WO2018047589A1 - Polymère modifié par un composé thiol, et composition photodurcissable comprenant ce polymère ainsi qu'application de celle-ci - Google Patents

Polymère modifié par un composé thiol, et composition photodurcissable comprenant ce polymère ainsi qu'application de celle-ci Download PDF

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WO2018047589A1
WO2018047589A1 PCT/JP2017/029414 JP2017029414W WO2018047589A1 WO 2018047589 A1 WO2018047589 A1 WO 2018047589A1 JP 2017029414 W JP2017029414 W JP 2017029414W WO 2018047589 A1 WO2018047589 A1 WO 2018047589A1
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polymer
allyl
compound
thiol
resin composition
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PCT/JP2017/029414
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Japanese (ja)
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明穂 上西
英明 馬越
岩佐　成人
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株式会社大阪ソーダ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/14—Esters of polycarboxylic acids
    • C08F18/16—Esters of polycarboxylic acids with alcohols containing three or more carbon atoms

Definitions

  • 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 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).
  • PP polypropylene
  • PET polyethylene terephthalate
  • 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.
  • 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. .
  • 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.
  • a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • the present inventor in a photocurable resin composition containing a polymer obtained by modifying an allylic polymer having a specific structure with a thiol compound, is in close contact with a plastic substrate.
  • the present invention was completed by finding that a resin composition having excellent compatibility and good compatibility can be obtained.
  • Item 1 The following formula (1), [Wherein n represents an integer of 2 to 4, and Z represents an n-valent alicyclic hydrocarbon group] A polymer obtained by modifying an allyl polymer obtained by polymerizing an allyl compound represented by a thiol compound.
  • Item 2. The polymer according to Item 1, wherein the thiol compound is an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, or a mercaptoether.
  • Item 3. Item 3.
  • a photocurable resin composition comprising the polymer according to item 1 or 2.
  • Item 4 The photocurable resin composition according to Item 3, further comprising an ethylenically unsaturated compound (B). Item 5. Item 5. The photocurable resin composition according to Item 3 or 4, further comprising a photopolymerization initiator. Item 6. Item 6. An ink containing the photocurable resin composition according to any one of Items 3 to 5. Item 7. Item 6. A paint containing the photocurable resin composition according to any one of Items 3 to 5. Item 8. Item 8. The paint according to Item 7, which is an overprint varnish. It is.
  • the photocurable resin composition of this 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.
  • 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) is the NMR spectrum of polymer 1 used in Production Example 3
  • (B) is the NMR spectrum of 2-ethylhexyl 3-mercaptopropionate used in Production Example 3
  • (C) is used in Production Example 3.
  • Ingacure 184 NMR spectrum (D) represents the NMR spectrum of the thiol-modified polymer obtained in Production Example 3.
  • the NMR spectrum of polymer 2 is shown.
  • (A) is the NMR spectrum of the polymer 1 used in Production Example 4
  • (B) is the NMR spectrum of 1-dodecylthiol used in Production Example 4
  • (C) is the NMR spectrum of Ingacure 184 used in Production Example 4
  • (D) represents the NMR spectrum of the thiol-modified polymer obtained in Production Example 4.
  • the NMR spectrum of polymer 3 is shown.
  • (A) is the NMR spectrum of the polymer 1 used in Production Example 5
  • (B) is the NMR spectrum of 2-ethylhexylthiol used in Production Example 5
  • (C) is the 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.
  • the polymer modified with a thiol compound in the present invention is a polymer obtained by modifying an allyl polymer obtained by polymerizing an allyl compound represented by the following formula (1) with a thiol compound.
  • n represents an integer of 2 to 4
  • Z represents an n-valent alicyclic hydrocarbon group
  • the allyl polymer used for modification of the allyl polymer is obtained by polymerizing an allyl compound represented by the following formula (1). [Wherein n represents an integer of 2 to 4, and Z represents an n-valent alicyclic hydrocarbon group]
  • the n-valent alicyclic hydrocarbon group of Z in formula (1) preferably has 3 to 18 carbon atoms, and preferably 4 to 12 carbon atoms, forming the ring structure of the alicyclic hydrocarbon group. More preferably, it is 4 to 10, particularly preferably 5 to 7. n is an integer of 2 to 4, preferably 2 to 3, more preferably 2.
  • the n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group and may partially have an unsaturated bond, but may be a saturated n-valent alicyclic ring. It is preferably a formula hydrocarbon group.
  • an alicyclic means the hydrocarbon group which has a cyclic structure which does not have 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 straight chain 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. Note that the n-valent alicyclic hydrocarbon group does not necessarily have an alkyl group.
  • 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 formula (5) to the formula (7) is preferred).
  • n is an integer of 2 to 4.
