WO2018047588A1 - Résine de phtalate de diallyle modifiée par un composé thiol, et composition de résine photodurcissable comprenant cette résine ainsi qu'application de celle-ci - Google Patents

Résine de phtalate de diallyle modifiée par un composé thiol, et composition de résine photodurcissable comprenant cette résine ainsi qu'application de celle-ci Download PDF

Info

Publication number
WO2018047588A1
WO2018047588A1 PCT/JP2017/029413 JP2017029413W WO2018047588A1 WO 2018047588 A1 WO2018047588 A1 WO 2018047588A1 JP 2017029413 W JP2017029413 W JP 2017029413W WO 2018047588 A1 WO2018047588 A1 WO 2018047588A1
Authority
WO
WIPO (PCT)
Prior art keywords
diallyl phthalate
resin composition
thiol
modified
phthalate resin
Prior art date
Application number
PCT/JP2017/029413
Other languages
English (en)
Japanese (ja)
Inventor
明穂 上西
英明 馬越
岩佐　成人
Original Assignee
株式会社大阪ソーダ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社大阪ソーダ filed Critical 株式会社大阪ソーダ
Priority to JP2018538326A priority Critical patent/JP6795037B2/ja
Publication of WO2018047588A1 publication Critical patent/WO2018047588A1/fr

