JPH1087566A - Hydroxyalkylphenone derivative, its polymer, and photopolymerization initiator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful for printing ink, coating materials, adhesives, etc., and having both of a photopolymerization initiating group and a polymerizable group in the molecule. SOLUTION: This compound is represented by formula I [A is formula II or III (R<3> to R<6> are each H or methyl), etc.; R<1> is Z (Z is formula IV); R<2> is H, a 1-12C alkyl, phenyl, benzyl, Z, etc.], e.g. itaconic aid bis[2- 4-(2-hydroxy-2- methylpropionyl)phenoxy}ethyl]. The compound of formula I is obtained by charging, e.g. 1- 4-(2-hydroxyethoxy)phenyl}-2-hydroxy-2-methylpropane-1-one, pyridine and MEK into a reactor and dropping itaconic acid dichloride and MEK thereto and reacting the above compound with itaconic acid dichloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydroxyalkylphenone derivative having a photopolymerization initiation group and a polymerizable group in a molecule and a polymer thereof, which is used for printing inks, paints, adhesives and the like. It relates to a photopolymerization initiator.

[0002]

2. Description of the Related Art A photo-curing method using ultraviolet rays or the like can be cured at a lower temperature and more quickly than a method of drying or curing a coating film by heat, and thus has many advantages such as improvement in productivity, energy saving, and no pollution. is there. In addition, since this photocuring method can be selectively cured, printing inks, paints, adhesives,
It is widely used for processing printing plates and printed wiring boards.

[0003] In the photo-curing method, a photo-polymerization initiator which generates radicals by light irradiation is generally used, and various photo-polymerization initiators have been developed up to the present.
For example, benzoin, benzoin ethers, substituted acetophenones, benzyl ketals, oxime derivatives,
Photopolymerization initiators, such as benzophenones, thioxanthones, xanthates, and organic peroxides, that generate radicals upon irradiation with ultraviolet rays are known.

[0004] However, in the photocured coating film obtained using these photopolymerization initiators, unreacted photopolymerization initiators,
There are low molecular weight compounds generated by cleavage of the photopolymerization initiator, and these bleed on the surface of the coating film, causing a problem of deterioration and discoloration of the coating film.

As a method for solving this problem, a photopolymerization initiator having a (meth) acrylate group as a polymerizable group in the molecule (for example, JP-A-62-81345, JP-A-64
JP-A-70440, JP-A-2-270844,
JP-A-5-310635, JP-A-7-89925
And a polymer having a photopolymerization initiating group (for example, JP-B-2-36582, JP-A-1-9614).
No. 5, publication No. 5, etc.), and monomer-type and polymer-type photopolymerization initiators have been proposed.

The above-mentioned monomer-type and polymer-type photopolymerization initiators are used by adding them to a photocurable composition when photocuring. In this case, the monomer-type photopolymerization initiator is used as a photopolymerization initiator, or the monomer-type photopolymerization initiator is polymerized alone, or the polymer-type photopolymerization initiator copolymerized with another monomer is a photopolymerization initiator. Used as a polymerization initiator.

[0007]

However, a conventional photopolymerization initiator having a (meth) acrylate group is (meth) acrylate.
Since the acrylate group has poor copolymerizability with, for example, an unsaturated dibasic acid-based monomer, it is difficult to use a monomer other than the (meth) acrylate-based monomer as a component of the photocurable composition. When such a monomer is used, there is a problem that the curing is insufficient, the hardness is lowered, and the adhesion is deteriorated.

Moreover, since the conventional monomer-type photopolymerization initiator has a (meth) acrylate group as a polymerizable group, a monomer which can be copolymerized when producing a polymer-type photopolymerization initiator is used. Types and types of compounds used as components of the photocurable composition are limited. Therefore, there is a problem that the characteristics of a cured product obtained by photocuring are also limited.

The present invention has been made by focusing on the problems existing in the prior art as described above. An object of the present invention is to provide a hydroxyalkylphenone derivative, a polymer thereof, and a photopolymerization initiator capable of preventing deterioration due to an unreacted photopolymerization initiator and obtaining a cured product having high hardness and good adhesion. Is to do. Another object of the present invention is to provide a hydroxyalkylphenone derivative, a polymer thereof, and a photopolymerization initiator which can broaden a selection range of a copolymerizable monomer and a compound used as a component of a photocurable composition. It is in.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the object can be achieved by a novel compound, and have completed the present invention.

