived from the photopolymerization initiator composition can be reduced.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited only to the following. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Synthesis example 1
A three-necked flask equipped with a stirrer was used as a reaction vessel. To this, 20 parts of the following compound (A), 20 parts of 4-methoxybenzoyl chloride, 10 parts of pyridine, and 100 parts of tetrahydrofuran were added and reacted for 3 hours with stirring to obtain compound (7). (Yield 79%).

Compound (A)

Synthesis example 2
The compound (42) shown in Table 1 was produced from the corresponding oxime according to the method described in Synthesis Example 1 using the corresponding acid chloride.

Synthesis example 3
Using a three-necked flask equipped with a stirrer as a reaction vessel, 50 parts of the following compound (B), 30 parts of acetic anhydride, 11 parts of NaOAc and 250 parts of tetrahydrofuran were added and reacted for 5 hours with stirring to obtain compound (4). (Yield 84%).

Compound (B)

Synthesis example 4
Compound (24) shown in Table 1 was produced from the corresponding oxime according to the method described in Synthesis Example 3.

Manufacture of varnish (mixture of resin, monomer, etc.) Dap tote DT170 (diallyl phthalate resin manufactured by Toto Kasei Co., Ltd.) 10%, ditrimethylolpropane tetraacrylate 89.9%, hydroquinone 0.10% are mixed and heated and melted. did.

Production Example 1A of Photocurable Varnish
Photocurable varnish (1A): A varnish, a photopolymerization initiator (compound (7)), and a photosensitizer (EAB, DETX, EPA) were mixed to obtain a photocurable varnish. The formulation is shown in Table 3.

Example 1B
Photocurable varnish (1B): A varnish, a photopolymerization initiator (compound (24)) and a photosensitizer (EAB, DETX, EPA) were mixed to obtain a photocurable varnish. The formulation is shown in Table 3.

Example 1C
Photocurable varnish (1C): A varnish, a photopolymerization initiator (compound (42)), and a photosensitizer (EAB, DETX, EPA) were mixed to obtain a photocurable varnish. The formulation is shown in Table 3.

Comparative Example 1D
Photocurable varnish (1D): A varnish, a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) and a photosensitizer (EAB, DETX, EPA) were mixed to obtain a photocurable varnish. The formulation is shown in Table 3.

Comparative Example 1E
Photocurable varnish (1E): A varnish, a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) and a photosensitizer (EAB, DETX, EPA) were mixed to obtain a photocurable varnish. The formulation is shown in Table 3.

The performance evaluation of the photocurable varnish was performed as follows. Table 4 describes the photocurable varnish performance evaluation of Examples 1A to 1C and Comparative Examples 1D and 1E.
-(1) Curability: In the case of each photo-curing varnish, the photo-curing varnish is printed with a bar coater # 2, irradiated with ultraviolet rays (high pressure mercury lamp 160W / cm1 lamp), and then rubbed with a cotton cloth so that the film is not damaged. Judged by conveyor speed. The larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.
(2) Solvent resistance: The printed material cured under the same conditions as the curability was rubbed with a cotton swab containing methyl ethyl ketone and judged at a conveyor speed at which the film was not damaged. The larger the number in the conveyor speed (m / min) of the ultraviolet irradiation device, the better the solvent resistance.
・ (3) Odoriness: Printed material cured under the same conditions as the curability is finely cut and packed in a glass bottle. The panelists of 5 persons have judged the odor relatively, and 1 (bad) to 5 (good) ).
(4) Bleed amount: An unprinted paper was placed on a printed material cured under the same conditions as the curability, and left for one day at a temperature of 60 ° C. and a pressure of 15 g / cm ² , and transferred to an unprinted paper. The amount of unreacted initiator and other compositions were quantified.

  From the results of Table 4, the photocurable varnish containing the photopolymerization initiator described in claim 1 of the present invention has excellent curability as compared with the photocurable varnish containing the conventional general-purpose photoinitiator composition. And was found to exhibit excellent solvent resistance. As a result, the amount of unreacted initiator in the cured film and the amount of exudation such as volatilization and elution of other compositions can be suppressed, and furthermore, it originates from the photopolymerization initiator and other compositions. Odor can be reduced.

  When a photocurable varnish is offset-printed as an OP varnish on the printed ink, there is an effect of suppressing a piling phenomenon depending on the type of the photopolymerization initiator. The photocurable varnish of the present invention exhibited excellent printing characteristics during offset printing, and no particular pyring phenomenon was observed. In addition, in the photocurable varnish using the compound (49) shown in Table 5 as the photopolymerization initiator, a piling phenomenon was observed during offset printing. Therefore, in order to evaluate the emulsification suitability of the varnish, which is an indicator of the piling phenomenon, the maximum water content of the photocurable varnish was measured.

Example 2A
The photocurable varnish was prepared in the same manner as in Example 1A using the compound (4) as a photopolymerization initiator. The measurement method is to mix a certain amount of light-curing varnish and a certain amount of purified water with high speed mixer while mixing to remove excess purified water that was not taken into the light-curing varnish, and then emulsify The water content of the photocured varnish was measured with a Karl Fischer moisture meter. The results are shown in Table 5. In order to obtain excellent printability, an allowable amount (maximum water content) capable of receiving dampening water in the inside of the photocurable varnish is generally 20%.

Comparative Example 2B
The water content of the emulsified photocurable varnish was measured in the same manner as in Example 2A, except that the compound (49) shown in Table 5 was used instead of the compound (4). The results are shown in Table 6.

  As a result of the measurement of the maximum moisture content of the photocurable varnish, Example 2A was within the range of about 20% in which the maximum moisture content was considered appropriate. As a result, it was found that Comparative Example 2B had a small maximum water content. These results are presumed to be attributable to the methyl group and ethyl group sites in the compounds (4) and (49), respectively.

  From the results shown in Table 6, the photocurable varnish containing the photopolymerization initiator described in claim 1 of the present invention has an emulsification ability that has an effect of suppressing the piling phenomenon, and is an OP varnish that is offset printed. It was found to be a photocurable varnish suitable for the application.

Claims (3)

A photocurable varnish comprising a resin, a monomer, and a photopolymerization initiator represented by the following general formula (1).
General formula (1)

(However, in the formula, R _{1 to} R ₅ each independently represents a hydrogen atom or a monovalent organic residue, and at least one of R _{1 to} R ₅ may be an alkoxy group which may have a substituent, or In addition, R _{1 to} R ₅ may be a cyclic structure in which adjacent substituents are bonded to each other in an integrated manner.
R6 represents a monovalent organic residue. )   A printed matter obtained by printing the photocurable varnish according to claim 1 on a substrate and curing it by light irradiation.   The manufacturing method of the printed matter which prints the photocurable varnish of Claim 1 on a base material, and is hardened | cured by light irradiation.