Links

Images

Classifications

    • 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
    • C08F18/18—Diallyl phthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L31/06—Homopolymers or copolymers of esters of polycarboxylic acids
    • C08L31/08—Homopolymers or copolymers of esters of polycarboxylic acids of phthalic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a diallyl phthalate resin modified with a specific thiol compound, a photocurable resin composition containing the modified diallyl phthalate resin, and an ink and a coating material using the resin composition. More specifically, the present invention relates to a photocurable resin composition having excellent adhesion to a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET).
  • 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 has added a diallyl phthalate resin modified with a specific thiol compound in a photocurable resin composition containing an ethylenically unsaturated compound, thereby producing a plastic.
  • the present invention was completed by finding that a resin composition excellent in adhesion to the substrate and having good compatibility was obtained.
  • the present invention is a diallyl phthalate resin that is modified with a specific thiol compound.
  • a photocurable resin composition containing a diallyl phthalate resin modified with a specific thiol compound (and further containing an ethylenically unsaturated compound) is a photocurable resin composition having excellent adhesion to a plastic substrate, Become.
  • this photocurable resin composition is particularly excellent in adhesion to PP (polypropylene) resin. This is a combination that is preferable in terms of adhesion to the PP resin by modifying the pendant allyl group of the diallyl phthalate resin with a thiol compound to reduce the polarity of the diallyl phthalate resin and approach the polarity of the PP resin. This is considered to be because.
  • a composition using a conventional diallyl phthalate resin is suitable as a component for inks and paints for PP resins, for which it was difficult to increase the adhesion.
  • the diallyl phthalate resin modified with a thiol compound can constitute a composition having good compatibility with a low-polarity ethylenically unsaturated compound that is incompatible with conventional diallyl phthalate resins.
  • the photocurable resin composition of the present invention preferably further contains a photopolymerization initiator.
  • a photopolymerization initiator By containing a photopolymerization initiator, polymerization by light irradiation proceeds smoothly, so that a higher molecular weight polymer can be obtained in a short time.
  • the ink of the present invention is characterized by containing the photocurable resin composition of the present invention.
  • This ink is suitable as an ink for printing on a plastic substrate, and particularly suitable as an ink for printing on a substrate such as a PP resin sheet or film.
  • the paint of the present invention is characterized by containing the photocurable resin composition of the present invention.
  • This paint is suitable as a paint for drawing on a plastic substrate, and particularly suitable as a paint for drawing on a substrate such as a PP resin sheet or film.
  • the coating material of this invention is an overprint varnish.
  • 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.
  • NMR spectrum is shown.
  • (A) is the NMR spectrum of the diallyl phthalate resin used in Production Example 2
  • (B) is the NMR spectrum of 1-dodecylthiol used in Production Example 2
  • (C) is the NMR spectrum of Irgacure 184 used in Production Example 2
  • (D) represents the NMR spectrum of the thiol-modified diallyl phthalate resin obtained in Production Example 2. NMR spectrum is shown.
  • (A) is the NMR spectrum of the diallyl phthalate resin used in Production Example 3
  • (B) is the NMR spectrum of 2-ethylhexylthiol used in Production Example 3
  • (C) is the NMR spectrum of Irgacure 184 used in Production Example 3
  • (D) represents the NMR spectrum of the thiol-modified diallyl phthalate resin obtained in Production Example 3.
  • Diallyl phthalate resin modified with a thiol compound The diallyl phthalate resin modified with a thiol compound in the present invention is used without particular limitation as long as it is modified by subjecting a pendyl allyl group of the diallyl phthalate resin to an thiol compound. be able to.
  • the diallyl phthalate resin used for modification can be used without any particular problem as long as it has a pendant allyl group, for example, diallyl phthalate resins such as diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer and the like. These may be used singly or as a mixture of two or more.
  • the diallyl phthalate resin may be a prepolymer made of a copolymer of two or more kinds of diallyl monomers such as diallyl orthophthalate monomer, diallyl isophthalate monomer, diallyl terephthalate monomer. In this case, a hydrogen atom on the benzene ring may be substituted with a halogen atom such as chlorine or bromine. Of these, diallyl isophthalate resin is preferable.
  • the molecular weight of the diallyl phthalate resin used for modification is not particularly limited, but the weight average molecular weight (Mw) is preferably 5,000 to 200,000 from the viewpoint of improving solubility in a solvent and curability. More preferably from 20,000 to 100,000, even more preferably from 20,000 to 60,000.
  • “weight average molecular weight” can be determined by using gel permeation chromatography (GPC system, manufactured by Shimadzu Corporation) at 40 ° C. and using a standard polystyrene calibration curve.
  • the weight average molecular weight of the thiol-modified diallyl phthalate resin diallyl phthalate resin modified with a thiol compound
  • the iodine value of the diallyl phthalate resin used for modification is not particularly limited.
  • the iodine value may be in the range of 40 to 110 g / 100 g, and is preferably in the range of 45 to 100 g / 100 g.
  • the iodine value is a value obtained by converting the amount of halogen bonded to 100 g of the sample into g of iodine, and represents the degree of unsaturation of the sample (JIS K6235). It shows that the degree of unsaturation of a sample is so small that an iodine number (g / 100g) is small.
  • the thiol compound used for thiol compound modification can be used without any particular problem as long as it can react with the pendant allyl group of the diallyl phthalate resin.
  • an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercapto ether 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-ethylhexane
  • 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 Compounds and the like.
  • an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercapto ether are preferable, an aliphatic thiol compound, Mercaptocarboxylic acid ester compounds are more preferred, and mercaptocarboxylic acid ester compounds are more preferred. If it is the said thiol compound, the pendant allyl group of diallyl phthalate resin can be modified
  • Enthiol reaction proceeds by bringing an unsaturated compound (such as an allyl compound or diallyl phthalate resin) into contact with a thiol compound.
  • an unsaturated compound such as an allyl compound or diallyl phthalate resin
  • the reaction system containing an allyl compound and a thiol compound has an active energy (or active energy). You may make it react (enthiol reaction) by providing a line
  • 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 for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a mercury xenon lamp, a halogen lamp, a UV-LED lamp, a laser light source (helium-cadmium laser)
  • a light source such as an excimer laser).
  • the wavelength of light may be, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm).
  • the amount of irradiation light 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 enthiol reaction is not particularly limited, but can be calculated by the following calculation method.
  • the number of functional groups of the diallyl phthalate resin is obtained from the iodine value of the diallyl phthalate resin used for the enthiol reaction, and the number of functional groups in 1 g of diallyl phthalate resin (the number of functional groups of the diallyl phthalate resin) is calculated from the molecular weight of the diallyl phthalate resin and the Avogadro constant.