That is, the hydroxyalkylphenone derivative of the first invention in the present invention has the following general formula (1)
It is represented by

[0012]

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[Where A is

[0014]

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Wherein R ¹ represents Z, R ² represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a benzyl group or Z, and R ³ , R ⁴ , R ⁵ ,
R ⁶ is each independently hydrogen or a methyl group, and Z is

[0016]

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## EQU1 ## The polymer of the second invention is formed from the hydroxyalkylphenone derivative represented by the general formula (1) of the first invention.

Further, the monomer type photopolymerization initiator of the third invention comprises the hydroxyalkylphenone derivative represented by the general formula (I) of the first invention as an active ingredient. In addition, the polymer type photopolymerization initiator of the fourth invention is
The polymer of the second invention is an active ingredient.

[0019]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. The novel hydroxyalkylphenone derivative is a compound represented by the general formula (1). This hydroxyalkylphenone derivative has a combination of a hydroxyalkylphenone group as a photopolymerization initiating group represented by Chemical Formula 3 and an unsaturated dibasic acid group as a polymerizable group represented by Chemical Formula 2 in a molecule. It is a compound with a structure. The polymerizable groups each have a symmetrical structure as represented by Chemical Formula 2.

The compounds represented by the general formula (1) include (i) maleic acid ester derivatives, (ii) fumaric acid ester derivatives and (iii) itaconic acid ester derivatives. The following are specific examples of these.

(I) Maleic acid ester derivatives Bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl maleate, mono [2- {4- (2-hydroxy-2-)-maleate] Methylpropionyl) phenoxydiethyl], methyl maleate [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], ethyl maleate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], propyl maleate [2- {4- (2-
(Hydroxy-2-methylpropionyl) phenoxy} ethyl], isopropyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], butyl maleate [2- {4- (2-hydroxy- 2-methylpropionyl) phenoxydiethyl], pentyl maleate [2- {4- (2-hydroxy-2-
Methylpropionyl) phenoxydiethyl], hexyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], cyclohexyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) ) Phenoxydiethyl], maleic acid (2
-Ethylhexyl) [2- {4- (2-hydroxy-2
-Methylpropionyl) phenoxy} ethyl], decyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], dodecyl maleate [2- {4- (2-hydroxy-2-methyl) Propionyl) phenoxy {ethyl], phenyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], benzyl maleate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], bis [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxy} ethyl], mono [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl citraconic acid], methyl citraconic acid [2- {4- (2 -Hydroxy-2-methylpropionyl) phenoxydiethyl],
Ethyl citraconic acid [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxydiethyl], isopropyl citraconic acid [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxy} ethyl], butyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], sec-butyl citraconic acid [2- {4- (2-hydroxy-2) -Methylpropionyl) phenoxy} ethyl], neopentyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], hexyl citraconic acid [2- {4- (2-hydroxy-2-methyl) Propionyl) phenoxydiethyl], heptyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], citraconic acid (2-
Ethylhexyl) [2- {4- (2-hydroxy-2-
Methylpropionyl) phenoxydiethyl], nonyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], isodecyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) ) Phenoxydiethyl], dodecyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], phenyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy] [Ethyl], benzyl citraconic acid [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] 2,3-dimethylmaleate, mono [2- {4- (2 -Hydroxy-2-methylpropionyl) phenoxydiethyl], methyl 2,3-dimethylmaleate [2- {4- (2-hydroxy-2-
(Ii) fumaric acid ester derivatives bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] fumarate and mono [2- {4- (2-) fumarate Hydroxy-2-methylpropionyl) phenoxydiethyl], methyl fumarate [2- {4
-(2-hydroxy-2-methylpropionyl) phenoxy} ethyl], ethyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], propyl fumarate [2- {4- ( 2-hydroxy-2-methylpropionyl) phenoxydiethyl], isopropyl fumarate [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxy} ethyl], t-butyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], pentyl fumarate [2- {4- (2-hydroxy-2) -Methylpropionyl) phenoxydiethyl], hexyl fumarate [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], cyclohexyl fumarate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], octyl fumarate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], (2-ethylhexyl) fumarate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], decyl fumarate [2- {4- (2
-Hydroxy-2-methylpropionyl) phenoxy}
Ethyl], isodecyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], dodecyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] Phenyl [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] fumarate, benzyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], mesacon Acid bis [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], mesaconic acid mono [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxy} ethyl], methyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], ethyl mesaconate [2- {4- (2 -Hydroxy-2-methylpropionyl) phenoxydiethyl], isopropyl mesaconate [2- {4- (2-hydroxy-
2-methylpropionyl) phenoxydiethyl], isobutyl mesaconate [2- {4- (2-hydroxy-2-
Methylpropionyl) phenoxy} ethyl], neopentyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], hexyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) ) Phenoxydiethyl], heptyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], (2-ethylhexyl) mesaconate [2- {4- (2-hydroxy-2- Methylpropionyl) phenoxy} ethyl], nonyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], isodecyl mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) ) Phenoxydiethyl], dodecyl mesaconate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], phenyl mesaconate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], benzyl mesaconate [2- {4- (2-
Hydroxy-2-methylpropionyl) phenoxydiethyl], bis [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], 2,3-dimethylfumaric acid mono [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], methyl 2,3-dimethylfumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (iii) itacone Acid ester derivatives bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl itaconate], mono [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl itaconate] , Methyl itaconate [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], ethyl itaconate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], propyl itaconate [2- {4- (2-
(Hydroxy-2-methylpropionyl) phenoxy} ethyl], isopropyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], butyl itaconate [2- {4- (2-hydroxy- 2-methylpropionyl) phenoxydiethyl], isobutyl itaconate [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxydiethyl], sec-butyl itaconate [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxy} ethyl], t-butyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], pentyl itaconate [2- {4- (2-hydroxy-2) -Methylpropionyl) phenoxy} ethyl], neopentyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], hexyl itaconate [2- {4- (2-hydroxy-2-methyl) Propionyl) phenoxydiethyl], cyclohexyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], heptyl itaconate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], octyl itaconate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl], itaconic acid (2-ethylhexyl) [2
-{4- (2-hydroxy-2-methylpropionyl)
Phenoxydiethyl], nonyl itaconate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxy} ethyl], decyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl], isodecyl itaconate [2- {4- (2 -Hydroxy-2-methylpropionyl) phenoxydiethyl], dodecyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxydiethyl],
Phenyl itaconate [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxy} ethyl], benzyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] In the above compounds, citraconic acid ester,
Mesaconic acid esters and itaconic acid esters are those in which R ¹ and R ^{2 in} formula (1) are different,
-{4- (2-hydroxy-2-methylpropionyl)
In the case other than phenoxy [ethyl] ester, there are the following two types of structures, respectively. Each upper structural R ¹ is 4-position an ester bonded to R ² is the 1-position, the structure of the lower are the ester bonded to R ¹ is the 1-position, R ² is 4-position . 1) Citraconate

