WO2018047588A1

WO2018047588A1 - Diallyl phthalate resin modified by thiol compound, photo-curable resin composition including said resin, and use thereof

Info

Publication number: WO2018047588A1
Application number: PCT/JP2017/029413
Authority: WO
Inventors: 明穂上西; 英明馬越; 岩佐　成人
Original assignee: 株式会社大阪ソーダ
Priority date: 2016-09-06
Filing date: 2017-08-15
Publication date: 2018-03-15
Also published as: JP6795037B2; TW201829481A; JPWO2018047588A1

Abstract

The purpose of the invention is to provide a photo-curable resin composition capable of constituting a composition that has excellent adhesion to plastic base materials such as polypropylene (PP) and polyethylene terephthalate (PET), and that has excellent compatibility with ethylenically unsaturated compounds. The invention provides: a photo-curable resin composition comprising a diallyl phthalate resin characterized by being modified by any one thiol compound from among aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiol compounds, mercaptocarboxylate compounds, mercaptocarboxylic acids, and mercaptoethers; and an ink and a coating comprising said photo-curable resin composition.

Description

Diallyl phthalate resin modified with thiol compound, photocurable resin composition containing the resin, and use thereof

The present invention relates to a diallyl phthalate resin modified with a specific thiol compound, a photocurable resin composition containing the modified diallyl phthalate resin, and an ink and a coating material using the resin composition. More specifically, the present invention relates to a photocurable resin composition having excellent adhesion to a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET).

Conventionally, various resin compositions that are cured by light (for example, ultraviolet rays) are used in inks, paints, adhesives, photoresists, and the like. For example, UV-curing type printing inks are highly evaluated and have been put to practical use because of their fast curing speed, which can be cured in a short time, compatibility with the environment because they do not use solvents, and resource and energy savings. It has spread.

Among such resin compositions, a resin composition containing a diallyl phthalate resin derived from diallyl phthalate (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, etc.) is employed as a UV ink for paper. .

However, it is known that when diallyl phthalate resin is blended when used as an ink, adhesion to a plastic substrate is not sufficient (for example, Patent Document 1). In recent years, various types of plastic products such as polyethylene terephthalate (PET) and polypropylene (PP) have been marketed, and improvement in adhesion to a plastic substrate, which is a drawback of diallyl phthalate resin, has been demanded.

Japanese Patent Laid-Open No. 52-4310

An object of the present invention is a photocuring that can form a composition having excellent adhesion to a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET) and having good compatibility with an ethylenically unsaturated compound. It is an object to provide a conductive resin composition.

As a result of diligent research to solve the above problems, the present inventor has added a diallyl phthalate resin modified with a specific thiol compound in a photocurable resin composition containing an ethylenically unsaturated compound, thereby producing a plastic. The present invention was completed by finding that a resin composition excellent in adhesion to the substrate and having good compatibility was obtained.

That is, the present invention is a diallyl phthalate resin that is modified with a specific thiol compound.

Further, a photocurable resin composition containing a diallyl phthalate resin modified with a specific thiol compound (and further containing an ethylenically unsaturated compound) is a photocurable resin composition having excellent adhesion to a plastic substrate, Become.
Moreover, this photocurable resin composition is particularly excellent in adhesion to PP (polypropylene) resin.
This is a combination that is preferable in terms of adhesion to the PP resin by modifying the pendant allyl group of the diallyl phthalate resin with a thiol compound to reduce the polarity of the diallyl phthalate resin and approach the polarity of the PP resin. This is considered to be because.
For this reason, a composition using a conventional diallyl phthalate resin is suitable as a component for inks and paints for PP resins, for which it was difficult to increase the adhesion.
Moreover, the diallyl phthalate resin modified with a thiol compound can constitute a composition having good compatibility with a low-polarity ethylenically unsaturated compound that is incompatible with conventional diallyl phthalate resins.

The photocurable resin composition of the present invention preferably further contains a photopolymerization initiator. By containing a photopolymerization initiator, polymerization by light irradiation proceeds smoothly, so that a higher molecular weight polymer can be obtained in a short time.

The ink of the present invention is characterized by containing the photocurable resin composition of the present invention. This ink is suitable as an ink for printing on a plastic substrate, and particularly suitable as an ink for printing on a substrate such as a PP resin sheet or film.

