JPWO2018047589A1 - Polymer modified with thiol compound, and photocurable composition containing the polymer and use thereof - Google Patents

Abstract

The object of the present invention is a photo-curing property that is excellent in adhesion to a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET), and can constitute a composition having good compatibility with an ethylenically unsaturated compound. It is to provide a resin composition. The present invention includes a photocurable composition comprising a polymer obtained by modifying an allyl polymer obtained by polymerizing an allyl compound represented by the following formula (1) with a thiol compound. About. [Chemical formula 1]

Description

  The present invention relates to a polymer modified with a specific thiol compound, a photocurable resin composition containing the modified polymer, and an ink and a paint formed using the resin composition. More specifically, the present invention relates to a photocurable resin composition excellent in 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 light) are used for inks, paints, adhesives, photoresists, and the like. For example, ultraviolet curing type printing inks have high curing speed and can be cured in a short time, and because they do not use solvents, they are highly evaluated for their compatibility with the environment, resource saving and energy saving, etc. It has spread.

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

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

Japanese Patent Application Laid-Open No. 52-4310

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

  MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, this inventor is adhesion with a plastic base material in the photocurable resin composition containing the polymer which modified | denatured the allylic polymer which has a specific structure by the thiol compound. The present invention has been completed by finding that a resin composition having excellent properties and compatibility is obtained.

［式中、ｎは２〜４のいずれかの整数を表わし、Ｚはｎ価の脂環式炭化水素基である］
で表されるアリル化合物を重合して得られるアリル系重合体を、チオール化合物で変性したことを特徴とするポリマー。
項２． 前記チオール化合物が、脂肪族チオール化合物、芳香族チオール化合物、脂肪族ポリチオール化合物、メルカプトカルボン酸エステル化合物、メルカプトカルボン酸、メルカプトエーテルのいずれかのチオール化合物である項１に記載のポリマー。
項３． 項１又は２に記載のポリマーを含有する光硬化性樹脂組成物。
項４． 更に、エチレン性不飽和化合物（Ｂ）を含有する項３に記載の光硬化性樹脂組成物。
項５． 更に、光重合開始剤を含有する項３又は４に記載の光硬化性樹脂組成物。
項６． 項３〜５のいずれかに記載の光硬化性樹脂組成物を含有するインキ。
項７． 項３〜５のいずれかに記載の光硬化性樹脂組成物を含有する塗料。
項８． オーバープリントワニスである項７に記載の塗料。
である。According to the invention
Item 1. Following formula (1),

[Wherein, n represents any integer from 2 to 4 and Z is an n-valent alicyclic hydrocarbon group]
A polymer characterized in that an allyl-based polymer obtained by polymerizing an allyl compound represented by the above is modified with a thiol compound.
Item 2. The polymer according to item 1, wherein the thiol compound is a thiol compound of any of an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid and a mercaptoether.
Item 3. The photocurable resin composition containing the polymer as described in claim 1 or 2.
Item 4. The photocurable resin composition according to Item 3, further comprising an ethylenically unsaturated compound (B).
Item 5. 5. The photocurable resin composition according to item 3 or 4, further comprising a photopolymerization initiator.
Item 6. An ink containing the photocurable resin composition according to any one of Items 3 to 5.
Item 7. The coating material containing the photocurable resin composition in any one of claim 3-5.
Item 8. 8. The paint according to item 7, which is an overprint varnish.
It is.

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

The NMR spectrum of polymer 1 is shown. (A) NMR spectrum of polymer 1 used in Production Example 3, (B) NMR spectrum of 2-ethylhexyl 3-mercaptopropionate used in Production Example 3, (C) use in Production Example 3 The NMR spectrum of Ingacure 184, which is shown in FIG. The NMR spectrum of polymer 2 is shown. (A) NMR spectrum of polymer 1 used in Production Example 4, (B) NMR spectrum of 1-dodecylthiol used in Production Example 4, (C) NMR spectrum of Ingacure 184 used in Production Example 4, (D) shows the NMR spectrum of the thiol modified polymer obtained in Production Example 4. The NMR spectrum of polymer 3 is shown. (A) NMR spectrum of polymer 1 used in Production Example 5, (B) NMR spectrum of 2-ethylhexylthiol used in Production Example 5, (C) NMR spectrum of Ingacure 184 used in Production Example 5, (D) represents the NMR spectrum of the thiol modified polymer obtained in Production Example 5.

Hereinafter, the present invention will be described in detail.

［式中、ｎは２〜４のいずれかの整数を表わし、Ｚはｎ価の脂環式炭化水素基である］ Polymer Modified with Thiol Compound The polymer modified with a thiol compound in the present invention is a polymer obtained by modifying an allyl-based polymer obtained by polymerizing an allyl compound represented by the following formula (1) with a thiol compound.