[0022]

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2) Mesaconic acid ester

[0024]

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3) Itaconic acid ester

[0026]

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The hydroxyalkylphenone derivative represented by the general formula (1) is produced, for example, by a usual esterification reaction. Specifically, the following three manufacturing methods can be mentioned.

(1) Monochloride or dichloride of unsaturated dibasic acid is converted to sodium hydroxide, potassium hydroxide,
A method of reacting with 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one in the presence of a base catalyst such as pyridine.

(2) An unsaturated dibasic acid is converted to 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2- in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid.
A method of reacting with methylpropan-1-one.

(3) Unsaturated dibasic acid anhydride is converted to 1- {4-
A method of reacting with (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one.
If the reaction temperature for producing the hydroxyalkylphenone derivative is too high, gelation or the like may occur due to the polymerization of the polymerizable group.
0 ° C. or lower is more preferable.

In conducting the reaction, benzene, toluene, cyclohexane, methyl ethyl ketone,
A reaction solvent such as ethyl acetate is used. The reaction is preferably carried out by adding a polymerization inhibitor such as hydroquinone or methoquinone, or in a stream of oxygen or air in order to suppress gelation. Further, a polymerization inhibitor may be added and the reaction may be carried out under a stream of oxygen or air.

Next, a polymer of a hydroxyalkylphenone derivative is produced by polymerizing the compound represented by the general formula (1) alone or together with another ethylenically unsaturated compound.

This polymerization is carried out by a conventional radical polymerization initiator,
Specifically, t-butylperoxypivalate, t-butylperoxyneodecanate, benzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxyacetate, -Butyl peroxybenzoate, 1,1
Organic peroxides such as -di (t-butylperoxy) cyclohexane and dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,
Azo compounds such as 4-dimethylvaleronitrile) are used.

The polymerization temperature varies depending on the polymerization initiator used, but is usually preferably in the range of 50 to 150 ° C.,
A range of 30 ° C. is more preferred. As a polymerization method, a general method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method is employed.

