JP2005264024A - Photopolymerization initiator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To lower or eliminate exudation or odor of a material derived from a photopolymerization initiator in a coating film cured after photopolymerization. <P>SOLUTION: The photopolymerization initiator has at least two partial structures represented by the formula and at least two polymerizable unsaturated double bond groups [in formula (1) R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each an hydrogen atom or the like]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photopolymerization initiator for photopolymerization of an ethylenically unsaturated compound-containing system. The initiator significantly reduces or eliminates the exudation and odor from the cured coating in applications where photoinitiator leaching or odor remaining in the cured coating after photopolymerization is a problem. can do.

  In recent years, a large amount of photocurable compositions, particularly curable compositions using ultraviolet rays, have been used. For example, printing ink, overcoat varnish, paint, adhesive, photoresist and the like can be mentioned. These consist of photoinitiators, resins (including both resins having radical polymerizability and resins not having radical polymerizability), monomers having radical polymerizability, pigments (which may not be contained), additives, and the like. .

  Commonly used photoinitiators include benzophenone series such as methyl o-benzoylbenzoate, acetophenone series such as 2,2-diethoxyacetophenone, 4-phenoxy-2,2-dichloroacetophenone, 2-hydroxy-2 Propiophenones such as 4-methylpropiophenone and 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Oxime series such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], benzyl dimethyl ketone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone series, etc. it can.

  These photoinitiators are copolymerizable with resins used in photocurable compositions (including both radically polymerizable resins and non-radically polymerizable resins), and radically polymerizable monomers. Does not have. Therefore, these photoinitiators remain in the final cured film as an excess of unreacted residue or as a decomposition product generated by photoreaction, causing problems in the form shown below, for example .

Part of the residue is volatilized, causing odors in the printing / coating field or printed / coated material.
In applications that require transparency, such as films and overcoat varnishes, the residue causes color changes that occur over time, such as yellowing.
In the process of stacking and winding up printed materials / coating materials, the residue exudes / transfers from the printed surface or coated surface to other surfaces, and the exuded / transferred material touches the inclusions etc. This has an undesirable effect on the inclusion (for example, in the case of a beverage, the taste changes).
When used in electronic materials, the residue diffuses into the surrounding medium, causing electrical trouble in addition to problems such as yellowing and odor.

  In order to solve such a problem, a method using a copolymer of a photoinitiator derivative or a resin used for a photocurable composition (a resin having a radical polymerization property and a radical polymerization property has been used so far). Photoinitiators having copolymerizability are disclosed with respect to monomers having radical polymerizability).

  For example, polymer-type and copolymer-type initiators in which a benzophenone derivative is introduced by polymerization are disclosed, but all of these are improved in terms of odor, exudation, and migration, but the reactivity of the benzophenone derivative to ultraviolet rays is low, Sufficient curability was not obtained with a practical irradiation dose (see Patent Documents 1 to 3).

  Further, although a copolymerizable monoacrylate photoinitiator has been disclosed, monoacrylate has a low probability of being copolymerized at the time of ultraviolet irradiation, and could not completely prevent odor, oozing and migration (Patent Document 4). reference).

  Furthermore, an initiator having both a photoinitiator skeleton and a copolymerizable functional group or co-reactive group is disclosed as a co-reactive photoinitiator.

  However, since these initiators have only one copolymerizable functional group, the probability of being copolymerized at the time of ultraviolet irradiation is low, and it is impossible to completely prevent odor, oozing and migration, and these co-reactions The functional group has a slower reaction rate than the photopolymerization system, and it is highly possible that it will remain unreacted at a practical light dose. When such a functional group remains unreacted in the photocurable composition In addition to odor, exudation, and migration, which are problems in curing systems due to light irradiation, new problems derived from unreacted functional groups (such as poor stability over time of the composition, side reactions, and yellowing) may occur. When these functional groups are allowed to react completely, in addition to light irradiation, another operation such as heating is often required (see Patent Document 5).

Also disclosed are benzophenone-based initiators having a bifunctional or higher functional (meth) acryl group. By making it bifunctional or more, the probability of copolymerization at the time of ultraviolet irradiation increases, but the reactivity of the benzophenone skeleton itself to ultraviolet rays is low, and particularly in systems containing pigments, sufficient curability is not possible at practical irradiation doses. It was not obtained (see Patent Documents 6 and 7).
European Patent Publication No. 0017364 German patent application 24111169 European Patent Publication No. 2046848 European Patent (EP) 377191 Japanese Patent Laid-Open No. 10-175908 JP-A-9-20729 Japanese Patent Laid-Open No. 10-195026

  An object of the present invention is to reduce or eliminate the exudation and odor of a compound derived from a photopolymerization initiator from a cured coating film after photopolymerization.