[Wherein, n represents any integer from 2 to 4 and Z is an n-valent alicyclic hydrocarbon group]

［式中、ｎは２〜４のいずれかの整数を表わし、Ｚはｎ価の脂環式炭化水素基である］ The allyl-based polymer used for allyl-based polymer modification is obtained by polymerizing an allyl compound represented by the following formula (1).

[Wherein, n represents any integer from 2 to 4 and Z is an n-valent alicyclic hydrocarbon group]

In the n-valent alicyclic hydrocarbon group for Z in the formula (1), the number of carbon atoms forming the ring structure of the alicyclic hydrocarbon group is preferably 3 to 18, and it is 4 to 12 More preferably, it is particularly preferably 4 to 10, and most preferably 5 to 7.
n is an integer of 2 to 4, preferably 2 to 3, and more preferably 2.
The n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group, and may have a unsaturated bond in part, but a saturated n-valent alicyclic group It is preferably a formula hydrocarbon group. In the present invention, alicyclic means a hydrocarbon group having a cyclic structure having no aromaticity.
Z may be crosslinked in the molecule, and examples of Z crosslinked in the molecule include adamantane, norbornene, norbornane and the like.

  The n-valent alicyclic hydrocarbon group may have an alkyl group. The alkyl group may be a linear or branched chain having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. One or two or more alkyl groups may be present at substitutable positions of the alicyclic hydrocarbon group. The n-valent alicyclic hydrocarbon group may not necessarily have an alkyl group.

  When Z in the formula (1) is an n-valent alicyclic hydrocarbon group, specific allyl compounds include the following general formulas (2) to (9) (in particular, the formulas (5) to (7) is preferable, and the allyl compound of (7) can be illustrated.

［式中、ｎは２〜４のいずれかの整数である。］

[Wherein, n is an integer of 2 to 4]. ]

The substitution position of the COOCH ₂ CH = CH ₂ group on the ring of the formulas (2) to (9) may be any combination or a mixture thereof. In particular, when two COOCH ₂ CH = CH ₂ groups are bonded to a six-membered ring, the two COOCH ₂ CH = CH ₂ groups may be either ortho-orientation or meta-or para-orientation, but ortho-orientation or para-orientation. It is preferable that it is orientation.

  Specific examples of the allyl compound when Z in the formula (1) is an n-valent alicyclic hydrocarbon group include diallyl cyclobutanedicarboxylate, diallyl cycloheptanedicarboxylate, diallyl cyclohexanedicarboxylate (hexahydrophthalic acid) Diallyl), norbornane dicarboxylic acid diallyl, cyclobutene dicarboxylic acid diallyl, cycloheptene dicarboxylic acid diallyl, cyclohexene dicarboxylic acid diallyl (tetrahydrolyl phthalic acid diallyl) and norbornene dicarboxylic acid diallyl, 3-methyl-hexahydro-1,2-diallyl phthalate; 4-Methyl-hexahydro-1,2-diallyl phthalate, 3-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 4-methyl-1,2,3,6-tetrahydro-1, 2- diallyl Rate, 3,6-endomethylene-3-methyl-1,2,3,6-tetrahydro-1,2-diallyl phthalate, 3,6-endomethylene-4-methyl-1,2,3,6-tetrahydrofuran Exemplarily exemplifying 1,2-diallyl phthalate, diallyl 4-cyclohexene-1,2-dicarboxylate, diallyl 2-cyclohexene-1,2-dicarboxylate, tetraallyl 1,2,3,4-butanetetracarboxylate and the like Can. Among these, diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, and diallyl norbornanedicarboxylate are preferable, and diallyl 1,2-cyclohexanedicarboxylate is more preferable.

[式中、ｎ、及びＺに関しては、前記一般式（１）におけるｎ、及びＺと同じ意味である。]The allyl compound represented by the formula (1) of the present invention is a carboxylic acid compound represented by the following general formula (10), or an acid anhydride thereof and an allyl halide or allyl alcohol, for example, an acidic substance, basicity It can be produced by reacting in the presence of a substance, a catalyst and a solvent. The carboxylic acid compounds represented by the general formula (10) are available as reagents and industrial chemicals. Of course, as the allyl compound represented by the formula (1), a commercial product of the allyl compound represented by the formula (1) may be used.

[In the formula, n and Z have the same meaning as n and Z in the general formula (1). ]

  Examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide and the like. Although the amount of allyl halide used is not particularly limited, it is usually preferably in the range of 2 to 20 equivalents based on the carboxylic acid compound represented by the general formula (10), and from the viewpoint of reaction rate and volume efficiency Is more preferably in the range of 2.3 to 10 equivalents. These halogenated allyl compounds are available as reagents and industrial chemicals.

  Allyl alcohol is available as a reagent or industrial chemical. Although the amount of allyl alcohol used is not particularly limited, it is usually preferably in the range of 2 to 10 equivalents, more preferably in the range of 2 to 5 equivalents relative to the carboxylic acid compound represented by the general formula (10) Is more preferred.