The other ethylenically unsaturated compound that can be used for the copolymerization is not particularly limited.
Unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and derivatives of these unsaturated carboxylic acids, for example, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Monoesters such as acrylate, hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, aminoalkyl esters such as dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, (Meth) acrylamide, N-substituted (meth) acrylamides, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers, styrene, alkylstyrene, halogenated styrene, N-vinylpyrroli Vinyl compounds such emissions and the like.

Among them, those having good copolymerizability with unsaturated dibasic acid groups, specifically, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and their alkyl esters and anhydrides And the like are preferred examples.

If the amount of the ethylenically unsaturated compound in the polymer is too large, the number of photopolymerization initiator groups in the polymer becomes small and the performance as a photopolymerization initiator cannot be sufficiently exhibited. Is preferred.

The number average molecular weight (Mn) of the polymer is not particularly limited. However, if the number average molecular weight (Mn) is too large, the solubility becomes poor when used as a photopolymerization initiator. It becomes difficult to express performance.
Therefore, the number average molecular weight is 5,000 to 200,000.
Is preferable.

The hydroxyalkylphenone derivative represented by the general formula (1) and a polymer thereof are used alone or as a mixture with other components to be used as a monomer type photopolymerization initiator or a polymer type photopolymerization initiator. That is, the monomer-type photopolymerization initiator or the polymer-type photopolymerization initiator is used for photopolymerization or photocuring of one or more kinds of radically polymerizable unsaturated compounds.

At this time, additives such as commonly used pigments, fillers, dyes, polymerization inhibitors, plasticizers, polymers for binders, solvents, sensitizers, and other known photopolymerization initiators are appropriately compounded. You can also.

The photocurable composition thus obtained is used for paints, adhesives, printing inks, printing plates, printed wiring boards, photoresists and the like. Examples of the radical polymerizable unsaturated compound that can be photopolymerized or photocured by blending a photopolymerization initiator include a polymerizable monomer, a polymerizable oligomer, and a polymerizable unsaturated polymer.

The polymerizable monomer is a compound having one or more polymerizable double bonds and includes, for example, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. And derivatives of these unsaturated carboxylic acids, for example, monoesters such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Hydroxyalkyl esters such as (meth) acrylate, aminoalkyl esters such as dimethylaminoethyl (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Polyesters such as acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylonitrile, (meth) ) Acrylamide and N-substituted (meth)
Acrylamides, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers, styrene, alkylstyrene, halogenated styrene, divinylbenzene, N-vinylpyrrolidone, diallyl phthalate, diallyl malate, triallyl isocyanate and triallyl phosphate And the like.

Of these, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid and derivatives of these unsaturated carboxylic acids are preferred because of their good copolymerizability with the compound represented by the above general formula (1). preferable.

Examples of the polymerizable oligomer or polymerizable unsaturated polymer include curable resins having a fumarate group, a maleate group, an allyl group, and a (meth) acrylate group, unsaturated polyesters, unsaturated acrylic resins, and isocyanate-modified acrylics. Oligomers, polyester acrylic oligomers, polyepoxy acrylic oligomers and the like.

The amount of the photopolymerization initiator used is basically preferably 0.01 to 20% by weight, more preferably 0.1% by weight, based on the radically polymerizable unsaturated compound in the case of a monomer type photopolymerization initiator. 1 to 10% by weight. In the case of a polymer type photopolymerization initiator, it is preferably 0.1 to 50% by weight, more preferably 0.1 to 50% by weight, based on the radically polymerizable unsaturated compound.
5 to 30% by weight. However, the amount used is appropriately set according to the type and amount of the additive. For example, when a pigment having poor light transmittance is mixed, it may be necessary to increase the amount. However, if the amount is too large, unreacted photopolymerization initiator may remain in the polymer. If the amount is too small, the polymerization is not completed, and unreacted unsaturated compounds remain.

The photopolymerization or photocuring is preferably carried out with respect to a radical polymerizable unsaturated compound containing a photopolymerization initiator.
50 to 500 nm, more preferably 300 to 400 n
This is performed by a known method of irradiating light in a wavelength range of m.

Examples of usable light sources include sunlight, mercury lamps, hydrogen discharge tubes, xenon lamps, flash discharge tubes, tungsten lamps, halogen lamps, and various lasers such as dye lasers, excimer lasers, and ion lasers.