  A photoinitiator skeleton having a high reactivity to ultraviolet light and a residue after photoreaction hardly remaining in the system, that is, at least two functional groups represented by the general formula (1) and at least two It has been found that the above-mentioned problems can be solved by using a photopolymerization initiator having a polymerizable unsaturated double bond group.

That is, the present invention includes at least two partial structures represented by the following general formula (1):
The present invention relates to a photopolymerization initiator having at least two polymerizable unsaturated double bond groups.

General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent. Further, they may be combined to form a ring.
R ³ represents a hydrogen atom or a substituent. )

Moreover, this invention relates to the said photoinitiator shown by following General formula (2).
General formula (2)

(In the formula, R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituent. R ¹ and R ² , and R ⁴ and R ⁵ may be combined to form a ring.
R ⁹ represents a tetravalent organic residue.
R ^{10 to} R ¹³ represent a divalent organic residue.
Ar ¹ and Ar ² each independently represent an arylene group that may be substituted. )

  The present invention also relates to a photopolymerizable composition comprising the photopolymerization initiator (A) and a compound having a polymerizable unsaturated double bond group other than (A).

The present invention also relates to a compound having a carboxyl group (Y) obtained by reacting a compound having two or more carboxylic anhydride groups with a compound (X) having a functional group capable of reacting with a carboxylic anhydride group. ) And a compound (Z) having a functional group capable of reacting with a carboxyl group, and at least two partial structures represented by the following general formula (1), and at least two polymerizable groups A method for producing a photopolymerization initiator having a saturated double bond group,
At least one of the compound (X) and the compound (Z) has a partial structure represented by the following general formula (1), and
A method for producing a photopolymerization initiator, wherein at least one of compound (X) and compound (Z) has an unsaturated double bond group.

General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent. Further, they may be combined to form a ring.
R ³ represents a hydrogen atom or a substituent. )

In the present invention, the compound (X) has a partial structure represented by the general formula (1), and
It is related with the manufacturing method of the said photoinitiator whose compound (Z) has an unsaturated double bond group.

  The present invention also relates to a method for producing a polymer, characterized in that the photopolymerization initiator is polymerized by irradiation with energy rays.

  The present invention also relates to a method for producing a polymer, wherein the photopolymerizable composition is polymerized by irradiation with energy rays.

  By this invention, the exudation of the compound derived from a polymerization initiator from the cured coating film after photopolymerization and the odor were reduced.

  The photopolymerization initiator (A) used in the present invention is a photopolymerization initiator having at least two partial structures represented by the general formula (1) and at least two polymerizable unsaturated double bond groups.

In the partial structure represented by the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a substituent, and may integrally form a ring such as a cyclo ring. R ³ represents a hydrogen atom or a substituent.

Here, the substituent includes a halogen atom, a cyano group, an amino group, and a monovalent organic residue.
Examples of the monovalent organic residue include alkyl groups such as a methyl group and an ethyl group, aromatic groups such as a phenyl group and a naphthyl group, and alkoxy groups such as a methoxy group and an ethoxy group.
In the partial structure of the general formula (1), one of the hydrogen atoms of the benzene ring on the left side of the general formula (1) serves as a bond and is bonded to the other structure of the photoinitiator (A). The position of the bond is not particularly limited, but a position corresponding to the p-position of the benzene ring is easily available.

  Specific examples of the partial structure of the general formula (1) include those shown below.

などが挙げられる。

Etc.

In particular, in the case where the cleaved fragment generated by cleaving the light of the partial structure represented by (i) does not directly participate in the photopolymerization reaction, one is combined with the other structure of the photoinitiator (A). Therefore, it does not cause exudation or odor, and the other that does not combine with other structures becomes a slight amount of acetone gas and volatilizes instantaneously, so that it does not easily cause exudation or odor (especially unpleasant odor).

  The polymerizable unsaturated double bond group of the present invention may be anything as long as it can participate in the polymerization mechanism that is initiated by irradiating the partial structure represented by the general formula (1) with energy rays. Examples include an acryloyl group, a methacryloyl group, a vinyl group, and a vinyl ether group.