  Examples of the acidic substance include sulfuric acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid, and the amount of the acidic substance used is 0.001 to 0.1 with respect to the carboxylic acid compound represented by the general formula (10). It is preferably in the range of equivalents, more preferably in the range of 0.005 to 0.05 equivalents.

  Examples of basic substances include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals such as sodium hydride and potassium hydride, carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonate Sodium bicarbonate, hydrogen carbonates such as potassium hydrogen carbonate, alcoholates and the like are generally used, but it is also possible to use quaternary ammonium compounds and organic bases such as aliphatic amines and aromatic amines. The amount of the basic substance used is preferably in the range of 0.5 to 30 equivalents, and more preferably in the range of 2 to 15 equivalents with respect to the carboxylic acid compound represented by the general formula (10).

As a catalyst, for example, transition metals and transition metal salts such as copper, iron, cobalt, nickel, chromium, vanadium and the like are used, and of these, copper compounds are preferably used.
The copper compound is not particularly limited, and most copper compounds are used, but cuprous chloride, cuprous bromide, cuprous oxide, cuprous iodide, cuprous cyanide, cuprous sulfate Cupric sulfate, cupric chloride, cupric hydroxide, cupric bromide, cupric phosphate, cuprous nitrate, cupric nitrate, copper carbonate, cuprous acetate, second acetate Copper and the like are preferred. Among them, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, copper sulfate and cupric acetate are particularly preferable because they are easily available and inexpensive. It is.

  The reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene; saturated aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether Ethers such as diethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; dimethylformamide, N-methylpyrrolidone, sulfolane and the like It can be mentioned. One of these may be used alone, or two or more may be used in combination. When a solvent is used, the amount thereof used is not particularly limited, but in general, it is preferably in the range of 0.01 to 20 times by weight with respect to the carboxylic acid compound represented by General Formula (11). More preferably, it is in the range of 1 to 10 times by weight. In the case of this reaction, an allyl compound can be efficiently produced without using any solvent.

  In particular, when a basic substance is used in the reaction as an aqueous solution, it is preferable to use a phase transfer catalyst to accelerate the reaction. The phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as trioctylmethyl ammonium chloride, tetrabutyl ammonium chloride and tetrabutyl ammonium bromide; phosphonium salts such as tetrabutyl phosphonium chloride; 15-crown-5, 18 -Crown ethers such as crown-6 etc. may be mentioned. When a phase transfer catalyst is used, the amount thereof used is preferably in the range of usually 0.001 to 1 equivalent to the carboxylic acid compound represented by the general formula (10), and 0.01 to 0. More preferably, it is in the range of 4 equivalents.

  The reaction temperature is preferably in the range of -30 to 150 ° C, preferably in the range of -10 to 130 ° C, in order to obtain a sufficient reaction rate and effectively suppress side reactions and obtain a high yield. It is more preferable that there be. The reaction time is preferably in the range of 10 minutes to 15 hours, and preferably in the range of 10 minutes to 10 hours from the viewpoint of side reaction suppression.

  The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. The reaction can be carried out under atmospheric pressure or under pressure, but from the viewpoint of production equipment, it is preferable to carry out under atmospheric pressure. The reaction can be carried out, for example, by charging the raw materials at once or in divided portions into a stirring type reactor and reacting for a predetermined time at a predetermined temperature as described above.

  After completion of the reaction, the reaction mixture obtained is neutralized, and if necessary, washed with water, saturated brine and the like, concentrated, and further commonly used in purification of organic compounds such as distillation and column chromatography. By carrying out the purification operation which is carried out, highly pure compounds can be obtained. An allyl-based polymer is obtained by polymerizing the obtained allyl compound by the polymerization method described later.

  The polymerization method of the allyl polymer is not particularly limited, and a usual polymerization reaction can be used. A polymerization initiator may be appropriately added to the polymerization reaction, if necessary. By using a polymerization initiator, a polymer of higher molecular weight can be obtained in a short time.

  As a polymerization initiator used for the polymerization reaction, azo initiators such as azobisisobutyronitrile and dimethyl 2,2'-azobisisobutyrate, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides and diacyl peroxides Peroxide initiators such as peroxydicarbonate, peroxyester, benzoyl peroxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1-hydroxycyclohexylphenyl Acetophenone such as ketone, benzoin such as benzoin and benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acyl phosphine oxide, sulfur such as thioxanthone, benzyl, 9, 10-phenanthrenequinone, etc. Benzyl-based photopolymerization initiators.

The addition amount of the polymerization initiator is preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less, and more preferably 0.001 to 3.0 parts by weight with respect to 100 parts by weight of the allyl compound. More preferably, it is a part.
It is preferable that it is 60-240 degreeC, and, as for the reaction temperature at the time of superposition | polymerization, it is more preferable that it is 80-220 degreeC. The reaction time is preferably 0.1 to 100 hours, and more preferably 1 to 30 hours.