The effects exerted by the above-described embodiment will be described below. (1) Since the hydroxyalkylphenone derivative represented by the general formula (1) has a specific photopolymerization initiation group and a polymerizable group, it is used as a curing agent when polymerizing and curing a radically polymerizable unsaturated compound. Even when the photopolymerization initiating group remains unreacted, the polymerizable group reacts and is taken into the curing system. Therefore, the cured product is prevented from deteriorating or yellowing due to bleeding of the unreacted photopolymerization initiator. (2) Further, the monomer-type or polymer-type photopolymerization initiator functions as a cross-linking agent at the time of curing the radically polymerizable unsaturated compound, and is highly cross-linked. Therefore, a cured product having high hardness can be obtained. (3) Since the polymerizable group is an unsaturated dibasic acid group, a monomer which is difficult to copolymerize with a conventional photopolymerization initiator having an acrylic polymerizable group, for example, an unsaturated dibasic acid ester It is possible to copolymerize with the like. Therefore, the selection range of the monomer composition for obtaining a photocured product can be expanded. (4) Further, by polymerizing the hydroxyalkylphenone derivative represented by the general formula (1), a polymer having a photopolymerization initiation group can be easily obtained. (5) Since the hydroxyalkylphenone derivative represented by the general formula (1) and the polymer thereof have a photopolymerization initiation group, they are preferably used as a photopolymerization initiator for a radically polymerizable unsaturated compound. Can be. (6) In addition, when a polymer is used as a photopolymerization initiator, since the photopolymerization initiator is a polymer in advance, there is little shrinkage due to polymerization, and the photopolymerization initiator serves as a cross-linking point to reduce distortion. Can be suppressed. Therefore, a photocured product having good performance such as adhesion and strength can be obtained.

[0049]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition,% in each Example and Comparative Example and Table represents weight%, and abbreviations are as follows. MMA: methyl methacrylate BMA: butyl methacrylate ST: styrene DMM: dimethyl malate DBF: dibutyl fumarate DEI: diethyl itaconate EGDA: ethylene glycol diacrylate M5700: ester acrylate resin (trade name “ARONIX M- 5700 ") M8060: Ester acrylate resin (trade name" Aronix M-8060 "manufactured by Toa Gosei Chemical Co., Ltd.) MEK: methyl ethyl ketone PGM: propylene glycol monomethyl ether LPO: lauroyl peroxide (trade name" Perloyl L "manufactured by NOF Corporation) D1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one [Ciba-Ge
trade name “Darocure 1173” manufactured by igy) Co., Ltd. I651: 1,2-diphenyl-2,2-dimethoxyethane-1-one [trade name “Irgacure 651” manufactured by Ciba Geigy Co., Ltd.] ZLI3331: 1- ｛4- ( 2-acryloyloxyethoxy) phenyl {-2-hydroxy-2-methylpropan-1-one KIP: 2-hydroxy-2-methyl-1- {4- (1
-Methylvinyl) phenyl @ propan-1-one oligomer (trade name "Ezacure KIP" manufactured by Sebel Haigner Japan) (Example 1) Equipped with a stirrer, a dropping funnel, a thermometer, a purge gas inlet, and a water-cooled condenser. 1- {4- (2-hydroxyethoxy) phenyl} in a 300 ml reaction vessel.
-2-Hydroxy-2-methylpropan-1-one ("Darocure 2959" manufactured by Ciba-Geigy) 26.9
g, pyridine 14.2 g, and MEK 80 g, and while stirring with passing air, itaconic acid dichloride 1 was added.
A mixed solution of 0.0 g and 40 g of MEK was added dropwise at 30 ° C. over 30 minutes. Then, stirring was continued for 5 hours.
After the precipitated solid was separated by filtration, the filtrate was washed successively with a 1% aqueous hydrochloric acid solution, a 1% aqueous sodium bicarbonate solution and water, dehydrated, and evaporated to remove the solvent. Thereafter, the mixture was purified by column chromatography using a mixed solvent of hexane / ethyl acetate, and 20 g of a colorless and transparent liquid was obtained.
I got

This compound was subjected to infrared absorption spectrum (I
R), nuclear magnetic resonance spectra ⁽¹ H-NMR), mass spectrum (MS), 1 was measured by elemental analysis,
It was as follows. This compound was confirmed to be bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] itaconate (hereinafter referred to as compound A).