As a preferable form of the photopolymerization initiator (A), a compound represented by the general formula (2) is exemplified.
In General formula (2), R < ¹ > -R < ⁸ > shows a hydrogen atom or a substituent each independently. Here, the substituent can illustrate the same thing as what was demonstrated by R < ¹ > -R < ³ > of General formula (1).
R ¹ and R ² , R ⁴ and R ⁵ may be combined to form a ring.
R ⁹ represents a tetravalent organic residue. R ^{10 to} R ¹³ represent a divalent organic residue. The organic residue in the present invention is an organic residue that described in R ¹ to R ³ in the general formula (1).

Ar ¹ and Ar ² are each an arylene group that may be independently substituted. The arylene group is a divalent functional group of an aromatic ring such as a benzene ring, a naphthalene ring, or a pyridine ring, and may have a substituent. Moreover, if the form of a bond is a benzene ring, o-, m-, p-, if it is a naphthalene ring, 1,2-, 1,3-, 1,4-, 2,3-, 1 , 5- and the like are not particularly limited.

Examples of the compound having at least two partial structures represented by the general formula (1) and at least two polymerizable unsaturated double bond groups include compounds represented by the general formula (2). The compound represented by (2) is, for example, a carboxyl group obtained by reacting a compound having two or more carboxylic anhydride groups with a compound (X) having a functional group capable of reacting with a carboxylic anhydride group. It is obtained by reacting the compound (Y) having a functional group capable of reacting with a carboxyl group, after obtaining the compound (Y) having a compound by synthesis or the like. At this time, at least one of the compound (X) and the compound (Z) has a partial structure represented by the general formula (1), and
At least one of compound (X) and compound (Z) has an unsaturated double bond group.

  The compound having two or more carboxylic acid anhydride groups of the present invention may be any compound having two or more carboxylic acid anhydride groups in one molecule. For example, tetracarboxylic dianhydride, hexa And polyvalent carboxylic acid anhydrides such as carboxylic acid dianhydride and maleic anhydride copolymer resin. In the present invention, these compounds can be used alone or in combination.

To illustrate in more detail,
Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfonetetracarboxylic dianhydride, butanetetracarboxylic dianhydride. Anhydride, Perylenetetracarboxylic dianhydride, Naphthalenetetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-10", "Ricacid MTA-15", "Ricacid TMEG series" manufactured by Shin Nippon Chemical Co., Ltd. ”,“ Licacid TDA ”and the like.
Maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Manufacturing Co., Ltd., and styrene maleic anhydride copolymer resins such as polyethylene maleic anhydride and α-olefin maleic anhydride copolymer resins such as polyethylene maleic anhydride. , "VEMA" (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., acrylic anhydride-modified polyolefin ("Aurolen series": manufactured by Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer An acrylic resin etc. are mentioned.
The compound having two or more carboxylic anhydride groups reacts with the compound (X) having a functional group capable of reacting with the carboxylic anhydride group to become a compound (Y) having a carboxyl group.

  Examples of the functional group capable of reacting with the carboxylic acid anhydride group of the present invention include a hydroxyl group, an epoxy group, a primary amino group, a secondary amino group, an isocyanate group, and a thioisocyanate group. Any functional group capable of reacting with an acid anhydride group may be used.

Specific examples of the compound (X) having a functional group capable of reacting with a carboxylic anhydride group.
First, those having an unsaturated double bond group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, 1,4-cyclohexanedimethanol monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl Methacrylate, glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate , Dipentaerythritol pentaacrylate, 1,4-butanediol diglycidyl ether acrylate, diethylene glycol diglycidyl ether acrylate, diglycerin polyglycidyl ether acrylate, “KAYARAD R-167”, “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd. “Aronix M-215”, “Aronix M-233”, “Aronix M-305”, “Aronix M-5700” manufactured by Synthetic Co., Ltd. “NK Oligo EA-5520”, “NK Oligo” manufactured by Shin-Nakamura Chemical Co., Ltd. “EA-5720”, “NK Oligo EA-5821”, “Blemmer GMR”, “Blemmer GAM”, “Blemmer G-FA”, “Blemmer GO”, “Blemmer G-SB”, “Blemmer QA” manufactured by NOF Corporation ”,“ Blemmer E ”,“ Blemmer PE-90 ”,“ Blemmer PE-200 ”,“ Blemmer PE-350 ”,“ `` Blemmer AE-90 '', `` Blemmer AE-200 '', `` Blemmer AE-400 '', `` Blemmer P '', `` Blemmer PP-1000 '', `` Blemmer PP-500 '', `` Blemmer PP-800 '', `` Blemmer AP- 150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50PEP-300, Blemmer 70PEP-350B, Blemmer AEP, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT, Blemmer 10PPB-500B ”,“ Blemmer 10APB-500B ”, hydroxyl-containing (meth) acrylates such as partially (meth) acrylated compounds of polyfunctional hydroxyl-containing compounds,

Glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, "CYCLOMER M-100", "CYCLOMER A-200", "M-GMA" manufactured by Daicel Chemical Industries, Ltd. ”, Epoxy compounds containing unsaturated double bond groups such as partially (meth) acrylated compounds of polyfunctional epoxy compounds,
Isocyanate group-containing (meth) acrylates such as methacryloyloxyethyl isocyanate, acryloyloxyethyl isocyanate, methacryloyl isocyanate, acryloyl isocyanate, partial (meth) acrylated compounds of polyfunctional isocyanate compounds,
Isothiocyanate group-containing (meth) acrylates such as methacryloyloxyethyl isothiocyanate, acryloyloxyethyl isothiocyanate, methacryloyl isothiocyanate, acryloyl isothiocyanate, partial (meth) acrylated compounds of polyfunctional isothiocyanate compounds,

2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 5-hydroxypentyl vinyl ether, 3-hydroxypropyl vinyl ether, trimethylolpropane divinyl ether, pentaerythritol trivinyl ether, di Hydroxyl-containing vinyl ethers such as pentaerythritol pentavinyl ether, partially vinyl etherified compounds of polyfunctional hydroxyl-containing compounds,

Epoxy group-containing vinyl ethers such as glycidyl vinyl ether, 4-hydroxybutyl vinyl ether glycidyl ether, tricyclodecane epoxy vinyl ether, and partial vinyl etherified compounds of polyfunctional epoxy compounds, vinyloyloxyethyl isocyanate, vinylyloyl isocyanate, polyfunctional isocyanate compounds Isocyanate group-containing vinyl ethers such as partially vinyl etherified compounds such as partially vinyl etherified compounds such as isocyanate group-containing vinyl ethers, vinyloyloxyethyl isothiocyanate, vinyliloyl isothiocyanate, and polyfunctional isothiocyanate compounds.

Moreover, as general things which do not have a specific structure, alkyl alcohols, such as methanol, ethanol, isopropanol, and butanol,
Ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1 , 3-butylene glycol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol,

N, N-dihydroxyethyl-n-butylamine, N, N-dihydroxypropyl-n-butylamine, N, N-dihydroxyethyl-tert-butylamine, N, N-dihydroxypropyl-tert-butylamine, N, N-dihydroxyethyl Isopropylamine, N, N-dihydroxypropylisopropylamine, N, N-dihydroxyethyl-n-stearylamine, N, N-dihydroxypropyl-n-stearylamine,
N, N-dihydroxyethyl-p-toluenesulfonamide, N, N-dihydroxypropyl-p-toluenesulfonamide,
N, N-dihydroxyethylaniline, N, N-dihydroxypropylaniline, N, N-dihydroxyethyl-m-toluidine, N, N-dihydroxypropyl-m-toluidine, N, N-dihydroxyethyl-p-toluidine, N , N-dihydroxypropyl-p-toluidine,
Hydroxyl-containing compounds such as N, N-dihydroxyethylbenzylamine, N, N-dihydroxypropylbenzylamine, N, N-dihydroxyethylpiperazine, N, N-dihydroxypropylpiperazine, polyfunctional alcohols,

Phenyl glycidyl ether, diglycidyl phthalate, hydroquinone diglycidyl ether, N-glycidyl phthalimide, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, glycerol poly Glycidyl ether, pentaerythrito Epoxy group-containing compounds such as polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyfunctional epoxy compound,

Amino group-containing compounds such as ethylamine, propylamine, butylamine, octylamine, benzylamine, cyclohexylamine, laurylamine, diethylamine, dibutylamine, stearylamine, hydrazine, adipic acid dihydrazide, polyfunctional amine compounds,

2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, isophorone Diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4 ' Isocyanates such as biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate Nate group-containing compounds,

2,4-tolylene diisothiocyanate, 2,6-tolylene isothiocyanate, m-phenylene diisothiocyanate, p-phenylene diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, tetramethylene diisothiocyanate, hexamethylene Diisothiocyanate, xylylene diisothiocyanate, lysine diisothiocyanate, isophorone diisothiocyanate, trimethylhexamethylene diisothiocyanate, 1,4-cyclohexylene diisothiocyanate, 4,4'-dicyclohexylmethane diisothiocyanate, 3,3 '-Dimethyl-4,4'-biphenylene diisothiocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisothiocyanate, 3,3'-dichloro-4,4'-biphenylene diisothiocyanate, 1, 5-Naphthalenediisothio Examples include cyanate and isothiocyanate group-containing compounds such as 1,5-tetrahydronaphthalene isothiocyanate.