  More specifically, an allyl having a monomer unit based on the allyl compound represented by the general formula (1) by polymerizing the allyl compound represented by the general formula (1) according to the above-mentioned method or the like Based polymers can be prepared.

  The weight average molecular weight of the allyl-based polymer in the present invention is preferably 500,000 or less, more preferably 400,000 or less, particularly preferably 2,000 to 150,000, 5, More preferably, it is in the range of 1000 to 140,000. In the specification, “weight-average molecular weight” can be determined at 40 ° C. using gel permeation chromatography (GPC system, manufactured by Shimadzu Corporation) and can be determined using a standard polystyrene calibration curve. The weight average molecular weight of the thiol modified polymer (polymer modified with a thiol compound) can also be measured by the same method.

  The content of the monomer unit based on the compound represented by the above formula (1) is preferably 20% by weight or more in 100% by weight in total of the monomer units constituting the allyl polymer, and 50 It is more preferably at least 80% by weight, particularly preferably at least 98% by weight, and may be 100% by weight.

The thiol compound used for thiol compound modification | denaturation (enthiol reaction) can be used without a problem in particular, if it can react with the pendant allyl group of an allyl-type polymer. For example, aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiol compounds, mercapto carboxylic acid ester compounds, mercapto carboxylic acids and mercapto ethers can be exemplified.

  Examples of aliphatic thiol compounds 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- Pentyl thiol, isopentyl thiol, 2-pentyl thiol, 3-pentyl thiol, 1-hexyl thiol, cyclohexyl thiol, 4-methyl-2-pentyl thiol, 1-heptyl thiol (n-heptyl mercaptan), 2-heptyl thiol 1-octylthiol (n-octylmercaptan), isooctylthiol, 2-ethylhexylthiol, 2,4,4-trimethyl-2-pentylthiol (tert-octylmercaptan), 1-nonylthio (N-nonyl mercaptan), tert-nonyl thiol (tert-nonyl mercaptan), isononyl thiol, 1-decyl thiol, 1-undecyl thiol, 1-dodecyl thiol, tert-dodecyl thiol (tert-dodecyl mercaptan) , Tridecylthiol, tetradecylthiol, 1-pentyldecylthiol, 1-hexyldecylthiol, 1-heptyldecylthiol, 1-octyldecylthiol, nonadecylthiol, eicosanethiol, triacontanthiol, tetracontanthiol, pentacone Tanthiol, hexacontanthiol, heptacontanthiol, octacontanthiol, nonacontanthiol, hextanthiol, 1-myristylthiol, cetylthiol, 1-stene Riruchioru, isostearyl thiol, 2-octyl-decyl thiol, 2-octyldodecyl thiol, can be exemplified 2-hexyl decyl thiol, behenyl thiols like. Among these, 1-dodecyl thiol and 2-ethylhexyl thiol 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, 1 , 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-trimercapto Starch, 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, 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, 1,2,3,4 Tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercapto) Ethyl) 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'-dimercaptobiphenyl 4,4'-thiobis-benzenethiol, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobiben , 2,5-toluene dithiol, 3,4-toluene dithiol, 1,4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,6-naphthalene dithiol, 2,7-naphthalene dithiol, 2,4-dimethyl benzene 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-merca) (Peptethylthio) 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-mercapto Benzimidazole, 2-mercaptobenzothiazole and the like can be exemplified.

  As aliphatic polythiol compounds, 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-nonane dithiol, 1,10-decanedithiol, 1,12-dodecane dithiol, 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- Dithiol 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), trimethylolpropane Trithiol compounds such as tris (3-mercaptopropionate), tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3- Le 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.

  As mercaptocarboxylic acid ester compounds, 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, trimethylolethane tris (3-mercaptopropionate), trimethylolethane tris ( 3-Mercaptobutylate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropio) ), Pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [2- (3-mercapto) Propionyloxy) ethyl] isocyanurate, tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate and the like can be exemplified. Among them, 2-ethylhexyl 3-mercaptopropionate is preferable.

  Other thiol compounds such as mercaptocarboxylic acids such as mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid, thioglycolic acid; 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 A compound etc. can be illustrated.

  Aliphatic thiol compounds, aromatic thiol compounds, aliphatic polythiols, mercaptocarboxylic acid ester compounds, mercaptocarboxylic acids and mercaptoethers are preferred, and aliphatic thiol compounds, from the viewpoint of the reactivity with the pendant allyl group of allylic polymers. Mercapto carboxylic acid ester compounds are more preferred. If it is the said thiol compound, the pendant allyl group of an allyl-type polymer can be modify | denatured without a problem.