[0051]

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Infrared absorption spectrum 3400 cm ^-1 (OH), 1720 cm ^-1 (ester C = O), 1660 cm ^-1 (ketone C = O) Nuclear magnetic resonance spectrum (δ) 1.6 ppm (12H, CH ₃ ) 3.4 ppm (2
H, CH ₂ —CO), 4.0 to 4.6 ppm (10H,
CH ₂ —O, OH), 5.7 to 6.4 ppm (2H, C
H ₂ = C), 6.9 to 8.1 ppm (8H, phenyl) Mass spectrum (m / e) 542 (molecular ion peak) Elemental analysis C: 64.15% (calculated value 64.20%), H: 6.3
8% (calculated value: 6.32%) (Examples 2 to 5) Instead of itaconic dichloride,
The production was carried out according to the production method described in Example 1 except that maleic acid dichloride, fumaric acid dichloride, citraconic acid dichloride and mesaconic acid dichloride were used, respectively. Each of the obtained compounds was analyzed in the same manner as in Example 1, and as a result, it was confirmed that the obtained compounds were the target compounds (hereinafter, referred to as Compounds B to E).

That is, the target compounds are bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl maleate (hereinafter referred to as compound B) and bis [2- {4- (2-hydroxy-
2-methylpropionyl) phenoxydiethyl] (hereinafter referred to as compound C), bis [2- {4-
(2-Hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound D), bis [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] mesaconate (hereinafter compound E) That)
Met.

The compounds and the results of each analysis are shown in Table 1.

[0055]

[Table 1]

Examples 6 to 13 Instead of itaconic acid dichloride, monomethyl maleate monochloride, mono (2-ethylhexyl) maleate monochloride, monododecyl maleate maleate,
A method according to the production method described in Example 1, except that monophenyl maleate monochloride, monoisopropyl monofumarate, monocyclohexyl fumarate, monododecyl monofumarate, and monobenzyl monofumarate are used. It was carried out in. Each of the obtained compounds was subjected to each analysis in the same manner as in Example 1, and as a result, it was confirmed that the obtained compounds were the target compounds (hereinafter, referred to as compounds FM).

That is, each of the target compounds is methyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound F
), Maleic acid (2-ethylhexyl) [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound G), dodecyl maleate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound G) Phenyl [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound I), isopropyl fumarate [2- {4- (2-hydroxy) -2-methylpropionyl) phenoxydiethyl] (hereinafter referred to as compound J),
Cyclohexyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound K), dodecyl fumarate [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound L), benzyl fumarate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter compound M) It is).

The compounds and the results of each analysis are summarized in Tables 2 and 3.

[0059]

[Table 2]

[0060]

[Table 3]

(Examples 14 to 21) Instead of itaconic acid dichloride, itaconic acid monomethyl monochloride (weight ratio of 1-position chloride compound / 4-position chloride compound (hereinafter referred to as 1-Cl / 4-Cl and Do)
Is a mixture of 40/60), monohexyl itaconate monochloride (1-Cl / 4-Cl = 23/77), monododecyl itaconate monochloride (1-Cl / 4-C
1 = 30/70), monobenzyl monochloride itaconate (1-Cl / 4-Cl = 25/75), monoethyl monochloride citraconic acid (1-Cl / 4-Cl = 3)
5/65), monododecyl citraconic acid monochloride (1-Cl / 4-Cl = 10/90), monobutyl monomethacrylate monochloride (1-Cl / 4-Cl = 45/5)
5), monodecyl mesaconate monochloride (1-Cl
/ 4-Cl = 12/88), except that the production method described in Example 1 was used. Then, each of the obtained compounds was analyzed in the same manner as in Example 1, and as a result, it was confirmed that the obtained compounds were the target compounds (hereinafter, compounds NU).

That is, the target compound is methyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as Compound N).
Hexyl itaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound O), dodecyl itaconate [2- {4- (2-hydroxy-2- Methylpropionyl) phenoxydiethyl] (hereinafter referred to as compound P),
Benzyl itaconate [2- {4- (2-hydroxy-2)
-Methylpropionyl) phenoxydiethyl] (hereinafter referred to as
Compound Q), ethyl citraconic acid [2- {4-
(2-hydroxy-2-methylpropionyl) phenoxydiethyl] (hereinafter referred to as compound R), dodecyl citraconic acid [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter compound S) Butyl) mesaconate [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl]
(Hereinafter referred to as compound T), decyl mesaconate [2-
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter referred to as compound U).

Further, it was confirmed that the obtained compound was a mixture having a ratio corresponding to the raw materials by liquid chromatography (L
C). The obtained compounds and the results of each analysis are summarized in Tables 4 and 5.