  • Thiol modification rate of pendant allyl group of diallyl phthalate resin in enethiol reaction is NMR peak integral value ((NMR peak integral value of diallyl phthalate resin before reaction ⁇ NMR peak integral value of thiol-modified diallyl phthalate resin after reaction) ⁇ reaction) It can be calculated from the NMR peak integral value of the previous diallyl phthalate resin).
  • the thiol modification rate of the pendant allyl group of the diallyl phthalate resin modified with a thiol compound may be 30% or more, preferably 50% or more, and more preferably 80% or more.
  • the weight average molecular weight (Mw) of the diallyl phthalate resin modified with a thiol compound is preferably 600,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, 200 It is particularly preferable that it is 1,000 or less, most preferably 100,000 or less, and most preferably 80,000 or less.
  • the Mw is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and 30 Most preferably, it is 1,000 or more.
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the diallyl phthalate resin modified with a thiol compound is preferably 1.0 to 10.0, and more preferably 3.0 to 5.0.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the diallyl phthalate resin modified with a thiol compound are values measured by the method described in Examples.
  • Photocurable resin composition of the present invention is a resin composition before curing, and is a composition containing at least the diallyl phthalate resin modified with the above-described thiol compound.
  • the content of the diallyl phthalate resin modified with a thiol compound in the photocurable resin composition may be in the range of 1 to 70% by weight with respect to the total amount of the photocurable resin composition, and is 2.5 to 65% by weight. %, Preferably 5 to 60% by weight.
  • the upper limit is more preferably 40% by weight, particularly preferably 30% by weight, and most preferably 20% by weight.
  • 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.
  • methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) are compatible with diallyl phthalate resin modified with a thiol compound and cured when photocured.
  • Alkyl (meth) acrylates such as acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acrylate such as glycerol di (meth) acrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified Tri (meth) acrylates such as trimethylolpropane triacrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, alkoxylated phenol acrylate, ethoxylated phenol acrylate, etc.
  • the content of the ethylenically unsaturated compound contained in the photocurable resin composition of the present invention is 50 to 1500 weights with respect to 100 parts by weight of the diallyl phthalate resin modified with a thiol compound in the photocurable resin composition. Parts, preferably 100 to 1200 parts by weight, more preferably 100 to 900 parts by weight.
  • the content of the ethylenically unsaturated compound contained in the photocurable resin composition is such that the viscosity of the photocurable resin composition is in the range of 1 to 3000 mPa ⁇ s (particularly 1 to 2000) (25 ° C.). It is preferable to add so that it may become inside.
  • 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 prepared by adding a diallyl phthalate resin modified with a thiol compound to an ethylenically unsaturated compound, if necessary, a photopolymerization initiator, a photoinitiator auxiliary agent, and an additive (for example, stable Agent, pigment).
  • the photocurable resin composition of the present invention is cured by irradiating light.
  • the light used for curing is generally ultraviolet light.
  • the curing device used for the curing reaction of the photocurable resin composition and the curing conditions are not particularly limited, and any method may be used as long as it is a normal photocuring reaction.
  • the use of the photocurable resin composition of the present invention is not particularly limited.
  • Ink for example, printing ink for photo-curable lithographic printing plate, silk screen ink, gravure ink, inkjet, etc.
  • paint for example, paint for paper, plastic, metal, woodwork, etc. Printing varnish
  • adhesives 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 diallyl phthalate resin modified with a thiol compound, a stabilizer and the like are dissolved in an ethylenically unsaturated compound with stirring at a temperature of 60 ° C. to 100 ° C. to prepare a varnish.
  • the ink is obtained by mixing the varnish with a pigment, a photopolymerization initiator, and other additives with a butterfly mixer and then kneading with a three-roll roll.
  • the overprint varnish can be prepared by the same procedure as that for ink except that no pigment is used.
  • Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of diallyl phthalate resin, diallyl phthalate resin modified with thiol compound The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using GPC. It is a value of weight average molecular weight and number average molecular weight in terms of standard polystyrene.
  • Iodine number measurement The iodine number of the diallyl phthalate resin used for production was measured according to the method defined in JIS K6235.
  • the integrated light quantity measurement was performed using an eye ultraviolet light integrated illuminometer: UVPF-A1 light receiver: PD-365 (manufactured by Eye Graphics). The measured value was 6100 mJ / cm 2 in 60 seconds.
  • the solution after the reaction was concentrated twice using a rotary evaporator.
  • the resulting reaction solution was added to 400 mL of stirred methanol to precipitate the resin.
  • the precipitated solid was vacuum dried at 40 ° C. for 6 hours to obtain a diallyl phthalate resin (resin 1) modified with a thiol compound.
  • the thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (41.1545) -thiol-modified diallyl after reaction) Calculated from NMR peak integral value of phthalate resin (1.7548)) ⁇ NMR peak integral value of diallyl phthalate resin before reaction (41.1545), 95.7% of allyl group was modified. NMR is shown in FIG.
  • the thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (42.6445))-thiol-modified diallyl after reaction Calculated from NMR peak integral value of phthalate resin (3.7247)) ⁇ NMR peak integral value of diallyl phthalate resin before reaction (42.6445), 90.9% of allyl group was modified. NMR is shown in FIG.
  • the thiol modification rate of the pendant allyl group of the thiol-modified diallyl phthalate resin is 5.9 ppm NMR peak integral value indicating the allyl group (NMR peak integral value of diallyl phthalate resin before reaction (53.1886))-thiol-modified diallyl after reaction Calculated from NMR peak integrated value of phthalate resin (6.7295)) ⁇ NMR peak integrated value of diallyl phthalate resin before reaction (53.1886), 87.3% of allyl groups were modified. NMR is shown in FIG.
  • the components shown in Table 1 are as follows. The composition amounts shown in Table 1 are parts by weight. Resin 1; Modified diallyl phthalate resin resin 2 obtained in Production Example 1; Modified diallyl phthalate resin resin 3 obtained in Production Example 2; Modified diallyl phthalate resin DAP resin obtained in Production Example 3; Osaka Soda Co., Ltd.
  • DPGDA Dipropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 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. 5: The cured film does not peel when the tape is peeled off quickly. 4: When the tape is peeled quickly, the cured film peels 50%. 3: The cured film does not peel when the tape is slowly peeled off. 2: When the tape is slowly peeled, the cured film peels 50%. 1: When the tape is slowly peeled off, the cured film is completely peeled off.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (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 fournit une composition de résine photodurcissable qui comprend une résine de phtalate de diallyle caractéristique en ce qu'elle est modifiée par un des composés thiol suivants : un composé thiol aliphatique, un composé thiol aromatique, un composé polythiol aliphatique, un composé ester d'acide mercaptocarboxylique, un acide mercaptocarboxylique et un mercaptoéther. L'invention fournit également une encre comprenant cette composition de résine photodurcissable et une peinture.
PCT/JP2017/029413 2016-09-06 2017-08-15 Résine de phtalate de diallyle modifiée par un composé thiol, et composition de résine photodurcissable comprenant cette résine ainsi qu'application de celle-ci WO2018047588A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018538326A JP6795037B2 (ja) 2016-09-06 2017-08-15 チオール化合物で変性したジアリルフタレート樹脂、及び当該樹脂を含有する光硬化性樹脂組成物とその用途

