JP2005272801A - Method for producing photopolymerization initiator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a photopolymerization initiator capable of giving a good polymer under a relatively mild condition, even when the polymer is polymerized to have a high molecular weight, without using an amine-based catalyst which causes malodors/yellowing of a cured material. <P>SOLUTION: This method for producing the photopolymerization initiator comprises reacting a compound (A) which has a photopolymerization initiating functional group and a carboxy group with a compound (B) which has two or more polymerizable unsaturated double bonds, wherein at least one of the polymerizable unsaturated double bonds comprises a vinyloxy group, so that the carboxy group of the compound (A) is reacted with the vinyloxy group of the compound (B) in the method for producing the photopolymerization initiator. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a photopolymerization initiator.

Although the conventional low molecular weight photopolymerization initiator used in the energy ray curable coating composition is excellent in reactivity, the unreacted polymerization initiator and the decomposition residue of the polymerization initiator are volatilized at the time of curing or from the cured product. As a result, there are problems such as generation of odor, migration of the initiator in the cured coating film to deteriorate the working environment, and contamination of the adherend when used as an adhesive or pressure-sensitive adhesive. In addition, because the photopolymerization initiator itself has a low molecular weight, depending on the processing conditions, it is sublimated from the uncured product, or extracted when the uncured product comes into contact with hot water, etc., and effective initiation in the uncured product There was a problem that the agent concentration could not be maintained. In order to solve such problems, it has been proposed to use an energy ray curable resin imparted with radical polymerization initiating ability in the polymer (see Patent Document 1). However, since synthesis of this high molecular weight photopolymerization initiator requires an amine-based catalyst, it has an odor during curing and causes yellowing of the coating film. Furthermore, although a photoinitiator having photopolymerization reactivity has been proposed (see Patent Document 2), the photocuring property of the unreacted material generated during the synthesis of the photoinitiator is poor, and thus the initiator composition Addition sometimes caused bleeding.
Japanese Patent Laid-Open No. 10-287787 JP-A-6-206975

  Therefore, the present invention does not use an amine-based catalyst that causes odor and yellowing of the cured product, and gives a good polymer even at a high molecular weight under relatively mild conditions. An object of the present invention is to provide a method for producing a photopolymerization initiator that can improve the above.

  The present inventors use a reaction between a vinyloxy group and a carboxyl group that proceeds under relatively mild conditions without using a catalyst, and without using an amine-based catalyst that causes yellowing of the coating film or odor. It has been found that the photopolymerization initiator can give a good polymer even with a high molecular weight and solves the above problems.

That is, the present invention is a photopolymerization characterized by reacting a compound (A) having a photopolymerization initiating functional group and a carboxyl group and a compound (B) having two or more polymerizable unsaturated double bonds. An initiator manufacturing method comprising:
At least one of the polymerizable unsaturated double bonds is a vinyloxy group;
A photopolymerization initiator for reacting a carboxyl group of a compound (A) having a photopolymerization-initiating functional group and a carboxyl group with the vinyloxy group of a compound (B) having two or more polymerizable unsaturated double bonds It relates to the manufacturing method.

  Moreover, this invention relates to the manufacturing method of the said photoinitiator whose compound (A) which has a photoinitiation functional group and a carboxyl group is an o-substituted benzoic acid derivative.

  Further, the present invention provides a compound (A) having two or more vinyloxy groups in the compound (B) having two or more polymerizable unsaturated double bonds and having a photopolymerization initiating functional group and a carboxyl group. It is related with the manufacturing method of the said photoinitiator whose carboxyl group molar equivalent is 0.5-0.8 with respect to vinyloxy group molar equivalent 1 of the compound (B) which has two or more polymerizable unsaturated double bonds.

  Moreover, this invention relates to the manufacturing method of the said photoinitiator whose at least 1 of a polymerizable unsaturated double bond is a (meth) acryl group.

  The present invention further relates to a method for producing a polymer photopolymerization initiator, characterized by radical polymerization of a photopolymerization initiator produced by the above production method.