  Moreover, as a compound of the present invention having a functional group capable of reacting with a carboxylic anhydride group and a partial structure represented by the general formula (1), 4- (2-hydroxyethoxy) -phenyl-2-hydroxy- 2-propyl ketone, 4- [2- (oxiranylmethoxy) -ethoxy] -phenyl-2-hydroxy-2-propyl ketone, 4- (2-aminoethoxy) -phenyl-2-hydroxy-2-propyl ketone 4-oxiranylmethoxyphenyl-2-hydroxy-2-propylketone, 4- (oxiranylmethoxycarbonylmethoxy) -phenyl-2-hydroxy-2-propylketone, 4-oxiranylmethoxyphenyl-α- Isopropoxybenzyl ketone, 4-oxiranylmethoxyphenyl-α, α-dimethoxybenzyl ketone, 4- (2-iso Anatoethoxy) -phenyl-2-hydroxy-2-propylketone, 4- (2-isothiocyanatoethoxy) -phenyl-2-hydroxy-2-propylketone, 4- (2-hydroxy-2-methylpropionyl)- Phenoxyacetamide, 4- (2-hydroxy-2-methylpropionyl) -phenoxyacetohydrazide, N- [4- (2-hydroxy-2-methylpropionyl) -phenoxyacetyl] -hydroxylamine, 4-isocyanatomethoxyphenyl- 2-hydroxy-2-propyl ketone, 4-isothiocyanatomethoxyphenyl-2-hydroxy-2-propyl ketone, and the like. In the present invention, these compounds can be used alone or in combination.

  The said compound (Y) which has a carboxyl group reacts with the compound (Z) which has a functional group which can react with a carboxyl group, and turns into a compound shown by General formula (1).

  Examples of the functional group capable of reacting with a carboxyl group in the present invention include an epoxy group, an amino group, an isocyanate group, a carbodiimide group, a vinyl ether group, an oxazoline group, and the like, and other functional groups capable of reacting with a carboxyl group. Anything is fine.

Specific examples of the compound having a functional group capable of reacting with a carboxyl group and a polymerizable unsaturated double bond group according to the present invention include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 4-hydroxybutyl. Methacrylate glycidyl ether, Daicel Chemical Industries, Ltd. “CYCLOMER M-100”, “CYCLOMER A-200”, “M-GMA”, Epoxy group containing (meth) acrylated compound of polyfunctional epoxy compound (meth) Acrylates,
Isocyanate group-containing (meth) acrylates such as methacryloyloxyethyl isocyanate, acryloyloxyethyl isocyanate, methacryloyl isocyanate, acryloyl isocyanate, partial (meth) acrylated compounds of polyfunctional isocyanates,
(Meth) acrylates containing isothiocyanate groups such as methacryloyloxyethyl isothiocyanate, acryloyloxyethyl isothiocyanate, methacryloyl isothiocyanate, acryloyl isothiocyanate, partially acrylated compound of polyfunctional isothiocyanate,

Carbodiimide group-containing (meth) acrylates such as partially (meth) acrylated compounds of polyfunctional carbodiimide compounds,
Containing vinyloxy groups such as 2-vinyloxyethyl acrylate, 2-vinyloxyethyl methacrylate, 2- (2′-vinyloxyethoxy) ethyl acrylate, 2- (2′-vinyloxyethoxy) ethyl methacrylate (meta ) Acrylate, vinyloxy group-containing styrene such as 2-vinyloxyethoxystyrene, 2-vinyloxyethylstyrene, “FX-VEEA”, “FX-VEEM” manufactured by Nippon Shokubai Co., Ltd., partial (meth) acrylate of polyfunctional vinyl ether compound Vinyl ether group-containing (meth) acrylates such as fluorinated compounds, vinyl oxazoline, isopropenyl oxazoline, and polymerizable unsaturated double bond group-containing oxazoline derivatives such as “VOZO” and “IPOZO” manufactured by Kojin Co., Ltd. . In the present invention, these compounds can be used alone or in combination.

Reaction of a carboxylic anhydride group with a functional group capable of reacting with a carboxylic anhydride group,
Alternatively, the reaction between the carboxyl group and the functional group capable of reacting with the carboxyl group can utilize known reaction conditions.