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016173718 2016-09-06
JP2016-173718 2016-09-06

Publications (1)

Publication Number Publication Date
WO2018047588A1 true WO2018047588A1 (fr) 2018-03-15

Family

ID=61562757

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/029413 WO2018047588A1 (fr) 2016-09-06 2017-08-15 Résine de phtalate de diallyle modifiée par un composé thiol, et composition de résine photodurcissable comprenant cette résine ainsi qu'application de celle-ci

Country Status (3)

Country Link
JP (1) JP6795037B2 (fr)
TW (1) TW201829481A (fr)
WO (1) WO2018047588A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58213022A (ja) * 1982-06-07 1983-12-10 Sumitomo Bakelite Co Ltd 放射線硬化可能な樹脂組成物
JPS62212436A (ja) * 1986-03-14 1987-09-18 Sumitomo Bakelite Co Ltd 紫外線硬化性樹脂組成物
JP2001109360A (ja) * 1998-08-12 2001-04-20 Agency Of Ind Science & Technol ホログラム記録材料組成物、ホログラム記録媒体およびその製造法
JP2001282082A (ja) * 2000-01-25 2001-10-12 Natl Inst Of Advanced Industrial Science & Technology Meti ホログラム記録材料組成物、ホログラム記録媒体およびその製法
WO2015082244A1 (fr) * 2013-12-02 2015-06-11 Allnex Belgium , S.A. Stabilisateur pour compositions thiol-ène
WO2016125663A1 (fr) * 2015-02-03 2016-08-11 株式会社大阪ソーダ Composition de résine photodurcissable, encre, et revêtement
JP2016186017A (ja) * 2015-03-27 2016-10-27 株式会社大阪ソーダ チオール化合物で変性したジアリルフタレート樹脂、及び当該樹脂を含有する光硬化性樹脂組成物とその用途