  • substitution positions of the COOCH 2 CH ⁇ CH 2 groups on the rings of formulas (2) to (9) may be any combination, or a mixture thereof.
  • the two COOCH 2 CH ⁇ CH 2 groups may be either ortho-orientated, meta-orientated, or para-orientated. The orientation is preferable.
  • Specific allyl compounds in the case where Z in formula (1) is an n-valent alicyclic hydrocarbon group include diallyl cyclobutanedicarboxylate, diallyl cycloheptanedicarboxylate, diallylcyclohexanedicarboxylate (hexahydrophthalic acid) Diallyl), diallyl norbornane dicarboxylate, diallyl cyclobutene dicarboxylate, diallyl cycloheptene dicarboxylate, diallyl cyclohexene dicarboxylate (diallyl tetrahydrophthalate) and diallyl norbornene dicarboxylate, 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 Talate, 3,
  • 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.
  • the allyl compound represented by the formula (1) of the present invention includes 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, a basic It can manufacture by making it react in the presence of a substance, a catalyst, and a solvent.
  • the carboxylic acid compound represented by the general formula (10) is available as a reagent or industrial chemical.
  • a commercially available allyl compound represented by the formula (1) may be used as the allyl compound represented by the formula (1). [Wherein n and Z have the same meanings as n and Z in formula (1). ]
  • allyl halide examples include allyl chloride, allyl bromide, allyl iodide and the like.
  • the amount of allyl halide to be used is not particularly limited, but it is usually preferably in the range of 2 to 20 equivalents relative to the carboxylic acid compound represented by the general formula (10), from the viewpoint of reaction rate and volume efficiency. Is more preferably in the range of 2.3 to 10 equivalents.
  • These allyl halide 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 and preferably in the range of 2 to 5 equivalents with respect to the carboxylic acid compound represented by the general formula (10). Is more preferable.
  • the acidic substance examples include sulfuric acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and the like.
  • the amount of the acidic substance used is 0.001 to 0.1 relative 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 the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride, carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonate Bicarbonates such as sodium and potassium bicarbonate, alcoholates and the like are generally used, but quaternary ammonium compounds, organic bases such as aliphatic amines and aromatic amines can also be used.
  • the amount of the basic substance used is preferably in the range of 0.5 to 30 equivalents, more preferably in the range of 2 to 15 equivalents, relative to the carboxylic acid compound represented by the general formula (10).
  • transition metals and transition metal salts such as copper, iron, cobalt, nickel, chromium, and vanadium are used.
  • 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, cupric acetate Copper or the like is preferable.
  • cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, copper sulfate, cupric acetate are particularly suitable because they are readily 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.
  • 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 and sulfolane Can be mentioned.
  • the amount used is not particularly limited, but it is usually preferably in the range of 0.01 to 20 times the weight of the carboxylic acid compound represented by the general formula (11). The range of 1 to 10 times the weight is more preferable. In the case of this reaction, an allyl compound can be produced efficiently without using any solvent.
  • phase transfer catalyst when a basic substance is used in the reaction as an aqueous solution, it is preferable to use a phase transfer catalyst in order to accelerate the reaction.
  • phase transfer catalyst there are no particular limitations on the phase transfer catalyst, but for example, quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide; phosphonium salts such as tetrabutylphosphonium chloride; 15-crown-5,18 -Crown ethers such as crown-6.
  • the amount used is usually preferably in the range of 0.001 to 1 equivalent with respect to the carboxylic acid compound represented by the general formula (10). A range of 4 equivalents is more preferred.
  • 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 to effectively suppress side reactions and to obtain a high yield. More preferably.
  • the reaction time is preferably in the range of 10 minutes to 15 hours, and from the viewpoint of suppressing side reactions, it is preferably in the range of 10 minutes to 10 hours.
  • the reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Further, the reaction can be carried out under atmospheric pressure or under pressure, but it is preferably carried out under atmospheric pressure from the viewpoint of production equipment.
  • the reaction can be carried out, for example, by charging raw materials into a stirring type reactor at once or divided and reacting at a predetermined temperature described in “0028” for a predetermined time.
  • the resulting reaction mixture is neutralized, washed with water, saturated saline, etc. as necessary, concentrated, and further used for purification of organic compounds such as distillation and column chromatography.
  • a highly pure compound can be obtained by performing the purification operation.
  • An allyl 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 normal polymerization reaction can be used.
  • a polymerization initiator may be appropriately added to the polymerization reaction as necessary. By using a polymerization initiator, a higher molecular weight polymer can be obtained in a short time.
  • Polymerization initiators used for the polymerization reaction include azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and diacyl peroxide.
  • azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, and diacyl peroxide.
  • 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 acylphosphine oxide, sulfur such as thioxanthone, benzyl, 9,10-phenanthrenequinone It includes benzylic photopolymerization initiator.