  The present invention is further characterized in that the photopolymerization initiator produced by the above production method is radically polymerized together with the compound (C) having one or more other polymerizable unsaturated double bonds. The present invention relates to a method for producing a polymer photopolymerization initiator.

  Moreover, this invention relates to the photoinitiator manufactured by the said manufacturing method.

  The present invention also relates to a photopolymerizable composition comprising a photopolymerization initiator produced by the production method and a compound (C) having one or more polymerizable unsaturated double bonds.

  The present invention also relates to a polymer obtained by photopolymerizing the photopolymerizable composition.

  According to the present invention, there is provided a method for producing a photopolymerization initiator that gives a good polymer even under high molecular weight under relatively mild conditions without using an amine-based catalyst that causes odor and yellowing of a cured product. Could be provided.

  The compound (A) having a photopolymerization initiating functional group and a carboxyl group used in the present invention is not limited as long as it is a photoinitiator having a carboxyl group, and may be a self-cleavage type or a hydrogen abstraction type. A hydrogen abstraction type photoinitiator that does not generate a decomposition residue that causes odor during polymerization is preferable. For example, a benzophenone-based photoinitiator is preferable, and specific examples include o-benzoylbenzoic acid.

As the polymerizable unsaturated double bond of the compound (B) having two or more polymerizable unsaturated double bonds used in the present invention, a (meth) acrylate group, a maleic acid residue, a vinyl group, an allyl group, Examples thereof include a vinyloxy group and an allyloxy group, but at least one of them must be in the form of a vinyloxy group.
All the polymerizable unsaturated double bonds of the compound (B) may be a vinyloxy group alone or may contain a vinyloxy group and other polymerizable unsaturated double bonds.
Carboxyl groups are known to react with polymerizable unsaturated double bonds, but vinyloxy groups are particularly easier to react than other polymerizable unsaturated double bonds. The polymerizable unsaturated double bond remaining without reacting with the carboxyl group serves as a foothold when polymerizing in the final photopolymerization reaction or partially polymerizing to form a polymer photopolymerization initiator.

As the compound containing a vinyloxy group, a divinyl ether compound or a polyfunctional polyvinyl ether compound can be used.
Specific examples of divinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexane divinyl ether, hydroquinone divinyl ether Ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified bisphenol A divinyl ether, and ethylene oxide-modified bisphenol S divinyl ether.

  Examples of tri- or higher functional polyvinyl ether compounds include glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane. Examples thereof include tetravinyl ether and ditrimethylolpropane polyvinyl ether.

Polyfunctional or higher-functional polyvinyl ether compounds may be synthesized from the reaction of polyfunctional isocyanates with alcohols containing vinyloxy groups. Specific examples of the polyfunctional isocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4′-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,4 6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ' , 4 ''-triphenylmethane triisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4,4-trimethylhexame Range isocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethyl Xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4-4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) Cyclohexane, isophorone diisocyanate, lysine It is possible to increase the isocyanate and the like. Further, a trimethylolpropane adduct of the above polyisocyanate, a biuret reacted with water, a trimer having an isocyanurate ring, and the like can be used in combination. Examples of the alcohol having a vinyloxy group include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, hydroxypropenyl vinyl ether, hydroxypentyl vinyl ether, and cyclohexanedimethanol monovinyl ether.
Examples of compounds having both a vinyloxy group and other polymerizable unsaturated double bonds include 2-vinyloxyethyl acrylate (VEA), 2-vinyloxyethyl methacrylate (VEM), and 2- (2′-vinyloxyethoxy) acrylate. ) Vinyloxy group-containing (meth) acrylates such as ethyl (VEEA) and 2- (2'-vinyloxyethoxy) ethyl methacrylate (VEEM), vinyloxy groups such as 2-vinyloxyethoxystyrene and 2-vinyloxyethylstyrene Styrene is mentioned.