Enthiol reaction The enethiol reaction proceeds by contacting the unsaturated compound (allyl compound, allylic polymer obtained by polymerizing an allyl compound, etc.) with a thiol compound, but in general, in a reaction system containing an allyl compound and a thiol compound, It may be made to react (enthiol reaction) by giving active energy (or active energy ray). By the application of activation energy, the enethiol reaction can easily proceed.

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

  When applying (or heating) thermal energy, the heating temperature may be, for example, about 50 to 250 ° C., preferably 60 to 200 ° C., and 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.

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

  As the light source, for example, in the case of ultraviolet light, Deep UV lamp, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, mercury xenon lamp, halogen lamp, UV-LED lamp, laser light source (helium-cadmium laser Or a light source such as an excimer laser can be used. The wavelength of light may be, for example, about 150 to 800 nm, preferably about 150 to 600 nm, and more preferably about 200 to 400 nm (particularly about 300 to 400 nm). The irradiation light amount (irradiation energy) is not particularly limited, and can be selected from the 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, more preferably 10 It may be about -2000 W (e.g., 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 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, and dialkyl peroxides (di-tert-butylpermer as a thermal polymerization initiator) Oxides, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxides (lauroyl peroxide, etc.), diaroyl peroxides (benzoyl peroxide, benzoyl toluyl peroxide, etc.), peroxy esters Organic compounds such as peracetic acid alkyl esters such as peracetic acid tert-butyl, tert-butyl peroxy octoate, tert-butyl peroxy benzoate and the like, ketone peroxides, peroxy carbonates and peroxy ketals Oxide; 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 compound {2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide} etc., azoamidine compound {2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] di Hydrochlorides etc., azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopentanoic acid) etc.], oxime skeleton Azo compounds [2,2'-azobis (2-methylpropionamide oxime), etc.] azo compounds such as having can be exemplified.

  Benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether as a photopolymerization initiator; 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) propanone oligomer; 2-methyl anthraquinone, 2-amyl anthraquinone, 2-tert-butyl anthraquinone, 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 meso chloride; 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-butylperoxy carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N- Dimethyl-N Benzophenones such as-[2- (1-oxo-2-propenyloxy) ethyl] benzenemethaminium bromide, (4-benzoylbenzyl) trimethylammonium chloride; acyl phosphine oxides and xanthones, 1,2-octane Oxime ester such as dione, 1- [4- (phenylthio)-, 2, (0-benzoyloxime)], iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophos Examples of onium salt systems such as phosphate and triarylsulfonium hexafluorophosphate can be given. Among them, acetophenones are preferred.

  The use amount of the thiol compound in the enethiol reaction is not particularly limited, but can be calculated by the following calculation method. The functional group number of the allyl polymer is determined from the iodine value of the allyl polymer used for the enethiol reaction, and the number of functional groups in 1 g of the allyl polymer (the functional group number of the allyl polymer) from the molecular weight of the allyl polymer and the Avogadro constant. Calculate). The number of molecules in 1 g of the thiol compound (the number of molecules of the thiol compound) is calculated from the molecular weight of the thiol compound used for the enethiol reaction and the Avogadro constant. From the calculated value, (number of functional groups of allyl polymer / number of molecules of thiol compound) × weight of allyl polymer used = the amount of the thiol compound used for the enethiol reaction can be determined. The iodine value of the allyl polymer can be measured according to the method defined in JIS K6235.

  The thiol modification rate of the pendant allyl group of the allyl-based polymer in the enethiol reaction is the NMR peak integral value ((NMR peak integral value of the allyl-based polymer before the reaction-NMR peak integral value of the polymer after the reaction) It can be calculated from the NMR peak integral value of the allyl polymer. The thiol modification rate of the pendant allyl group of the polymer modified with a thiol compound may be 30% or more, preferably 50% or more, and more preferably 80% or more. Also, the weight average molecular weight of the thiol modified polymer is greater than the weight average molecular weight of the polymer before modification.

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

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer 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 a polymer modified with a thiol compound are values measured by the methods described in the 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 a polymer modified with the above-mentioned thiol compound.

  The content of the polymer 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 2.5 to 65% by weight It is preferably in the range, and more preferably in the range of 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 which is curable by light irradiation. The ethylenically unsaturated compound preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10 carbons, and still more preferably 1 to 6 carbons. Examples of the ethylenically unsaturated compound include (meth) acrylic acid ester compounds, (meth) allyl compounds and vinyl compounds. Moreover, it is also possible to use a mixture of two or more types of ethylenically unsaturated compounds.