The paint of the present invention is characterized by containing the photocurable resin composition of the present invention. This paint is suitable as a paint for drawing on a plastic substrate, and particularly suitable as a paint for drawing on a substrate such as a PP resin sheet or film. Moreover, it is preferable that the coating material of this invention is an overprint varnish.

According to the present invention, it is possible to obtain a photocurable resin composition in which ink, paint, adhesive, and photoresist have excellent adhesion to a synthetic polymer substrate, particularly a plastic substrate. Moreover, the photocurable resin composition of this invention can be used suitably for ink and a coating material.

NMR spectrum is shown. (A) NMR spectrum of diallyl phthalate resin used in Production Example 1, (B) NMR spectrum of 2-ethylhexyl 3-mercaptopropionate used in Production Example 1, (C) used in Production Example 1. Irgacure 184 NMR spectrum, (D) represents the NMR spectrum of the thiol-modified diallyl phthalate resin obtained in Production Example 1. NMR spectrum is shown. (A) is the NMR spectrum of the diallyl phthalate resin used in Production Example 2, (B) is the NMR spectrum of 1-dodecylthiol used in Production Example 2, (C) is the NMR spectrum of Irgacure 184 used in Production Example 2, (D) represents the NMR spectrum of the thiol-modified diallyl phthalate resin obtained in Production Example 2. NMR spectrum is shown. (A) is the NMR spectrum of the diallyl phthalate resin used in Production Example 3, (B) is the NMR spectrum of 2-ethylhexylthiol used in Production Example 3, (C) is the NMR spectrum of Irgacure 184 used in Production Example 3, (D) represents the NMR spectrum of the thiol-modified diallyl phthalate resin obtained in Production Example 3.

Hereinafter, the present invention will be described in detail.

Diallyl phthalate resin modified with a thiol compound The diallyl phthalate resin modified with a thiol compound in the present invention is used without particular limitation as long as it is modified by subjecting a pendyl allyl group of the diallyl phthalate resin to an thiol compound. be able to.

The diallyl phthalate resin used for modification can be used without any particular problem as long as it has a pendant allyl group, for example, diallyl phthalate resins such as diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer and the like. These may be used singly or as a mixture of two or more. The diallyl phthalate resin may be a prepolymer made of a copolymer of two or more kinds of diallyl monomers such as diallyl orthophthalate monomer, diallyl isophthalate monomer, diallyl terephthalate monomer. In this case, a hydrogen atom on the benzene ring may be substituted with a halogen atom such as chlorine or bromine. Of these, diallyl isophthalate resin is preferable.

The molecular weight of the diallyl phthalate resin used for modification is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 200,000 from the viewpoint of improving solubility in a solvent and curability. More preferably from 20,000 to 100,000, even more preferably from 20,000 to 60,000. In the specification, “weight average molecular weight” can be determined by using gel permeation chromatography (GPC system, manufactured by Shimadzu Corporation) at 40 ° C. and using a standard polystyrene calibration curve. The weight average molecular weight of the thiol-modified diallyl phthalate resin (diallyl phthalate resin modified with a thiol compound) can also be measured by the same method.

The iodine value of the diallyl phthalate resin used for modification is not particularly limited. For example, the iodine value may be in the range of 40 to 110 g / 100 g, and is preferably in the range of 45 to 100 g / 100 g. The iodine value is a value obtained by converting the amount of halogen bonded to 100 g of the sample into g of iodine, and represents the degree of unsaturation of the sample (JIS K6235). It shows that the degree of unsaturation of a sample is so small that an iodine number (g / 100g) is small.

The thiol compound used for thiol compound modification (ene thiol reaction) can be used without any particular problem as long as it can react with the pendant allyl group of the diallyl phthalate resin. For example, an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercapto ether can be exemplified.