  The reaction between the vinyloxy group and the carboxyl group is already known, and the compound (B) and the compound (A) are mixed in a known organic solvent, and a polymerizable unsaturated double bond other than the vinyloxy group is a radical reaction. It is preferable to make it react on the conditions which do not raise | generate. Specifically, the temperature is 130 ° C. or lower, preferably 90 ° C. or lower, and the reaction is preferably performed while blowing oxygen having a radical reaction inhibiting action, or a small amount of a radical polymerization inhibitor is added. When adding the radical polymerization inhibitor, it is preferable to use about 0.001 wt% to 0.1 wt% with respect to the photoinitiator composition in order not to deteriorate the photopolymerization initiating ability of the initiator composition.

  Further, in this reaction, a catalyst can be used as necessary. Examples of the type of catalyst that can be used include phosphate ester acid catalysts such as di-n-butyl phosphate, 2-ethylhexyl phosphate, monooctyl phosphate, and the like. The addition amount of the catalyst is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight, with respect to 100 parts by weight of the total of the compound (A) and the compound (B). The reaction can be carried out in a solvent-free system, but a general-purpose organic solvent can also be used to control the reaction. In this case, the active ingredient concentration is preferably 20 to 95% by weight, more preferably 30 to 90% by weight. A concentration lower than this is not preferable because the reactivity decreases.

  The reaction ratio between the compound (A) and the compound (B) is appropriately determined according to the purpose, but when the unreacted compound (A) remains in the initiator composition produced according to the present invention, the coating film May bleed up and cause odor and migration. On the other hand, if the proportion of the compound (A) having photopolymerization initiating ability in the initiator composition is too small, sufficient curability cannot be obtained. Therefore, the molar reaction ratio between the compound (A) and the compound (B) in the reaction is preferably set to the maximum value at which the compound (A) does not remain by the reaction. The carboxyl group molar equivalent of the compound (A) is preferably 1 or less, more preferably about 0.5 to 0.8, when the vinyloxy group molar equivalent of the compound (B) is 1. In this case, the compound (B) may remain unreacted in the system even after the reaction with the compound (A), but since it has a polymerizable unsaturated double bond, It can also serve as the compound (C) having one or more polymerizable unsaturated double bonds.

  As the organic solvent used in this reaction, a general organic solvent can be used. In particular, since use as a photoinitiator is performed under solvent-free conditions, a solvent having a low boiling point that can be stripped before use as a photoinitiator is desirable. In addition, the photoinitiator composition can be reacted in the absence of a solvent if the compound (B) remains, and the photoinitiator is diluted with the low-viscosity compound B. This is particularly preferable because it is not diluted with a solvent.

  When the compound (B) has a polymerizable unsaturated double bond other than the vinyloxy group, the polymerizable unsaturated double bond can remain even after the reaction between the carboxyl group and the vinyloxy group. Further, the remaining polymerizable unsaturated double bond may be used as a polymer by radical polymerization. At this time, it may be polymerized or copolymerized with a compound (C) having one or more other polymerizable unsaturated double bonds. The compound (C) to be copolymerized is not particularly limited as long as it has a polymerizable unsaturated double bond, but the vinyloxy group of the compound (B) remaining in the reaction system may become a crosslinking point, and the compound ( It is preferable to use styrene which is easy to selectively polymerize other than the vinyloxy group of B). Furthermore, although a general-purpose solvent can be used for radical polymerization, the active ingredient concentration is preferably 10 to 40 wt% so that the remaining compound (B) does not act as a crosslinking agent.

As the initiator, organic oxides such as benzoyl peroxide, cumene hydroxy peroxide, t-butyl hydroxy peroxide, diisopropyl peroxy carbonate, di t-butyl peroxide, t-butyl peroxybenzoate, 2,2 ′ -Azo compounds such as azobisisobutyronitrile. In particular, in order not to polymerize the remaining vinyloxy group, it is desirable to use an azo compound, and a compound having a low decomposition temperature is desirable.

  In addition, when the vinyloxy group of the compound (B) remains, a radical polymerizable unsaturated compound having a carboxyl group is further added to the remaining vinyloxy group, so that the radical polymerizable unsaturated divalent compound is added to the photoinitiator itself. A double bond may be provided. Examples of the radical polymerizable unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid and phthalic acid.