In the present invention, the compound having a polymerizable unsaturated double bond group other than (A) may be any compound having at least one polymerizable unsaturated double bond group. For example, (meth) acrylate Compounds, nitrogen-containing unsaturated compounds, fatty acid vinyl compounds, α-olefin compounds, vinyl compounds, vinyl ether compounds, and the like. In the present invention, these compounds can be used alone or in combination.
More specifically, examples of mono (meth) acrylate compounds include alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene glycol mono (meth) acrylate. And alkylene glycol type (meth) acrylates such as

Examples of the compound having two or more (meth) acrylate groups include 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayalad R-167, hydroxypivalic acid neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: alkyl type such as Nippon Kayaku Kayrad HX series (meta Acrylate,

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate : Nagase Sangyo Denacol DA (M) -811, epichlorohydrin-modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Epichlorohydrin modified pro glycol di (meth) acrylate: Nagase Denacol DA (M) -911 alkylene glycol type, such as (meth) acrylate,

Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentylglycol-modified trimethylolpropane di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) Acrylate: Sartomer SR-454, Propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA-310, Epichlorohydrin modified trimethylolpropane tri (meth) acrylate: Trimethylol such as Nagase Sangyo DA (M) -321 Propane type (meth) acrylate,

Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate: Toagosei Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylates, alkyl-modified dipentaerythritol poly (meth) acrylates: Kaprorad-modified dipentaerythritol poly (meth) acrylates such as Nippon Kayaku Kayrad D-310, 320, 330, etc .: Nippon Kayaku Kayrad DPCA-20 , 30, 60, 120, etc., pentaerythritol type (meth) acrylate, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) Acrylate: Nagase Denacol DA (M) -314, glycerol type (meth) acrylates such as triglycerol di (meth) acrylate,
Dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) such as Sanyo Kokusaku Pulp CAM-200 Acrylate,
Tris (acryloxyethyl) isocyanurate: Isocyanurates such as Toagosei Aronix M-315, tris (methacryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate Examples include type (meth) acrylate.

  Furthermore, as a compound having a urethane bond among (meth) acrylate compounds, for example, phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer: Kyoeisha Chemical AH-600, phenylglycidyl ether acrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical AT-600, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer: Kyoeisha Chemical UA-306H, phenylglycidyl ether acrylate isophorone diisocyanate urethane prepolymer: Kyoeisha Chemical AI-600, glycerin dimethacrylate tolylene diisocyanate urethane prepolymer: Kyoeisha Chemical UA-101T, glycerin dimethacrylate isophor Diisocyanate urethane prepolymer Kyoeisha Chemical UA-101I, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer Kyoeisha Chemical UA-306T, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer and the like Kyoeisha Chemical UA-306I and the like.

  In addition, among (meth) acrylate compounds, polyester (meth) acrylate is exemplified as a compound having an ester bond, and epoxy (meth) acrylate is exemplified as a compound obtained by modifying an epoxy group.

  Examples of the nitrogen-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- (meth) acrylamide. , N-butoxymethyl- (meth) acrylamide, monoalkylol (meth) acrylamide such as N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl ( (Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, Acrylamide-type unsaturated compounds such as dialkyrol (meth) acrylamides such as N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide,

Unsaturated compounds having a dialkylamino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like, and Cl ⁻ , Br ⁻ , I as counter ions ^- a halogen ion or QSO ₃ of ^-: and the like quaternary ammonium salts of dialkylamino group-containing unsaturated compound having a (Q 1 -C 12 alkyl group carbon atoms).

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.

  Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

Examples of vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, and chlorostyrene. Can be mentioned.
Examples of vinyl ether compounds include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, cyclohexane monovinyl ether, cyclohexane divinyl ether, tetrahydrofurfuryl monovinyl ether, ethylcyclohexanol vinyl ether, tertiary butyl vinyl ether, methoxy Ethyl vinyl ether, ethoxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxypentyl vinyl ether, diethylaminoethyl vinyl ether, tricyclodecane epoxy vinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol Such Lumpur hexa vinyl ether.

  Examples of the energy rays of the present invention include X-rays, α rays, β rays, γ rays, neutron rays, ultraviolet rays, visible light, infrared rays, radio waves, and the like. Useful.

  Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited thereto. In the following production examples and examples, “part” means part by weight unless otherwise specified.

<Production of initiator (a)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,

Pyromellitic dianhydride 32 parts,
68 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
0.5 part of 1,8-diazabicyclo [5.4.0] -7-undecene,
25 parts of methyl ethyl ketone was charged, the temperature was gradually raised while stirring, and the reaction was performed at 90 degrees under a nitrogen atmosphere. The IR measurement of the reaction product confirmed that the acid anhydride group peaks, that is, peaks near 1780 cm ⁻¹ and 1850 cm ⁻¹ had disappeared, and then cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 173 mg KOH / g.
Subsequently, 64 parts of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.) in this solution,
0.5 parts dimethylbenzylamine,
0.02 part of methoquinone,
Was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained initiator (a) was 2 mgKOH / g.