  As the (meth) acrylic acid ester compound, alkyl alcohol, alkyl diol, phenoxy alcohol, pentaerythritol, dipentaerythritol, dipropylene glycol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin (Meth) acrylic acid ester compounds of alcohols such as polyethylene glycol and polypropylene glycol, and (meth) acrylic acid ester compounds obtained by adding an alkylene oxide such as ethylene oxide and propylene oxide thereto; bisphenols such as bisphenol A and bisphenol F (Meth) acrylic esters of ethylene oxide, propylene oxide and other alkylene oxides added Compounds; (meth) acrylic acid ester compounds such as epoxy (meth) acrylate, urethane (meth) acrylate, alkyd (meth) acrylate; and (meth) acrylic acid ester compounds such as epoxidized soybean oil acrylate Preferably, alkyl alcohol, alkyl diol, phenoxy alcohol, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, glycerin, polyethylene glycol, polypropylene glycol, etc. (Meth) acrylic acid ester compounds of alcohols of the following types, and alkylene oxides such as ethylene oxide and propylene oxide added thereto (meta Acrylic acid ester compounds, more preferably (meth) acrylic acid ester compounds of alcohols such as alkyl alcohol, alkyl diol, phenoxy alcohol, pentaerythritol, dipentaerythritol, trimethylol propane, dipropylene glycol, ditrimethylol propane, etc. And (meth) acrylic acid ester compounds obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide thereto.

As a (meth) allyl compound, tri (meth) allyl isocyanurate etc. can be illustrated.
Examples of vinyl compounds include styrene, divinylbenzene, N-vinylpyrrolidone, vinyl acetate and the like.

  Among them, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, from the viewpoint of compatibility with a polymer modified with a thiol compound and curability upon photocuring. Alkyl (meth) acrylates such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di ( Di) (meth) acrylate such as meta) acrylate, triethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylol Tri (meth) acrylates such as loppan triacrylate, benzyl (meth) acrylates, phenoxyethyl (meth) acrylates, alkoxylated phenol acrylates, phenoxy (meth) acrylates such as ethoxylated phenol acrylates, ditrimethylolpropane tetraacrylate, dipropylene glycol Diacrylate, tripropylene glycol diacrylate, ethoxy-diethylene glycol acrylate, trimethylolpropane triacrylate, propoxylated (2) neopentyl glycol diacrylate, epoxy acrylate, 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 parts by weight with respect to 100 parts by weight of the polymer modified with the thiol compound in the photocurable resin composition. It is preferably 50 to 1200 parts by weight, more preferably 100 to 900 parts by weight.

  In addition, the content of the ethylenically unsaturated compound contained in the photocurable resin composition is in the range of 1 to 3000 mPa · s (particularly, 1 to 2000) (25 ° C.) of the viscosity of the photocurable resin composition. It is preferable to add so that it is inside. Specifically, the ratio of the polymer modified with the thiol compound to the ethylenically unsaturated compound is preferably in the range of 5:95 to 70:30 of the polymer modified with the thiol compound: ethylenic unsaturated compound, 5 More preferably, it is in the range of 95:60:40.

Other Additives The photocurable resin composition of the present invention may contain a polymerization initiator, and preferably contains a photopolymerization initiator. The photopolymerization initiator contained in the photocurable resin composition is an acetophenone such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 1-hydroxycyclohexyl phenyl ketone, etc. Benzoin such as benzoin and benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acyl phosphine 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, preferably 0.5 to 12%, with respect to the entire photocurable resin composition. The range of% is more preferable, and the range of 1 to 10% by weight is more preferable.

You may use together a photoinitiator adjuvant (for example, amine type photoinitiator adjuvants, such as a triethanolamine, etc.) with a photocurable resin composition.
The amount of the photoinitiator 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 total weight of the photocurable resin composition.

  The photocurable resin composition of the present invention comprises various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone and methoquinone), pigments (for example, cyanine blue, disazoero, carmine 6B, latex C, Various additives such as colorants such as carbon black and titanium white), fillers, and viscosity modifiers can be contained according to the purpose. The amount of 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 total weight of the photocurable resin composition. The 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, based on the total weight of the photocurable resin composition.

The photocurable resin composition of the present invention is a polymer modified with a thiol compound, and if necessary, an ethylenically unsaturated compound, and further, a photopolymerization initiator, a photopolymerization assistant, an additive (for example, a stabilizer, It can be produced by mixing pigments).
The photocurable resin composition of the present invention is cured by irradiation with light. The light used for curing is generally ultraviolet light.

  The curing apparatus 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 used for a normal photocuring reaction.

  The application of the photocurable resin composition of the present invention is not particularly limited. Ink (for example, photocurable lithographic printing ink, silk screen ink, gravure ink, printing ink for inkjet, etc.), paint (for example, for paper, plastic, metal, woodworking, etc. It can be used in the technical fields such as printing varnishes), adhesives, and photoresists.

  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. The paint of the present invention is preferably an overprint varnish.

  For example, the general preparation method of the ink is as follows. A polymer obtained by modifying an ethylenically unsaturated compound with a thiol compound, a stabilizer and the like are dissolved with stirring at a temperature of 60 ° C. to 100 ° C. to prepare a varnish. A pigment, a photopolymerization initiator and other additives are stirred and mixed in this varnish with a butterfly mixer and then kneaded with a triple roll or the like to obtain an ink. Moreover, preparation of overprint varnish can be performed according to the procedure similar to ink except not using a pigment.