[0064]

[Table 4]

[0065]

[Table 5]

Example 22 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropane was placed in a 200 ml reaction vessel equipped with a stirrer, thermometer, purge gas inlet, and water-cooled condenser. -1-one 44.8 g, itaconic anhydride 24.4 g, MEK 80 g
And stirred at 50 ° C. for 5 hours while passing air through. The solvent was distilled off under reduced pressure, and the precipitated crystals were recrystallized with a mixed solvent of MEK / hexane to obtain 45.5 g of white crystals.

The compound was subjected to infrared absorption spectrum, nuclear magnetic resonance spectrum, mass spectrum,
The results of measurement by elemental analysis were as shown in Table 6. That is, this compound is a compound of the formula [I]
{4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl] (hereinafter compound V). Further, the substitution position of the ester was determined by LC analysis to be:
It was confirmed that it was a mixture of 13% of 1-position ester and 87% of 4-position ester. (Examples 23 and 24) The procedure was performed in accordance with the production method described in Example 11 except that maleic anhydride and citraconic anhydride were used instead of itaconic anhydride. Each of the obtained compounds was obtained in Example 1
As a result of performing each analysis in the same manner as in Example 1, the target compound (hereinafter, referred to as
Compound W, X) was confirmed.

That is, those compounds are composed of mono [2- {4- (2-hydroxy-2-methylpropionyl) phenoxy} ethyl maleate (hereinafter referred to as compound W) and mono [2- {4-citraconic acid]. (2-hydroxy-2-methylpropionyl) phenoxydiethyl] (hereinafter referred to as compound X). The compound obtained when citraconic anhydride was used as a raw material had an ester substitution position of 1-position ester / 4-position ester = 19.
/ 81 was confirmed by LC analysis.
Table 6 summarizes the obtained compounds and the results of each analysis.

[0069]

[Table 6]

(Example 25) 30 units equipped with a stirrer, a dropping funnel, a thermometer, a purge gas inlet, and a water-cooled condenser.
100 g of PGM was placed in a 0 ml reaction vessel, heated to 100 ° C. under a nitrogen stream, and stirred. In addition, 50 g of compound A synthesized in Example 1, 25 g of DEI, MMA 2
A mixture of 5 g of the monomer and 1 g of LPO as a polymerization initiator was dropped at a constant rate over 2 hours.

After the completion of the dropwise addition, stirring was continued for another 2 hours to complete the polymerization. The resulting mixture is petroleum ether 50
The precipitate was filtered and dried to obtain 98 g of a polymer. The number average molecular weight (M
n) was replaced by gel permeation chromatography (GP)
It was 12000 as measured by C). (Examples 26 to 30) Polymer b was treated in the same manner as in Example 25 except that the monomers described in Table 7 were used.
To f.

[0072]

[Table 7]

(Examples 31 to 37) A photocurable resin composition having the composition shown in Table 8 was coated on an acrylic plate to a thickness of 100 μm.
m and a conveyor-type ultraviolet irradiation device equipped with one 1 kW high-pressure mercury lamp, and a conveyor speed of 10
Ultraviolet rays were irradiated at an irradiation distance of 10 cm at a rate of 10 m / min to cure the resin. In addition, the irradiation light amount of 365 nm in one pass of the conveyor was 100 mW / cm ³ . The following evaluation was performed about the obtained cured film. Table 8 shows the results. (1) Curing speed The number of passes under a light source required to reach cured drying (JIS K-5400), which does not adhere after rubbing the coating film strongly with a finger, was expressed as the number of Passes. The smaller the number of passes, the faster the curing speed. (2) Coating film hardness A pencil scratch test was performed in accordance with JIS K-5400, and the coating film hardness was represented by pencil hardness. (3) Adhesion According to the cross cut tape method of JIS K-5400, cut the coating film vertically and horizontally with a cutter knife to make 100 cross cuts (cut pieces) that reach the base material, and adhere to cellophane. A tape (manufactured by Nichiban Co., Ltd.) was attached and peeled in the direction perpendicular to the adhesive surface, and the number of crosscuts remaining without peeling was represented by the following symbol.

○: 100/100, Δ: 80/100 or more, ×: less than 80/100 (4) Extraction test 0.5 g of the cured coating film was pulverized, and 50 ml of acetonitrile was obtained.
And sonicated for 2 hours. After allowing to stand for 24 hours, the supernatant was taken and the amount of unreacted photopolymerization initiator was determined by liquid chromatography. The results were expressed as a residual ratio (%) with respect to the charged amount of the photopolymerization initiator.

[0075]

[Table 8]

(Comparative Examples 1 to 4) Photocuring was carried out by the method described in the Examples except that the photocurable resin compositions having the compositions shown in Table 9 were used. Table 9 shows the results.