Examples of the aliphatic thiol compound include methyl thiol, ethyl thiol, 1-propyl thiol (n-propyl mercaptan), isopropyl thiol, 1-butyl thiol (n-butyl mercaptan), isobutyl thiol, tert-butyl thiol, 1- Pentylthiol, isopentylthiol, 2-pentylthiol, 3-pentylthiol, 1-hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol (n-heptylmercaptan), 2-heptylthiol 1-octylthiol (n-octyl mercaptan), isooctylthiol, 2-ethylhexylthiol (2-ethylhexanethiol), 2,4,4-trimethyl-2-pentylthiol (tert-octyl) Lumercaptan), 1-nonylthiol (n-nonylmercaptan), tert-nonylthiol (tert-nonylmercaptan), isononylthiol, 1-decylthiol, 1-undecylthiol, 1-dodecylthiol (1-dodecanethiol) ), Tert-dodecylthiol (tert-dodecylmercaptan), tridecylthiol, tetradecylthiol, 1-pentyldecylthiol, 1-hexyldecylthiol, 1-heptyldecylthiol, 1-octyldecylthiol, nonadecylthiol, eico Sunthiol, Triacontanethiol, Tetracontanethiol, Pentacontanethiol, Hexacontanethiol, Heptacontanethiol, Octacontanethiol, Nonacontanethiol, Hectanthi Lumpur, 1-myristyl thiol, cetyl thiol, 1-stearyl thiol, isostearyl thiol, 2-octyl-decyl thiol, 2-octyldodecyl thiol, can be exemplified 2-hexyl decyl thiol, behenyl thiols like. Of these, 1-dodecylthiol and 2-ethylhexylthiol are preferable.

As aromatic thiol compounds, benzenethiol, phenylmethanethiol, xylenethiol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, , 4-bis (2-mercaptoethyl) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethylene) Oxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercap Benzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl)

benzene

1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5-tris (2-mercaptoethyl) benzene, 1,2, 3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris (2-mercaptoethyleneoxy) benzene, 1,2,3 4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3 Tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2- Mercaptoethyl) benzene, 1,2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2 -Mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2'-dimercapto Biphenyl, 4,4'-thiobis-benzenethiol, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibe Zyl, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene -1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2 -Mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethylthiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) Benzene, 1,2,3-tris (2-mercaptoethylthio) benzene, 1,2,4-tris (2-mer Captoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) benzene, 1,2,3,5-tetrakis ( 2-mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) benzene, benzylthiol, m-toluenethiol, p-toluenethiol, 2-naphthalenethiol, 2-pyridylthiol, 2 -Examples include mercaptobenzoimidazole and 2-mercaptobenzothiazole.

Aliphatic polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,7-heptane Dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3-propanedithiol, 3-methyl-1,5 -Pentanedithiol, 2-methyl-1,8-octanedithiol, 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2 , 2,1] hepta-exo-cis-2,3-dithio 1, di-thiol compounds such as 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate); 1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol, trimethylolpropane tris (2-mercaptoacetate), trimethylol Trithiol compounds such as propanetris (3-mercaptopropionate) and tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3 Mercaptopropionate), pentaerythritol tetrakis (3-mercapto pig sulfonate), can be exemplified thiol compounds having a dipentaerythritol hexa-3-mercaptopropionate SH group such as 4 or more.

Mercaptocarboxylic acid ester compounds include methyl mercaptoacetate, methyl 3-mercaptopropionate, 4-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, 3-mercaptopropion Stearyl acid, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethanetris (3-mercaptopropionate), trimethylolethanetris ( 3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropiate) Nate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [2- (3-mercaptopropionyl) Examples thereof include oxy) ethyl] isocyanurate and tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate. Of these, 2-ethylhexyl 3-mercaptopropionate is preferable.

Other thiol compounds include mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid, thioglycolic acid and the like; di (mercapto) Mercapto ethers such as ethyl) ether; mercapto alcohol compounds such as 2-mercaptoethanol and 4-mercapto-1-butanol; silane-containing thiols such as (γ-mercaptopropyl) trimethoxysilane and (γ-mercaptopropyl) triethoxysilane Compounds and the like.

In terms of reactivity with the pendant allyl group of the diallyl phthalate resin, an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercapto ether are preferable, an aliphatic thiol compound, Mercaptocarboxylic acid ester compounds are more preferred, and mercaptocarboxylic acid ester compounds are more preferred. If it is the said thiol compound, the pendant allyl group of diallyl phthalate resin can be modified | denatured without a problem.