(Example)
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples at all.

(Analytical method)
The analysis of the polymer modified with a thiol compound described later was performed using the method described below.

Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polymers modified with thiol compounds
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were measured using GPC. It is the value of the weight average molecular weight of standard polystyrene conversion, a number average molecular weight.
Column: Two Shodex LF-804 connected in series Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detector: RID-20A
Sample: 50 mg of a sample was dissolved in 5 mL of tetrahydrofuran to prepare a sample for measurement.

NMR Measurement Each NMR measurement of the allyl-based polymer, the thiol compound, the photopolymerization initiator, and the obtained thiol-modified polymer used for the preparation was measured by 1 H NMR (500 MHz, in CDCl 3). Each NMR spectrum measured is shown in FIGS.

Iodine Value Measurement The iodine value of the allyl polymer used for production was measured according to the method defined in JIS K6235.

Production Example 1 Synthesis of diallyl 1,2-cyclohexanedicarboxylate A diallyl 1,2-cyclohexanedicarboxylate was produced according to a method for producing an allyl compound in which cyclohexanedicarboxylic acid anhydride and allyl alcohol are described above. The obtained diallyl 1,2-cyclohexanedicarboxylate was used in the examples.

Production Example 2 Synthesis of 1,2-Cyclohexanedicarboxylic Acid Diallyl Polymer In a 3 L separable flask, 2400 g of diallyl 1,2-cyclohexanedicarboxylate obtained in Production Example 1 is added, 60 g of benzoyl peroxide is added, and the mixture is heated at 80 ° C. Heated and stirred. After reacting for 2.5 hours, it was cooled to 30 ° C. After cooling, methanol was added to the flask to precipitate a polymer. The obtained polymer was dried under reduced pressure at 40 ° C. for 16 hours (yield: 408 g, yield: 17%, Mw = 32,000, Mw / Mn = 2.8). The obtained polymer was referred to as polymer 1. The iodine number of the polymer 1 was 55.

Production Example 3 Synthesis of Polymer Resin Modified with Thiol Compound (Polymer 1) 4 g of the polymer 1 obtained in Production Example 2 was added to a 200 mL eggplant flask containing a stirring bar, and 20 g of methyl ethyl ketone was added. Stir for a minute to dissolve. Thereto, 1.9 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. The enthiol reaction is performed by irradiating for 60 seconds using a light irradiator (LIGHTNINGCURE LC6 model L 8858-01 manufactured by Hamamatsu Photonics, lamp type: mercury xenon lamp, central wavelength 365 nm, emission wavelength: 300 nm to 450 nm) while stirring at 25 ° C. went. In addition, integrated light quantity measurement was performed using an eye ultraviolet integrated luminance meter: UVPF-A1 light receiver: PD-365 (made by Eye Graphics Co., Ltd.). The measured value was 6100 mJ / cm ² at 60 seconds. The solution after reaction was concentrated twice by using a rotary evaporator. The resulting reaction solution was added to 400 mL of methanol under stirring to precipitate a polymer. The precipitated solid was subjected to vacuum drying at 40 ° C. for 6 hours to obtain a thiol compound-modified polymer (polymer 1). The NMR measurement and GPC measurement of the obtained thiol modified polymer were performed (yield: 4.1 g, Mw = 61,000, Mw / Mn = 3.9). The thiol modification rate of the pendant allyl group of the thiol modified polymer is an NMR peak integral value of 5.9 ppm indicating the allyl group (NMR peak integral value of allyl polymer before reaction (31.9502))-NMR of polymer after reaction The peak integration value (1.7774) was calculated from the NMR peak integration value (31.9502) of the allyl polymer before the reaction, and 94.4% of the allyl group was denatured.

Production Example 4 Synthesis of Polymer Resin Modified with Thiol Compound (Polymer 2) A polymer modified with a thiol compound was carried out in the same manner as in Production Example 3 except that the thiol compound in Example 3 was changed to 1.8 g of 1-dodecylthiol Got). The NMR measurement and GPC measurement of the obtained thiol modified polymer were performed (yield: 4.7 g, Mw = 43,000, Mw / Mn = 3.7). The thiol modification rate of the pendant allyl group of the thiol modified polymer is the NMR peak integral value of 5.9 ppm indicating the allyl group (NMR peak integral value of the allyl polymer before the reaction (773.9509))-NMR of the polymer after the reaction The peak integration value (110.6631) was calculated from the NMR peak integration value (773.9509) of the allyl polymer before the reaction, and 85.7% of the allyl group was denatured.