  • 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 0.001 to 3.0 parts by weight with respect to 100 parts by weight of the allyl compound. More preferably, it is part.
  • the reaction temperature at the time of polymerization is preferably 60 to 240 ° C, more preferably 80 to 220 ° C.
  • the reaction time is preferably 0.1 to 100 hours, and more preferably 1 to 30 hours.
  • an allyl compound having a monomer unit based on the allyl compound represented by the general formula (1) is obtained by polymerizing the allyl compound represented by the general formula (1) by the above-described method or the like.
  • System polymers can be prepared.
  • the weight average molecular weight of the allylic polymer in the present invention is preferably 500,000 or less, more preferably 400,000 or less, particularly preferably 2,000 to 150,000, More preferably, it is from 000 to 140,000.
  • “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 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 formula (1) is preferably 20% by weight or more in a total of 100% by weight of the monomer units constituting the allylic polymer. More preferably, it is more than 80% by weight, more preferably more than 80% by weight, particularly preferably more than 98% by weight, and may be 100% by weight.
  • the thiol compound used for thiol compound modification can be used without any particular problem as long as it can react with the pendant allyl group of the allyl polymer.
  • 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, 2,4,4-trimethyl-2-p
  • 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
  • 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
  • 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), dipentaerythr
  • 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 ( ⁇ -mercaptopropyl) trimethoxysilane and ( ⁇ -mercaptopropyl) triethoxysilane A compound etc. can be illustrated.
  • an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol, 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. If it is the said thiol compound, the pendant allyl group of an allyl polymer can be modified
  • Enthiol reaction proceeds by bringing an unsaturated compound (an allyl compound, an allyl polymer obtained by polymerizing an allyl compound, etc.) and a thiol compound into contact with each other. You may make it react (enthiol reaction) by providing active energy (or active energy ray). By applying active energy, the enethiol reaction can be easily advanced.
  • thermal energy and / or light energy can be used depending on the type of the polymerization initiator.
  • 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.
  • light energy for example, when using a photopolymerization initiator
  • radiation gamma rays, X-rays, etc.
  • ultraviolet rays visible rays, etc.
  • it is often ultraviolet rays.
  • thermal polymerization initiator as an initiator, irradiation of light energy is not necessarily required.
  • the light source examples include 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, and 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 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.
  • a 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.
  • 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.
  • 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'-
  • 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-
  • the amount of the thiol compound used in the enethiol reaction is not particularly limited, but can be calculated by the following calculation method.
  • the number of functional groups of the allyl polymer is obtained from the iodine value of the allyl polymer used for the enthiol reaction, and the number of functional groups in 1 g of the allyl polymer (the number of functional groups of the allyl polymer) is determined from the molecular weight of the allyl polymer and the Avogadro constant. ) Is calculated.
  • 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 polymer in the enethiol reaction is the NMR peak integral value ((NMR peak integral value of the allyl polymer before the reaction ⁇ NMR peak integral value of the polymer after the reaction) ⁇ before the reaction). NMR peak integral value of 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.
  • the weight average molecular weight of the thiol-modified polymer increases from the weight average molecular weight of the polymer before modification.
  • the polymer modified with the thiol compound preferably has a weight average molecular weight (Mw) of 600,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, and 200,000. It is particularly preferred that it is less than or equal to 100,000 and most preferred is 100,000 or less.
  • 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 polymer modified with a thiol compound is preferably 1.0 to 10.0, and more preferably 3.0 to 5.0.
  • 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 Examples.
  • Photocurable resin composition is a resin composition before curing, and is a composition containing at least a polymer modified with the above-described thiol compound.
  • the content of the polymer modified with the thiol compound in the photocurable resin composition may be in the range of 1 to 70% by weight, and 2.5 to 65% by weight with respect to the total amount of the photocurable resin composition.
  • the range is preferable, and the range of 5 to 60% by weight is more preferable.
  • the upper limit is more preferably 40% by weight, particularly preferably 30% by weight, and most preferably 20% by weight.
  • 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.
  • (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.
  • 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.
  • 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.
  • 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.
  • the photocurable resin composition of the present invention may contain a polymerization initiator, and particularly preferably contains a photopolymerization initiator.
  • 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
  • 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.
  • 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 photocurable resin composition of the present invention is a polymer modified with a thiol compound, an ethylenically unsaturated compound, if necessary, a photopolymerization initiator, a photoinitiator aid, an additive (for example, a stabilizer, Pigment) can be mixed.
  • 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 for 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.
  • a general method for producing ink is as follows.
  • a polymer modified with a thiol compound, an 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.
  • Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polymers modified with thiol compounds 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.
  • Iodine value measurement The iodine value of the allyl polymer used in the production was measured according to the method defined in JIS K6235.