Enthiol reaction The enthiol reaction proceeds by bringing an unsaturated compound (such as an allyl compound or diallyl phthalate resin) into contact with a thiol compound. Usually, the reaction system containing an allyl compound and a thiol compound has an active energy (or active energy). You may make it react (enthiol reaction) by providing a line | wire. By applying active energy, the enethiol reaction can be easily advanced.

As the active energy, thermal energy and / or light energy (particularly, at least light energy) can be used depending on the type of the polymerization initiator.

When applying (or heating) soaking energy, the heating temperature may be, for example, 50 to 250 ° C., preferably 60 to 200 ° C., more preferably about 80 to 180 ° C. The application (heating) of thermal energy may be performed not only when a thermal polymerization initiator is used as an initiator but also when a photopolymerization initiator is used.

In addition, when applying (or irradiating) light energy (for example, when using a photopolymerization initiator), as light, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used. Usually, it is often ultraviolet rays. In addition, when using a thermal polymerization initiator as an initiator, irradiation of light energy is not necessarily required.

As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a mercury xenon lamp, a halogen lamp, a UV-LED lamp, a laser light source (helium-cadmium laser) A light source such as an excimer laser). The wavelength of light may be, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). The amount of irradiation light (irradiation energy) is not particularly limited, and can be selected from a range of about 1 mW to 10000 W (for example, 0.05 to 7000 W), for example, 0.1 to 5000 W, preferably 1 to 3000 W, and more preferably 10 It may be about 2000 W (for example, 30 to 1000 W). The irradiation time is not particularly limited, and may be, for example, 5 seconds to 5 hours, preferably 10 seconds to 2 hours, more preferably about 30 seconds to 1 hour, and usually about 1 to 30 minutes. May be. Note that heat energy (heating) and light energy (light irradiation) may be combined.

The polymerization initiator used for the enethiol reaction may be selected from a thermal polymerization initiator and a photopolymerization initiator according to the type of active energy ray. As the thermal polymerization initiator, dialkyl peroxides (di-tert-butylperoxide) are used. Oxides, dicumyl peroxides, etc.), diacyl peroxides [diaalkanoyl peroxides (e.g. lauroyl peroxides), dialoyl peroxides (benzoyl peroxides, benzoyl toluyl peroxides, toluyl peroxides, etc.)], peroxide esters (Peroxyacetic acid alkyl esters such as tert-butyl peracetate, tert-butyl peroxyoctoate, and tert-butyl peroxybenzoate), ketone peroxides, peroxycarbonates, peroxyketals, etc. Peroxide: Azonitrile compound [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile) 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compounds {2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl)- 2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopentanoic acid), etc.], oxime bone Can be exemplified azo compounds [2,2'-azobis (2-methylpropionamide oxime), etc.] azo compounds such as having.

As photopolymerization initiators, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone, 4- (1-tert-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- 2-hydroxy-2-propyl) ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Acetophenones such as hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc. Anthraquinones; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Thioxanthones such as propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N- Dimethyl-N Benzophenones such as [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; acylphosphine oxides and xanthones, 1,2-octane Oxime esters such as dione, 1- [4- (phenylthio)-, 2, (0-benzoyloxime)], iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophos Examples thereof include onium salt systems such as fetus and triarylsulfonium hexafluorophosphate. Of these, acetophenones are preferable.

The amount of the thiol compound used in the enthiol reaction is not particularly limited, but can be calculated by the following calculation method. The number of functional groups of the diallyl phthalate resin is obtained from the iodine value of the diallyl phthalate resin used for the enthiol reaction, and the number of functional groups in 1 g of diallyl phthalate resin (the number of functional groups of the diallyl phthalate resin) is calculated from the molecular weight of the diallyl phthalate resin and the Avogadro constant. From the molecular weight of the thiol compound used for the enthiol reaction and the Avogadro constant, the number of molecules in 1 g of the thiol compound (the number of molecules of the thiol compound) is calculated. From the calculated value, (number of functional groups of diallyl phthalate resin / number of molecules of thiol compound) × weight of diallyl phthalate resin used = the amount of thiol compound used in the enethiol reaction can be determined.