Production Example 5 Synthesis of Polymer Resin Modified with Thiol Compound (Polymer 3) A polymer modified with a thiol compound was carried out by the same method except that the thiol compound in Production Example 3 was changed to 1.2 g of 2-ethylhexyl thiol (Polymer 3 Got). The NMR measurement and GPC measurement of the obtained thiol modified polymer were performed (yield: 4.4 g, Mw = 44,000, Mw / Mn = 3.6). The thiol modification rate of the pendant allyl group of the thiol modified polymer is the NMR peak integral value of 5.9 ppm indicating the allyl group (NMR peak integral value of the allyl polymer before the reaction (86.5927))-NMR of the polymer after the reaction The peak integration value (14.6921) was calculated from the NMR peak integration value (86.5927) of the allyl polymer before the reaction, and 83.0% of the allyl group was denatured.

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

表１に示した成分は下記のとおりである。
また、表１に示す組成量は重量部である。
ポリマー１；製造例３で得られた変性ポリマー
ポリマー２；製造例４で得られた変性ポリマー
ポリマー３；製造例５で得られた変性ポリマー
ＤＰＧＤＡ；ジプロピレングリコールジアクリレート （新中村化学工業（株）製）
Ｉｒｇａｃｕｒｅ１８４（ＢＡＳＦジャパン（株）製の１−ヒドロキシシクロヘキシルフェニルケトン）

The components shown in Table 1 are as follows.
Further, the composition amounts shown in Table 1 are parts by weight.
Polymer 1; modified polymer polymer 2 obtained in production example 3; modified polymer polymer 3 obtained in production example 4; modified polymer DPGDA obtained in production example 5; dipropylene glycol diacrylate (new Nakamura Chemical Industry (strain) ))
Irgacure 184 (1-hydroxycyclohexyl phenyl ketone manufactured by BASF Japan Ltd.)

Evaluation of fast 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 heated and mixed for evaluation of quick drying by heat mixing. The sample used was 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 the above sample prepared for use in the adhesion test using a wire bar (coating rod) It was cured with a metal halide lamp (a lamp distance of 14 cm, a light amount of about 200 mW / cm ² and light irradiation until the coating became tack free) with an output of 160 W / cm. The UV curing apparatus used was a box type UV curing apparatus manufactured by Ushio Inc. Quick drying was confirmed by touching the obtained coating film. The product cured at less than 4456 mJ / cm ² was evaluated as ○, and the product cured at 4456 mJ / cm ² or more as x. The evaluation results are shown in Table 2.

Adhesion Test The prepared photocurable resin composition was coated on a plastic film and cured in the same manner as the fast drying test. A 24mm wide SellotapeTM (product number: CT-24, adhesive strength: 4.01 N / 10 mm) manufactured by Nichiban Co., Ltd. is attached to the obtained coating film, and after strongly rubbing five times with a thumb, Sellotape (registered The trademark was pulled away. Evaluation criteria were as follows. The evaluation results are shown in Table 2.
3: One that does not peel at all even if pulled apart gradually.
2: Peeling by about 50% even if pulled apart gradually.
1: It peels even if it pulls apart gradually.

The viscosity adjusted photocurable resin composition was used, and samples were prepared in the same manner as in the fast drying test. The viscosity at 30 ° C. was measured using a Thermo Fisher SCIENTIFC HAAKE MARS3. The evaluation results are shown in Table 2.

実施例１〜３に示すように、チオール化合物で変性したポリマー１〜３を用いて調製した光硬化性樹脂組成物は、比較例１に示すようなチオール化合物で変性していない重合体を用いて調製した光硬化性樹脂組成物と同等の乾燥性を有する。そして、チオール化合物で変性していない重合体を用いて調製した比較例１や無添加の比較例２の光硬化性樹脂組成物では密着が難しいポリプロピレンシートへの密着性にも優れる。

As shown in Examples 1 to 3, the photocurable resin composition prepared using Polymers 1 to 3 modified with a thiol compound uses a polymer not modified with a thiol compound as shown in Comparative Example 1 It has the same drying property as the photocurable resin composition prepared as above. And in the photocurable resin composition of Comparative Example 1 prepared using the polymer which is not modified | denatured with the thiol compound and the additive-free comparative example 2, it is excellent also in the adhesiveness to a polypropylene sheet where adhesion is difficult.

Claims (8)

Following formula (1),

[Wherein, n represents any integer from 2 to 4 and Z is an n-valent alicyclic hydrocarbon group]
A polymer characterized in that an allyl-based polymer obtained by polymerizing an allyl compound represented by the above is modified with a thiol compound.   The polymer according to claim 1, wherein the thiol compound is a thiol compound of any of an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid and a mercaptoether.   The photocurable resin composition containing the polymer of Claim 1 or 2.   The photocurable resin composition according to claim 3, further comprising an ethylenically unsaturated compound (B).   The photocurable resin composition according to claim 3, further comprising a photopolymerization initiator.   The ink containing the photocurable resin composition in any one of Claims 3-5.   A paint containing the photocurable resin composition according to any one of claims 3 to 5.   The paint according to claim 7, which is an overprint varnish.

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