[0077]

[Table 9]

From the results of the examples in Table 8, when the monomer type photopolymerization initiators of the respective examples were used as the photopolymerization initiators (Examples 31 to 34), the photocuring rate was high and the coating film obtained was high. It is understood that the hardness of the photopolymerization is high and the amount of the remaining free photopolymerization initiator is small. When the polymer-type photopolymerization initiator of each example was used as a photopolymerization initiator (Examples 35 to 37), the adhesion of the coating film was good and there was no remaining free photopolymerization initiator. Recognize.

On the other hand, as shown in Comparative Examples 1 to 4 in Table 9, when the conventional photopolymerization initiator was used, the curing of the coating film was incomplete or the adhesion was poor. I do. Table 10 shows the relationship between the hydroxyalkylphenone derivatives of Examples 1 to 24 and the general formulas described in the claims. In Table 10, A shows the structure of the following chemical formula 11, and B shows the structure of the following chemical formula 12.

[0080]

[Table 10]

[0081]

Embedded image

[0082]

Embedded image

The technical ideas grasped from the above embodiment will be described below. (1) The method for producing a hydroxyalkylphenone derivative according to claim 1, wherein the esterification reaction is performed using 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one. .

According to this method, a novel hydroxyalkylphenone derivative can be efficiently produced. (2) The photopolymerization initiator according to claim 3 or 4, wherein the radically polymerizable unsaturated compound polymerized by the photopolymerization initiator is an unsaturated carboxylic acid or a derivative thereof.

In such a case, the radical polymerizable unsaturated compound can be smoothly polymerized while maintaining the polymerizability with the hydroxyalkylphenone derivative. (3) The amount of the photopolymerization initiator used is 0.01 to 20% by weight based on the radical polymerizable unsaturated compound.
The photopolymerization initiator according to the above.

With this configuration, the polymerization of the unsaturated compound can be completed without leaving the unreacted polymerization initiator and the unsaturated compound. (4) The photopolymerization initiator according to claim 4, wherein the amount of the photopolymerization initiator used is 0.1 to 50% by weight based on the radically polymerizable unsaturated compound.

With this configuration, the polymerization of the unsaturated compound can be effectively completed without leaving the unreacted polymerization initiator and the unsaturated compound.

[0088]

As described above in detail, according to the present invention, the following excellent effects can be obtained. According to the novel hydroxyalkylphenone derivative of the first invention, since it has both a specific photoinitiating group and a polymerizable group, when used as a curing agent, it prevents deterioration of the cured product due to unreacted photopolymerization initiator. In addition to this, a cured product having high hardness and good adhesion can be obtained. Moreover, since the polymerizable group of the hydroxyalkylphenone derivative is an unsaturated dibasic acid group, it is difficult to copolymerize with a conventional photopolymerization initiator having an acrylic polymerizable group, such as an unsaturated monomer. Copolymerization with dibasic acid esters and the like is possible, and the range of selection of copolymerizable monomers and compounds used as components of the photocurable composition can be expanded.

The polymer of the second invention has a photopolymerization initiating group, can be suitably used as an initiator for photopolymerization, and has radical polymerizability. According to the monomer type photopolymerization initiator of the third invention, the photopolymerization initiator has good photopolymerization initiation ability, and the photopolymerization initiator also functions as a crosslinker to highly crosslink. Therefore, a cured product having high hardness can be obtained.

According to the polymer type photopolymerization initiator of the fourth invention, the photopolymerization initiator has good photopolymerization initiating ability, and since the photopolymerization initiator is a polymer in advance, there is little shrinkage due to polymerization, and The polymerization initiator serves as a cross-linking point, thereby suppressing distortion of the cured product. Therefore, it is possible to obtain a photocured product having good performance such as adhesion and strength.

Claims (4)

[Claims] 1. A hydroxyalkylphenone derivative represented by the following general formula (1). Embedded image [Wherein A is R ¹ represents Z, R ² is hydrogen, and has 1 to 12 carbon atoms.
Represents an alkyl group, a cycloalkyl group, a phenyl group, a benzyl group, or Z, wherein R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen or a methyl group, and Z is Represents ] 2. A polymer formed from the hydroxyalkylphenone derivative represented by the general formula (1) according to claim 1. 3. A monomer type photopolymerization initiator comprising the hydroxyalkylphenone derivative represented by the general formula (1) according to claim 1 as an active ingredient. 4. A polymer type photopolymerization initiator comprising the polymer according to claim 2 as an active ingredient.