Thiol modification rate of pendant allyl group of diallyl phthalate resin in enethiol reaction is NMR peak integral value ((NMR peak integral value of diallyl phthalate resin before reaction−NMR peak integral value of thiol-modified diallyl phthalate resin after reaction) ÷ reaction) It can be calculated from the NMR peak integral value of the previous diallyl phthalate resin). The thiol modification rate of the pendant allyl group of the diallyl phthalate resin modified with a thiol compound may be 30% or more, preferably 50% or more, and more preferably 80% or more.

The weight average molecular weight (Mw) of the diallyl phthalate resin modified with a thiol compound is preferably 600,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, 200 It is particularly preferable that it is 1,000 or less, most preferably 100,000 or less, and most preferably 80,000 or less. The Mw is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and 30 Most preferably, it is 1,000 or more.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the diallyl phthalate resin modified with a thiol compound is preferably 1.0 to 10.0, and more preferably 3.0 to 5.0.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the diallyl phthalate resin modified with a thiol compound are values measured by the method described in Examples.

Photocurable resin composition The photocurable resin composition of the present invention is a resin composition before curing, and is a composition containing at least the diallyl phthalate resin modified with the above-described thiol compound.

The content of the diallyl phthalate resin modified with a thiol compound in the photocurable resin composition may be in the range of 1 to 70% by weight with respect to the total amount of the photocurable resin composition, and is 2.5 to 65% by weight. %, Preferably 5 to 60% by weight. The upper limit is more preferably 40% by weight, particularly preferably 30% by weight, and most preferably 20% by weight.

Ethylenically unsaturated compound The photocurable resin composition of the present invention preferably contains an ethylenically unsaturated compound that can be cured by light irradiation. The ethylenically unsaturated compound preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10, and still more preferably 1 to 6. Examples of the ethylenically unsaturated compound include (meth) acrylic acid ester compounds, (meth) allyl compounds, and vinyl compounds. The ethylenically unsaturated compound may be a mixture of two or more compounds.

Examples of (meth) acrylic acid ester compounds include alkyl alcohol, alkyl diol, phenoxy alcohol, pentaerythritol, dipentaerythritol, dipropylene glycol, trimethylol propane, ditrimethylol propane, neopentyl glycol, 1,6-hexanediol, and glycerin. (Meth) acrylic acid ester compounds of alcohols such as polyethylene glycol and polypropylene glycol, and (meth) acrylic acid ester compounds obtained by adding alkylene oxides such as ethylene oxide and propylene oxide thereto; bisphenols such as bisphenol A and bisphenol F (Meth) acrylic acid ester with addition of alkylene oxide such as ethylene oxide and propylene oxide Compounds; (meth) acrylic acid ester compounds such as epoxy (meth) acrylate, urethane (meth) acrylate, alkyd (meth) acrylate; (meth) acrylic acid ester compounds such as epoxidized soybean oil acrylate, Preferably, alkyl alcohol, alkyl diol, phenoxy alcohol, pentaerythritol, dipentaerythritol, trimethylol propane, ditrimethylol propane, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, glycerin, polyethylene glycol, polypropylene glycol, etc. (Meth) acrylic acid ester compounds of alcohols and alkylene oxides such as ethylene oxide and propylene oxide added to them ) Acrylic acid ester compounds, more preferably (meth) acrylic acid ester compounds of alcohols such as alkyl alcohols, alkyl diols, phenoxy alcohols, pentaerythritol, dipentaerythritol, trimethylol propane, dipropylene glycol, ditrimethylol propane, etc. And (meth) acrylic acid ester compounds in which alkylene oxides such as ethylene oxide and propylene oxide are added thereto.

Examples of the (meth) allyl compound include tri (meth) allyl isocyanurate.
Examples of the vinyl compound include styrene, divinylbenzene, N-vinylpyrrolidone, vinyl acetate and the like.

Among these, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) are compatible with diallyl phthalate resin modified with a thiol compound and cured when photocured. Alkyl (meth) acrylates such as acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acrylate such as glycerol di (meth) acrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified Tri (meth) acrylates such as trimethylolpropane triacrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, alkoxylated phenol acrylate, ethoxylated phenol acrylate, etc. Phenoxy (meth) acrylate, ditrimethylolpropane tetraacrylate, di Propylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy-diethylene glycol acrylate, trimethylolpropane triacrylate, propoxylated (2) neopentyl glycol diacrylate, epoxy acrylate and urethane acrylate are preferred.