  When photopolymerization is performed using the photoinitiator synthesized by the production method according to the present invention, when the compound (A) is a hydrogen abstraction type initiator, an amine coinitiator may be used in combination with the photoinitiator. desirable. The amine coinitiator is not limited as long as it becomes a hydrogen donor during photopolymerization, and examples thereof include triethanolamine, methyldiaminoethanol, ethyl dimethylaminobenzoate, and the like. In particular, those having a high molecular weight that is less affected by bleeding and odor from the coating film and those having photopolymerization reactivity such as unsaturated double bonds are desirable.

  When performing photopolymerization using the photoinitiator composition produced in the present invention, the monomer to be photopolymerized is not limited as long as it is photopolymerizable, but it is polymerized in terms of improving the curing rate and the hardness of the coating film. In order to lower the viscosity of the curable composition before photopolymerization, 2-vinyloxyethyl acrylate (VEA), 2-vinyloxyethyl methacrylate (VEM), 2-acrylic acid 2- It is desirable to use a low-viscosity photopolymerizable monomer such as (2′-vinyloxyethoxy) ethyl (VEEA) or 2- (2′-vinyloxyethoxy) ethyl methacrylate (VEEM).

  When using an energy beam irradiation device for photopolymerization, the light source usually has a light source containing light in the range of 200 to 500 nm, such as a high-pressure mercury lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp, etc. Can be used. The accumulated amount of energy rays is not limited because the required minimum accumulated amount of light depends on the application, film thickness, presence / absence of colorant, and type and amount of photopolymerization initiator. When curing with energy rays, it is not particularly necessary, but it is desirable to lower the oxygen concentration from air using an inert gas such as nitrogen.

  Although the photocurable composition formed by using the photoinitiator composition produced in the present invention can be used alone, there is a concern about bleeding of additives such as an initiator and a sensitizer. It is good to apply on the coating film and use it for the purpose of reducing bleeding from them. In particular, bleeding and odor on the surface of the coating film of the initiator and sensitizer from the coating film after photocuring containing a pigment or the like that requires high sensitivity curability can be reduced.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example shows a weight part and% shows weight%.

  In the following, the weight average molecular weight of the polymeric photopolymerization initiator was determined as follows.

<Weight average molecular weight> It was determined as a polystyrene equivalent value by gel permeation column chromatography (GPC) using THF as an eluent.

[Example 1] In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 21 parts of o-benzoylbenzoic acid, 2- (vinyloxyethoxy) ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., "VEEA") ) And 50 parts of methyl ethyl ketone (MEK) were added and stirred. Heat the liquid temperature to 80 ℃,
The reaction was carried out for 5 hours under an oxygen stream. The acid value of the reaction product was 3.4 mgKOH / g, and a photopolymerization initiator a having a photopolymerization initiator group and an acrylate group was obtained by this reaction.

  A flask was charged with 49 parts of methyl ethyl ketone and heated to 80 ° C. Under a nitrogen stream, 30 parts of the reactant a and 2.4 parts of a radical polymerization initiator AIBN were added dropwise over 2 hours using a dropping funnel, and after completion of the addition, radical polymerization was performed for another hour to obtain a polymer photoinitiator. The weight average molecular weight of the product by GPC measurement was Mw = 25500. This was designated as polymeric photopolymerization initiator b.

[Example 2] In a flask equipped with a stirrer, a thermometer, and a reflux condenser, 40 parts of 2-isocyanatoethyl-2,6-diisocyanate caproate (manufactured by Kyowa Hakko Kogyo Co., Ltd.), 2-hydroxylethyl vinyl ether 40 parts of (HEVE) (manufactured by Maruzen Petrochemical Co., Ltd.) and 0.016 part of methoxyphenol were added to the radical polymerization inhibitor. The solution was heated to 70 ° C, 0.05 parts of dibutyltin laurate (DBTDL) was added, and heated to 80 ° C when the reaction temperature was stable. After the reaction for 2 hours, the IR of the reaction product was measured, and the absorption derived from the isocyanate group disappeared. This confirmed that a trifunctional vinyl ether compound was obtained. To 31 parts of this reaction product, 19 parts of o-benzoylbenzoic acid and 50 parts of methyl ethyl ketone (MEK) were added, and the liquid temperature was heated to 80 ° C. and reacted for 6 hours under an oxygen stream. The acid value of the product after the reaction was 6.9 mgKOH / mg. As a result, a polymer photoinitiator c having an average of 1.8 polymerization initiating groups and 1.2 vinyl ether groups in the molecule was obtained.