<Production of initiator (b)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,

1,2,3,4-butanetetracarboxylic dianhydride 30 parts,
70 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
0.5 part of 1,8-diazabicyclo [5.4.0] -7-undecene,
Methyl ethyl ketone 25 parts

Was gradually heated with stirring and reacted at 90 ° under a nitrogen atmosphere. The IR measurement of the reaction product confirmed that the acid anhydride group peaks, that is, peaks near 1780 cm ⁻¹ and 1850 cm ⁻¹ had disappeared, and then cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 178 mg KOH / g.
Subsequently, 66 parts of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.),
0.5 parts dimethylbenzylamine,
0.02 part of methoquinone,
Was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained initiator (a) was 3 mgKOH / g.

<Production of initiator (c)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,

42 parts of benzophenone tetracarboxylic dianhydride,
58 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
0.5 part of 1,8-diazabicyclo [5.4.0] -7-undecene,
25 parts of methyl ethyl ketone was charged, the temperature was gradually raised while stirring, and the reaction was performed at 90 degrees under a nitrogen atmosphere. The IR measurement of the reaction product confirmed that the acid anhydride group peaks, that is, peaks near 1780 cm ⁻¹ and 1850 cm ⁻¹ had disappeared, and then cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 150 mgKOH / g.
Subsequently, 56 parts of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.),
0.4 parts dimethylbenzylamine,
0.02 part of methoquinone,
Was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air. While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained initiator (a) was 3 mgKOH / g.

<Production of initiator (d)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,

41 parts of benzophenone tetracarboxylic dianhydride,
59 parts of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one,
0.5 part of 1,8-diazabicyclo [5.4.0] -7-undecene,
Methyl ethyl ketone 25 parts

Was gradually heated with stirring and reacted at 90 ° under a nitrogen atmosphere. The IR measurement of the reaction product confirmed that the acid anhydride group peaks, that is, peaks near 1780 cm ⁻¹ and 1850 cm ⁻¹ had disappeared, and then cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 150 mgKOH / g.
Subsequently, 38 parts of glycidyl methacrylate in this solution,
0.3 parts dimethylbenzylamine,
0.01 parts of methoquinone,
Was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air.
While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained initiator (a) was 5 mgKOH / g.

<Manufacture of initiator (e)>
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, gas inlet tube, and dropping funnel,

Benzophenone tetracarboxylic dianhydride 57 parts,
β-hydroxyethyl acrylate 43 parts,
0.5 part of 1,8-diazabicyclo [5.4.0] -7-undecene,
25 parts of methyl ethyl ketone was charged, the temperature was gradually raised while stirring, and the reaction was performed at 90 degrees under a nitrogen atmosphere.
The IR measurement of the reaction product confirmed that the acid anhydride group peaks, that is, peaks near 1780 cm ⁻¹ and 1850 cm ⁻¹ had disappeared, and then cooled to stop the reaction. At this point, the acid value of the reaction product was measured by a conventional method and found to be 213 mg KOH / g.
Subsequently, 76 parts of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.) in this solution,
0.6 parts dimethylbenzylamine,
0.02 part of methoquinone,
Was added, the temperature was gradually raised, and the reaction was carried out at 90 degrees in the presence of dry air.
While the reaction was continued, the acid value of the reaction product was measured periodically. When the acid value became 5 mgKOH / g or less, the reaction product was cooled to stop the reaction. The final acid value of the obtained initiator (a) was 4 mgKOH / g.

(Examples 1-4, Comparative Examples 1-4)
The photosensitive resin composition was dissolved and mixed by adjusting the number of parts shown in Table 1.
The performance evaluation was performed by the following method.

(1) Tack A general-purpose PET film was coated with a photosensitive resin composition prepared according to the formulation shown in Table 1 using a bar coater # 8, irradiated with ultraviolet light (120 W / cm metal halide lamp, 1 light), and then touched. The number of times of UV irradiation when tack-free (dry and hardened) due to (1 time = 111 mJ / cm ² )
The smaller the value, the faster the curing speed.

(2) Number of times of MEK rubbing The number of times of rubbing when the coating cured under the same conditions as the tack was rubbed with a cotton swab soaked in methyl ethyl ketone, and the underlying PET film was exposed.
A larger numerical value indicates better curability.