  • 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 minutes to dissolve. To this, 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.
  • a photopolymerization initiator Irgacure 184
  • the thiol modification rate of the pendant allyl group of the thiol-modified polymer is the 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of the allyl polymer before the reaction (31.9502))-NMR of the polymer after the reaction Calculated from the peak integrated value (1.7774)) ⁇ NMR peak integrated value of the allyl polymer before the reaction (31.9502), 94.4% of the allyl group was modified.
  • the thiol modification rate of the pendant allyl group of the thiol-modified polymer is the 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of the allyl polymer before the reaction (7733.9509) ⁇ the NMR of the polymer after the reaction). Calculated from the peak integrated value (110.6631)) ⁇ NMR peak integrated value (7733.9509) of the allyl polymer before the reaction, 85.7% of the allyl group was modified.
  • the thiol modification rate of the pendant allyl group of the thiol-modified polymer is 5.9 ppm NMR peak integral value indicating allyl group (NMR peak integral value of allyl polymer before reaction (866.5927)) — NMR of the polymer after reaction. Calculated from the peak integrated value (14.6921)) ⁇ NMR peak integrated value of the allyl polymer before the reaction (866.5927), 83.0% of the allyl group was modified.
  • the components shown in Table 1 are as follows. 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 (Shin Nakamura Chemical Co., Ltd.) ) Made) Irgacure 184 (1-hydroxycyclohexyl phenyl ketone manufactured by BASF Japan Ltd.)
  • 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. 3: What does not peel at all even if it pulls apart gradually. 2: Even if it is gradually pulled apart, it peels about 50%. 1: A thing that peels even if it is gradually pulled apart.
  • 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 a drying property equivalent to the photocurable resin composition prepared in the above. And it is excellent also in the adhesiveness to the polypropylene sheet to which adhesion

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention a pour objet de fournir une composition de résine photodurcissable qui permet de configurer une composition dotée d'une excellente adhérence avec un matériau de base en plastique tel qu'un polypropylène (PP), un polyéthylène téréphtalate (PET), ou similaire, et présentant une compatibilité satisfaisante avec un composé éthyléniquement insaturé. Plus précisément, l'invention concerne une composition photodurcissable qui est caractéristique en ce qu'elle contient un polymère lui-même caractéristique en ce qu'un polymère allylique obtenu par polymérisation d'un composé allyle représenté par la formule (1), est modifié par un composé thiol.
PCT/JP2017/029414 2016-09-06 2017-08-15 Polymère modifié par un composé thiol, et composition photodurcissable comprenant ce polymère ainsi qu'application de celle-ci WO2018047589A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000508375A (ja) * 1997-02-03 2000-07-04 ユニロイヤル ケミカル カンパニー インコーポレイテッド 粘度指数改良性能を有する無灰耐摩耗性分散添加剤を含有する潤滑剤
JP2004107448A (ja) * 2002-09-17 2004-04-08 Toagosei Co Ltd 側鎖に環内オレフィンを有する脂環基を含有する重合体と、当該重合体を含有する活性エネルギー線硬化型組成物
JP2008519110A (ja) * 2004-11-08 2008-06-05 クィーンズ ユニバーシティー アット キングストン 官能化ポリオレフィン、湿分硬化型（ｍｏｉｓｔｕｒｅｃｕｒａｂｌｅ）ポリオレフィン樹脂およびそれらを製造する方法
JP2010079261A (ja) * 2008-08-26 2010-04-08 Tamura Kaken Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
WO2016104389A1 (fr) * 2014-12-22 2016-06-30 昭和電工株式会社 Composition durcissable par un rayonnement d'énergie active et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000508375A (ja) * 1997-02-03 2000-07-04 ユニロイヤル ケミカル カンパニー インコーポレイテッド 粘度指数改良性能を有する無灰耐摩耗性分散添加剤を含有する潤滑剤
JP2004107448A (ja) * 2002-09-17 2004-04-08 Toagosei Co Ltd 側鎖に環内オレフィンを有する脂環基を含有する重合体と、当該重合体を含有する活性エネルギー線硬化型組成物
JP2008519110A (ja) * 2004-11-08 2008-06-05 クィーンズ ユニバーシティー アット キングストン 官能化ポリオレフィン、湿分硬化型（ｍｏｉｓｔｕｒｅｃｕｒａｂｌｅ）ポリオレフィン樹脂およびそれらを製造する方法
JP2010079261A (ja) * 2008-08-26 2010-04-08 Tamura Kaken Co Ltd 感光性樹脂組成物、プリント配線板用のソルダーレジスト組成物およびプリント配線板
WO2016104389A1 (fr) * 2014-12-22 2016-06-30 昭和電工株式会社 Composition durcissable par un rayonnement d'énergie active et son utilisation

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