[Example 3] To a flask equipped with a stirrer, a thermometer, and a reflux condenser, 16.3 parts of trimethylolpropane trivinyl ether (TMPTVE), 33.6 parts of o-benzoylbenzoic acid, and 50 parts of methyl ethyl ketone (MEK) were added, The liquid temperature was heated to 80 ° C. and reacted for 6 hours under an oxygen stream. The acid value of the product after the reaction was 2.4 mgKOH / mg. As a result, a polymer photoinitiator d having an average of 1.8 polymerization initiating groups and an average of 1.2 vinyl ether groups in the molecule was obtained.

[Comparative Synthesis Example 1] A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 40.1 parts of pentaerythritol polyglycidyl ether (Denacol EX-411: manufactured by Nagase ChemteX Corp.) and o-benzoylbenzoic acid. 39.4 parts and 19.9 parts of methyl ethyl ketone (MEK) were added, the liquid temperature was heated to 90 ° C., 0.08 part of N, N-dimethylbenzylamine (DMBA) was added to the catalyst, and the reaction was carried out in an oxygen stream for 6 hours. The acid value of the product after the reaction was 5.4 mgKOH / mg. As a result, a polymer photoinitiator e having 1.6 polymerization initiating groups in the molecule was obtained.

Examples 1-3 In addition, an energy ray-curable varnish was prepared from the polymer photoinitiator obtained in Comparative Synthesis Example 1 according to the composition (parts by weight) shown in Table 1, and the curability of the coating film was evaluated. Energy ray curable clear varnish was applied to a 50 mm PET film with a No. 8 bar coater, heated at 80 ° C for 5 minutes to volatilize the solvent, and then irradiated with 111mJ / cm ² of energy rays to form a cured coating film. Obtained. The above results are summarized in Table 1.

Comparative Examples 1-3: Energy ray curable varnishes were prepared using low molecular weight initiators with compositions (parts by weight) as shown in Comparative Examples 1 to 3 in Table 1, and the curability / yellowing / odor of the coating film Evaluated. The energy ray curable clear varnish was applied on a 50 mm pet film with a No. 4 bar coater, and irradiated with 111 mJ / cm ² of energy rays to obtain a cured coating film. The above results are summarized in Table 1.

  Curability: 120W metal halide lamp (focal length 25cm, condensing type, 1 light: manufactured by Ushio Electric Co., Ltd.) The value divided by the number of passes is shown. In addition, MEK was added to the cotton swab and the number of times until the underlying PET was exposed on the cured coating was confirmed.

Odor: Cut the coated material (20cm x 20cm, PET film) hardened with an energy ray irradiation of 111mJ / cm ² into fine glass bottles and leave them overnight. Five panelists relatively judge the odor. It was expressed as an average value of (bad) 5 to 0 (good).

Yellowing: those coating prepared by curing with odor under the same conditions (20 cm × 20 cm, PET film) was cut into approximately 1 cm ² square and is 5 panelists were relatively determined yellowing of films piled Yes, (bad) 5 to 0 (good), expressed as an average value.

Evaluation of migration from the cured coating: Polycoated paper with polyethylene coating on the cured coating formed by irradiating the coated material coated on the PET film by the above method with an energy ray of 222 mJ / cm ² (15cm × 10cm) was piled and a 20kg weight was placed on it 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 the supernatant 15 g, 0.1 ml of 0.1 mg / ml polystyrene standard sample (Mw = 37200) THF solution is added, and 2 g of THF is added. GPC measurement was performed after dilution. GPC detection was performed with a UV detector (wavelength 254 nm), and the relative migration was evaluated by dividing the initiator peak intensity and styrene intensity ratio by the initiator benzophenone concentration (mmol / g). . The above results are summarized in Table 2.