The content of the ethylenically unsaturated compound contained in the photocurable resin composition of the present invention is 50 to 1500 weights with respect to 100 parts by weight of the diallyl phthalate resin modified with a thiol compound in the photocurable resin composition. Parts, preferably 100 to 1200 parts by weight, more preferably 100 to 900 parts by weight.

The content of the ethylenically unsaturated compound contained in the photocurable resin composition is such that the viscosity of the photocurable resin composition is in the range of 1 to 3000 mPa · s (particularly 1 to 2000) (25 ° C.). It is preferable to add so that it may become inside. Specifically, the ratio of the diallyl phthalate resin modified with the thiol compound and the ethylenically unsaturated compound is within the range of diallyl phthalate resin modified with the thiol compound: ethylenically unsaturated compound = 5: 95 to 70:30. Is preferable, and the range of 5:95 to 60:40 is more preferable.

Other Additives The photocurable resin composition of the present invention may contain a polymerization initiator, and particularly preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator contained in the photocurable resin composition include acetophenone series such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 1-hydroxycyclohexyl phenyl ketone, Examples thereof include benzoin such as benzoin and benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acylphosphine oxide, sulfur such as thioxanthone, and dibenzyl such as benzyl and 9,10-phenanthrenequinone.

The amount of the photopolymerization initiator contained in the photocurable resin composition is preferably in the range of 0.1 to 15% by weight, and preferably 0.5 to 12% by weight with respect to the entire photocurable resin composition. % Is more preferable, and the range of 1 to 10% by weight is more preferable.

A photoinitiator (for example, an amine photoinitiator such as triethanolamine) may be used in combination with the photocurable resin composition.
The amount of the photoinitiating aid is preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 3% by weight, based on the entire photocurable resin composition.

The photocurable resin composition of the present invention includes various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone and methoquinone), pigments (for example, cyanine blue, disazo yellow, carmine 6B, lake C, Various additives such as colorants such as carbon black and titanium white, fillers, viscosity modifiers and the like can be contained depending on the purpose. The amount of the stabilizer contained in the photocurable resin composition is preferably in the range of 0.01 to 2% by weight, preferably 0.1 to 1% by weight, based on the entire photocurable resin composition. A range is more preferred. The amount of the colorant is preferably in the range of 1 to 50% by weight and more preferably in the range of 1 to 45% by weight with respect to the entire photocurable resin composition.

The photocurable resin composition of the present invention is prepared by adding a diallyl phthalate resin modified with a thiol compound to an ethylenically unsaturated compound, if necessary, a photopolymerization initiator, a photoinitiator auxiliary agent, and an additive (for example, stable Agent, pigment). The photocurable resin composition of the present invention is cured by irradiating light. The light used for curing is generally ultraviolet light.

The curing device used for the curing reaction of the photocurable resin composition and the curing conditions are not particularly limited, and any method may be used as long as it is a normal photocuring reaction.

The use of the photocurable resin composition of the present invention is not particularly limited. Ink (for example, printing ink for photo-curable lithographic printing plate, silk screen ink, gravure ink, inkjet, etc.), paint (for example, paint for paper, plastic, metal, woodwork, etc. Printing varnish), adhesives, photoresists and the like.

The ink containing the photocurable resin composition of the present invention is the ink of the present invention, and the paint containing the photocurable resin composition of the present invention is the paint of the present invention. Moreover, it is preferable that the coating material of this invention is an overprint varnish.

For example, a general method for producing ink is as follows. A diallyl phthalate resin modified with a thiol compound, a stabilizer and the like are dissolved in an ethylenically unsaturated compound with stirring at a temperature of 60 ° C. to 100 ° C. to prepare a varnish. The ink is obtained by mixing the varnish with a pigment, a photopolymerization initiator, and other additives with a butterfly mixer and then kneading with a three-roll roll.
The overprint varnish can be prepared by the same procedure as that for ink except that no pigment is used.

(Example)
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples.

(Analysis method)
The analysis of the diallyl phthalate resin modified with a thiol compound described later and the diallyl phthalate resin used for the production were performed using the methods described below.

Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of diallyl phthalate resin, diallyl phthalate resin modified with thiol compound
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using GPC. It is a value of weight average molecular weight and number average molecular weight in terms of standard polystyrene.
Column: Two Shodex LF-804s connected in series Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detector: RID-20A
Sample: A sample for measurement was prepared by dissolving 50 mg of a sample in 5 mL of tetrahydrofuran.

Each NMR measurement of the diallyl phthalate resin, photopolymerization initiator, thiol compound, and thiol-modified diallyl phthalate resin obtained in the NMR measurement production was measured by 1H NMR (500 MHz, in CDCl 3). Each measured NMR spectrum is shown in FIGS.

Iodine number measurement The iodine number of the diallyl phthalate resin used for production was measured according to the method defined in JIS K6235.

Production Example 1 Synthesis of diallyl phthalate resin (resin 1) modified with a thiol compound To a 200 mL separable flask containing a stirring bar, 20 g of methyl ethyl ketone was added and stirred, diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd .; Daiso Isodap) : MW 41,000) 4 g was added and dissolved by stirring at 25 ° C. for 60 minutes. To this, 2.8 g of 2-ethylhexyl 3-mercaptopropionate (manufactured by Wako Pure Chemical Industries, Ltd.) and 118 mg of a photopolymerization initiator (Irgacure 184) were added and dissolved by stirring for 10 minutes. While stirring at 25 ° C., the enthiol reaction is performed by irradiating for 60 seconds using a light irradiation device (LIGHTNINGCURE LC6 model L8858-01, manufactured by Hamamatsu Photonics, lamp type: mercury xenon lamp, central wavelength 365 nm, emission wavelength: 300 nm to 450 nm). It was. The integrated light quantity measurement was performed using an eye ultraviolet light integrated illuminometer: UVPF-A1 light receiver: PD-365 (manufactured by Eye Graphics). The measured value was 6100 mJ / cm ² in 60 seconds. The solution after the reaction was concentrated twice using a rotary evaporator. The resulting reaction solution was added to 400 mL of stirred methanol to precipitate the resin. The precipitated solid was vacuum dried at 40 ° C. for 6 hours to obtain a diallyl phthalate resin (resin 1) modified with a thiol compound. The obtained thiol-modified diallyl phthalate resin was subjected to NMR measurement and GPC measurement (yield: 5.1 g, Mw = 65,000, Mw / Mn = 4.1). The thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (41.1545) -thiol-modified diallyl after reaction) Calculated from NMR peak integral value of phthalate resin (1.7548)) ÷ NMR peak integral value of diallyl phthalate resin before reaction (41.1545), 95.7% of allyl group was modified. NMR is shown in FIG.

Production Example 2 Synthesis of Diallyl Phthalate Resin Modified with Thiol Compound (Resin 2) The same procedure was followed except that the thiol compound of Production Example 1 was changed to 1-dodecanethiol (2.7 g), and diallyl modified with a thiol compound. A phthalate resin (Resin 2) was obtained. The obtained thiol-modified diallyl phthalate resin was subjected to NMR measurement and GPC measurement (yield: 4.1 g, Mw = 44,000, Mw / Mn = 4.8). The thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (42.6445))-thiol-modified diallyl after reaction Calculated from NMR peak integral value of phthalate resin (3.7247)) ÷ NMR peak integral value of diallyl phthalate resin before reaction (42.6445), 90.9% of allyl group was modified. NMR is shown in FIG.

Production Example 3 Synthesis of Diallyl Phthalate Resin Modified with Thiol Compound (Resin 3) The same procedure was followed except that the thiol compound of Production Example 1 was changed to 2-ethylhexanethiol (1.8 g), and modified with a thiol compound. A diallyl phthalate resin (Resin 3) was obtained. The obtained thiol-modified diallyl phthalate resin was subjected to NMR measurement and GPC measurement (yield: 4.9 g, Mw = 39,000, Mw / Mn = 3.6). The thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (53.1886))-thiol-modified diallyl after reaction Calculated from NMR peak integrated value of phthalate resin (6.7295)) ÷ NMR peak integrated value of diallyl phthalate resin before reaction (53.1886), 87.3% of allyl groups were modified. NMR is shown in FIG.

Examples 1, 2, and 3, Comparative Examples 1 and 2
The photocurable resin composition of each composition of following Table 1 was prepared, and the characteristic of the photocurable resin composition was evaluated.