(3) Odor The coated material cured under the same conditions as the tack was cut finely, packed in a glass jar, allowed to stand overnight, and five panelists judged the odor relative to each other. It was set to -5 (good).

(4) Exudate Peak Strength A general-purpose polyethylene-coated paper (15 cm × 10 cm) was layered on the coating cured under the same conditions as the tack evaluation, and a 20 kg weight was placed on the oven and left in an oven at 50 ° C. for 24 hours. The polyethylene-coated paper is finely chopped and immersed in 20 g of ethanol for 24 hours. After concentrating 15 g of the supernatant, 0.1 ml of a 0.1 mg / ml polystyrene standard sample (Mw = 37200) tetrahydrofuran solution is added as an internal standard. Further, it was diluted with 2 g of tetrahydrofuran and measured by gel permeation chromatography. Gel permeation chromatography is detected using a UV detector (wavelength: 254 nm), and the resulting chart is corrected so that the peak intensity of polystyrene is the same for the chart of polyethylene-coated paper measured in advance. did. A chart of only polyethylene-coated paper was subtracted from the corrected chart, and the peak intensity after subtraction was quantified as an exuded component extracted with ethanol.
The smaller the numerical value, the less the exudation component from the coated material and the better.

HCPK ⁽¹⁾ : Photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone
MOBB ⁽²⁾ : Photopolymerization initiator Methyl-2-benzoylbenzoic acid
Ebecryl P36 ⁽³⁾ : Photopolymerization initiator Daicel UCB Co., Ltd. Acrylic benzophenone compound
M-350 ⁽⁴⁾ : Toagosei Co., Ltd .: Trimethylolpropane EO-modified (3 mol) triacrylate
M-309 ⁽⁵⁾ : Toagosei Co., Ltd .: Trimethylolpropane triacrylate
M-210 ⁽⁶⁾ : Toagosei Co., Ltd .: Bisphenol AEO modified (4 mol) diacrylate
MDA ⁽⁷⁾ : N-methyldiethanolamine

  As is clear from the evaluation results of “tack” and “MEK rubbing frequency” in Table 1, the photopolymerization initiator of the present invention exhibited a photocurability equivalent to or higher than that of a conventional general photopolymerization initiator. . At the same time, as is clear from the evaluation results of “odor” and “exudate peak intensity” in Table 1, the photopolymerizable composition containing the photopolymerization initiator of the present invention is a conventional general photopolymerization. Odor and exudate were greatly reduced compared to the case where an initiator was used.

  The photopolymerization initiator of the present invention is excellent in photocurability, and the photopolymerizable composition containing the photopolymerization initiator of the present invention is suitable for various paints, printing inks, coating agents and the like.

Claims (7)

At least two partial structures represented by the following general formula (1);
A photopolymerization initiator having at least two polymerizable unsaturated double bond groups.
General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent. Further, they may be combined to form a ring.
R ³ represents a hydrogen atom or a substituent. ) The photoinitiator of Claim 1 shown by following General formula (2).
General formula (2)

(In the formula, R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituent. R ¹ and R ² , and R ⁴ and R ⁵ may be combined to form a ring.
R ⁹ represents a tetravalent organic residue.
R ^{10 to} R ¹³ represent a divalent organic residue.
Ar ¹ and Ar ² each independently represent an arylene group that may be substituted. ) A photopolymerizable composition comprising the photopolymerization initiator (A) according to claim 1 and a compound having a polymerizable unsaturated double bond group other than (A). A compound (Y) having a carboxyl group obtained by reacting a compound having two or more carboxylic anhydride groups with a compound (X) having a functional group capable of reacting with the carboxylic anhydride group, and a carboxyl group; A step of reacting a compound (Z) having a functional group capable of reacting, and at least two partial structures represented by the following general formula (1); and at least two polymerizable unsaturated double bond groups; A method for producing a photopolymerization initiator comprising:
At least one of the compound (X) and the compound (Z) has a partial structure represented by the following general formula (1), and
A method for producing a photopolymerization initiator, wherein at least one of compound (X) and compound (Z) has an unsaturated double bond group.
General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent. Further, they may be combined to form a ring.
R ³ represents a hydrogen atom or a substituent. ) Compound (X) has a partial structure represented by the general formula (1), and
The method for producing a photopolymerization initiator according to claim 4, wherein the compound (Z) has an unsaturated double bond group. A method for producing a polymer, wherein the photopolymerization initiator according to claim 1 or 2 is polymerized by irradiation with energy rays. A method for producing a polymer, wherein the photopolymerizable composition according to claim 3 is polymerized by irradiation with energy rays.