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5517112B2 (ja) * 2011-01-11 2014-06-11 ダイソー株式会社 光硬化性樹脂組成物とその用途
JP5786993B2 (ja) * 2014-03-10 2015-09-30 ダイソー株式会社 アリル系重合体およびその硬化性樹脂組成物とその用途

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58213022A (ja) * 1982-06-07 1983-12-10 Sumitomo Bakelite Co Ltd 放射線硬化可能な樹脂組成物
JPS62212436A (ja) * 1986-03-14 1987-09-18 Sumitomo Bakelite Co Ltd 紫外線硬化性樹脂組成物
JP2001109360A (ja) * 1998-08-12 2001-04-20 Agency Of Ind Science & Technol ホログラム記録材料組成物、ホログラム記録媒体およびその製造法
JP2001282082A (ja) * 2000-01-25 2001-10-12 Natl Inst Of Advanced Industrial Science & Technology Meti ホログラム記録材料組成物、ホログラム記録媒体およびその製法
WO2015082244A1 (fr) * 2013-12-02 2015-06-11 Allnex Belgium , S.A. Stabilisateur pour compositions thiol-ène
WO2016125663A1 (fr) * 2015-02-03 2016-08-11 株式会社大阪ソーダ Composition de résine photodurcissable, encre, et revêtement
JP2016186017A (ja) * 2015-03-27 2016-10-27 株式会社大阪ソーダ チオール化合物で変性したジアリルフタレート樹脂、及び当該樹脂を含有する光硬化性樹脂組成物とその用途

Also Published As

Publication number Publication date
TW201829481A (zh) 2018-08-16
JP6795037B2 (ja) 2020-12-02
JPWO2018047588A1 (ja) 2019-06-27

Similar Documents

Publication Publication Date Title
JP5801556B2 (ja) 紫外線ｌｅｄ照射用光硬化性樹脂組成物
US11084891B2 (en) Photocurable resin composition, ink and coating material
CN110546224B (zh) 粘接剂组合物
DE69909272T2 (de) Schwefelenthaltende additionsverbindungen von polythiolen und norbornenderivaten, verfahren zu ihrer herstellung und ihrer anwendung zur gewinnung von mittels radikalbildung vernetzen produkten
US10336836B2 (en) Photocurable resin composition, ink, and coating
JP6997942B2 (ja) 光硬化性樹脂組成物、インキ及び塗料
KR102319220B1 (ko) 광 중합 증감제 조성물과 그것을 포함하는 광 중합성 조성물
JP2015183139A (ja) エネルギー線重合性組成物
WO2018047588A1 (fr) Résine de phtalate de diallyle modifiée par un composé thiol, et composition de résine photodurcissable comprenant cette résine ainsi qu'application de celle-ci
JP2019019291A (ja) 光硬化性樹脂組成物、インキ及び塗料
JP2016186017A (ja) チオール化合物で変性したジアリルフタレート樹脂、及び当該樹脂を含有する光硬化性樹脂組成物とその用途
WO2018047589A1 (fr) Polymère modifié par un composé thiol, et composition photodurcissable comprenant ce polymère ainsi qu'application de celle-ci
JP6880543B2 (ja) 光硬化性樹脂組成物、インキ及び塗料
JP2019014867A (ja) 光硬化性樹脂組成物、表示素子用封止剤、有機ｅｌ素子用面封止剤、および面封止層
JP2011052148A (ja) 光硬化性樹脂組成物、その製造方法及び硬化樹脂
WO2018150764A1 (fr) Polymère modifié par thiol, ainsi que composition contenant ledit polymère et son utilisation
JP2017179005A (ja) 硬化性組成物、およびそれを用いる硬化物
JP2016224197A (ja) 光硬化性樹脂組成物
WO2018037912A1 (fr) Composition de résine photodurcissable, encre et matériau de revêtement
WO2019189276A1 (fr) Procédé de fabrication de polymère, polymère et composition de polymère
JP2020084085A (ja) 活性エネルギー線硬化性組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018538326

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17848532

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17848532

Country of ref document: EP

Kind code of ref document: A1