The components shown in Table 1 are as follows.
The composition amounts shown in Table 1 are parts by weight.
Resin 1; Modified diallyl phthalate resin resin 2 obtained in Production Example 1; Modified diallyl phthalate resin resin 3 obtained in Production Example 2; Modified diallyl phthalate resin DAP resin obtained in Production Example 3; Osaka Soda Co., Ltd. Made Daiso isopap (diallyl isophthalate resin; Mw = 41,000, Mw / Mn = 4.1, iodine value = 80)
DPGDA: Dipropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Irgacure 184 (1-hydroxycyclohexyl phenyl ketone manufactured by BASF Japan Ltd.)

Evaluation of solubility of photocurable resin composition A resin and an ethylenic compound (2-ethylhexyl acrylate) were added so as to be 30:70, and the mixture was heated and mixed at 100 ° C to prepare a photocurable resin composition. After cooling to room temperature, solubility was confirmed based on whether the appearance of one day passed was transparent. The one whose appearance was transparent even after cooling was rated as ◯, and the one that became cloudy was marked as x. The results are shown in Table 2.

Evaluation of quick-drying 10 parts by weight of Irgacure 184 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added to 100 parts by weight of each of the prepared photocurable resin compositions, and the quick-drying is evaluated by heating and mixing. Samples to be used were prepared.
A plastic base material (polypropylene base material: biaxially stretched film manufactured by Toyobo Co., Ltd., product name: pyrene film-OT P2161 thickness 50 μm) is coated with a wire bar (coating rod) on the sample prepared for use in the adhesion test. Then, it was cured with a metal halide lamp having an output of 160 W / cm (light irradiation for a time until the coating became tack-free at a lamp distance of 14 cm and a light amount of about 200 mW / cm ² ). As the UV curing device, a box type ultraviolet curing device manufactured by USHIO was used. Quick-drying property was confirmed by touching the obtained coating film. What hardened | cured with less than integrated light quantity 4456mJ / cm < ² > was made into (circle), and what hardened with integrated light quantity 4456mJ / cm < ² > or more was made into x. The evaluation results are shown in Table 2.

Adhesion test The prepared photocurable resin composition was coated on a plastic film in the same manner as the quick-drying test and cured. A 24 mm wide cello tape (registered trademark) manufactured by Nichiban Co., Ltd. (product number: CT-24, adhesive strength: 4.01 N / 10 mm) was applied to the obtained coating film, and rubbed strongly with the thumb 5 times. Trademark) was pulled apart. The evaluation criteria were as follows. The evaluation results are shown in Table 2.
5: The cured film does not peel when the tape is peeled off quickly.
4: When the tape is peeled quickly, the cured film peels 50%.
3: The cured film does not peel when the tape is slowly peeled off.
2: When the tape is slowly peeled, the cured film peels 50%.
1: When the tape is slowly peeled off, the cured film is completely peeled off.

Using the photocurable resin composition whose viscosity was adjusted, a sample was prepared in the same manner as in the quick drying test. Viscosity at 30 ° C. was measured using a Thermo Fisher SCIENTIFC HAAKE MARS3. The evaluation results are shown in Table 2.

As shown in Examples 1 to 3, photocurable resin compositions prepared using diallyl phthalate resins (resins 1 to 3) modified with a thiol compound were modified with a thiol compound as shown in Comparative Example 1. No diallyl phthalate resin dissolves in the ethylenically unsaturated compound that did not dissolve and has an equivalent quick-drying property. And it has the adhesiveness to the polypropylene sheet of the same or more than the comparative example 1 prepared using the diallyl phthalate resin which is not modified | denatured with the thiol compound.

Claims

A diallyl phthalate resin modified with any one of an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercapto ether.
A photocurable resin composition comprising the diallyl phthalate resin according to claim 1.
Furthermore, the photocurable resin composition of Claim 2 containing an ethylenically unsaturated compound.
Furthermore, the photocurable resin composition of Claim 2 or 3 containing a photoinitiator.
An ink containing the photocurable resin composition according to any one of claims 2 to 4.
A paint containing the photocurable resin composition according to any one of claims 2 to 4.
The paint according to claim 6, which is an overprint varnish.