  As is apparent from the results in Tables 1 and 2, the polymer photoinitiator obtained by the present invention has the same curable properties as the low molecular weight photoinitiator, but the odor and Yellowing was improved and little initiator migration to polycoated paper was observed compared to low molecular weight initiators. Further, the odor and yellowing of the coating film were improved as compared with the case of using an initiator synthesized using an amine-based catalyst at the time of synthesis.

  A flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with o-benzoylbenzoic acid (OBBA) and 2- (vinyloxyethoxy) ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., “VEEA”). At this time, the molar equivalent of the carboxyl group of o-benzoylbenzoic acid was changed to 0.2 to 1.4 as shown in Table 3 with respect to the molar equivalent of 1 of the vinyloxy group of 2- (vinyloxyethoxy) ethyl acrylate. Further, 0.03 part of methoxyphenol as a polymerization inhibitor was added to 100 parts of OBBA + VEEA, the reaction mixture was heated to 80 ° C. and reacted for 5 hours under an oxygen stream to prepare an initiator composition without solvent.

  9 parts of the initiator composition produced by the above method described in Table 3, 50 parts of Aronix M-210 (manufactured by Toagosei Co., Ltd.), 38 parts of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), methyldiethanolamine Three parts were mixed to create an energy ray curable varnish. Table 3 summarizes the results of the bleed test and odor test of the cured coating film performed in the same manner as described above.

From this result, when the molar equivalent of the carboxyl group of the compound (A) is 0.5 to 0.8 with respect to the molar equivalent 1 of the vinyloxy group of the compound (B), the curing rate (tack-free PASS frequency is low and MEK rubbing frequency is It was shown that an initiator composition excellent in (high) and having reduced bleed and odor due to unreacted compounds (low odor) was obtained.

The photoinitiator of the present invention can be widely used in applications using a photopolymerization resin such as paints, inks, adhesives and molded articles. In addition to light, the initiator can also be used in applications including a polymerization process by heat, electron beam or the like that can exhibit a polymerization initiation function.

Claims (9)

A method for producing a photopolymerization initiator, comprising reacting a compound (A) having a photopolymerization initiating functional group and a carboxyl group, and a compound (B) having two or more polymerizable unsaturated double bonds Because
At least one of the polymerizable unsaturated double bonds is a vinyloxy group;
A photopolymerization initiator for reacting a carboxyl group of a compound (A) having a photopolymerization-initiating functional group and a carboxyl group with the vinyloxy group of a compound (B) having two or more polymerizable unsaturated double bonds Manufacturing method. The method for producing a photopolymerization initiator according to claim 1, wherein the compound (A) having a photopolymerization initiating functional group and a carboxyl group is an o-substituted benzoic acid derivative. The compound (B) having two or more polymerizable unsaturated double bonds has two or more vinyloxy groups, and the carboxyl group molar equivalent of the compound (A) having a photopolymerization initiating functional group and a carboxyl group, The method for producing a photopolymerization initiator according to claim 1 or 2, wherein the compound (B) having two or more polymerizable unsaturated double bonds is 0.5 to 0.8 with respect to a molar equivalent 1 of the vinyloxy group. The method for producing a photopolymerization initiator according to any one of claims 1 to 3, wherein at least one of the polymerizable unsaturated double bonds is a (meth) acryl group. Furthermore, the photoinitiator manufactured by the manufacturing method of Claim 4 is radical-polymerized, The manufacturing method of the polymeric photoinitiator characterized by the above-mentioned. Furthermore, the polymer which carries out radical polymerization of the photoinitiator manufactured with the manufacturing method of Claim 4 with the compound (C) which has one or more other polymerizable unsaturated double bonds. A method for producing a photopolymerization initiator. The photoinitiator manufactured by the manufacturing method in any one of Claims 1-6. A photopolymerizable composition comprising a photopolymerization initiator produced by the production method according to claim 1 and a compound (C) having one or more polymerizable unsaturated double bonds. A polymer obtained by photopolymerizing the photopolymerizable composition according to claim 8.