WO2016117385A1 - Composition de résine durcissable - Google Patents

Composition de résine durcissable Download PDF

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Publication number
WO2016117385A1
WO2016117385A1 PCT/JP2016/050454 JP2016050454W WO2016117385A1 WO 2016117385 A1 WO2016117385 A1 WO 2016117385A1 JP 2016050454 W JP2016050454 W JP 2016050454W WO 2016117385 A1 WO2016117385 A1 WO 2016117385A1
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meth
component
resin composition
curable resin
group
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PCT/JP2016/050454
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English (en)
Japanese (ja)
Inventor
寛 田代
一洋 幸田
俊伸 藤村
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日油株式会社
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Priority to KR1020177004380A priority Critical patent/KR101850257B1/ko
Priority to JP2016570570A priority patent/JPWO2016117385A1/ja
Priority to CN201680000405.2A priority patent/CN106414556B/zh
Priority to TW105112896A priority patent/TWI585136B/zh
Publication of WO2016117385A1 publication Critical patent/WO2016117385A1/fr

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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0245—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to a curable resin composition capable of obtaining a cured film having excellent adhesion and flexibility to a substrate even in a cold region.
  • JP2012-246464 discloses a curable resin composition in which a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative are mixed with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds. is doing.
  • This curable resin composition does not require the addition of other adhesion assistants as in the case of using a silane coupling agent, and can exhibit excellent adhesion to an inorganic substrate.
  • JP 2012-246464 A a curable resin composition in which a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative are mixed with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds.
  • the product has excellent adhesion to the inorganic substrate and excellent storage stability of the resin composition, the cured film is poor in flexibility in cold regions, so cracks tend to occur when the cured film is bent, and adhesion It became clear that there were problems such as lack.
  • the curable resin composition includes (A) a thioether-containing (meth) acrylate derivative represented by the following formula 1, and (B) a polyfunctional (meth) having a weight average molecular weight of 200 to 50,000. Acrylate, and the mass ratio ((A) / (B)) of the component (A) to the component (B) is 0.05 to 30.
  • a in the formula is an integer from 1 to 2
  • b is an integer from 1 to 2
  • R 2 is A divalent group represented by the following formula 3 or 4.
  • the R 3 is a hydrocarbon group having 1 to 12 carbon atoms.
  • the curable resin composition may further contain (C) a photopolymerization initiator in addition to the components (A) to (B).
  • the component (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass as the total mass of the component (A) and the component (B).
  • the curable resin composition further includes (D) a weight average molecular weight of 90 to 700 in addition to the components (A) to (B) or the components (A) to (C).
  • An amine compound that is The component (D) is 0.01 to 50 parts by mass with respect to 100 parts by mass as the total mass of the component (A) and the component (B).
  • the polyfunctional (meth) acrylate (B) having a specific molecular weight is blended in a well-balanced manner while using the specific thioether-containing (meth) acrylate derivative (A) as an active ingredient for improving adhesion.
  • the cured film of the curable resin composition can realize excellent adhesion to the substrate without adding other adhesion assistants or the like as in the case of using a conventional silane coupling agent.
  • the obtained cured film exhibits excellent adhesion and flexibility to the substrate.
  • the curable resin composition of the present disclosure includes the following components (A) and (B) as essential components, and optionally further contains at least one of components (C) and (D).
  • “molecular weight” means “weight average molecular weight” unless otherwise specified.
  • “(Meth) acrylate” means a generic name including both acrylate and methacrylate
  • “(meth) acryloxy group” means a generic name including both an acryloxy group and a methacryloxy group.
  • the description of “XX to XX” indicating the numerical range includes the lower limit (“XX”) and upper limit (“XX”) unless otherwise specified. Means more than xx.
  • the (A) component thioether-containing (meth) acrylate derivative is a compound represented by the following formula 1.
  • a in the formula is an integer from 1 to 2
  • b is an integer from 1 to 2
  • R 2 is A divalent group represented by the following formula 3 or 4.
  • the R 3 is a hydrocarbon group having 1 to 12 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R 3 in the above formula 1, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.
  • R 4 in the above formula 2 is the same methylene group, ethylene group, or isopropylene group, and an ethylene group or isopropylene group is particularly preferable because the effect of improving adhesion is enhanced.
  • the polyfunctional (meth) acrylate as the component (B) has a (meth) acryloxy group at the terminal, and preferred examples thereof include a compound represented by the following formula 5.
  • the polyfunctional (meth) acrylate which is (B) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.
  • C is an integer of 2 to 30, and R 6 is a hydrocarbon group having 2 to 200 carbon atoms, a group consisting only of ether oxygen (—O—) having 2 to 300 carbon atoms and a hydrocarbon group, or An isocyanurate ring or a group consisting only of an isocyanurate ring and a hydrocarbon group, and R 7 is a hydrogen atom or a methyl group.
  • the (B) polyfunctional (meth) acrylate a polymer type can also be suitably used.
  • a polymer type polyfunctional (meth) acrylate a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate or a copolymer has a group that reacts with an epoxy group such as (meth) acrylic acid.
  • the polyfunctional (meth) acrylate has a weight average molecular weight of 200 to 50000, preferably 220 to 40000, more preferably 240 to 30000.
  • the (meth) acrylate equivalent of (B) polyfunctional (meth) acrylate is 80 to 6000 g / mol, preferably 80 to 4500 g / mol, more preferably 85 to 3000 g / mol.
  • the (meth) acrylate equivalent is less than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive, and the thiol group of the (A) thioether-containing (meth) acrylate derivative and the unreacted (meth) acryloxy group
  • the toughness of the cured film made of the curable resin composition is lowered, and the adhesion may be lowered.
  • the (meth) acrylate equivalent is larger than 6000 g / mol, the (meth) acryloxy group concentration is extremely low, so that the reaction efficiency with the thiol group of the (A) thioether-containing (meth) acrylate derivative is reduced, thereby curing. There is a possibility that the toughness of the cured film made of the adhesive resin composition is lowered and the adhesiveness is lowered.
  • the photopolymerization initiator as the component (C) is added to promote the reaction between the thiol group and the (meth) acryloxy group, and can reduce the light irradiation necessary for curing the curable composition.
  • the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator.
  • the photoradical polymerization initiator is preferably used for shortening the reaction time
  • the photocationic polymerization initiator is preferably used for reducing curing shrinkage
  • the photoanionic polymerization initiator is used in the field of electronic circuits and the like. It is preferable to use it when imparting adhesiveness.
  • Examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. It is.
  • Examples of the cationic photopolymerization initiator include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylsulfonium tetrafluoroborate, and diphenyl.
  • Iodonium hexafluorophosphate diphenyliodonium hexafluoroarsenate, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, triphenylsulfonium tetrafluoroborate, Examples thereof include triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, and tri-p-tolylsulfonium trifluoromethanesulfonate.
  • photoanionic polymerization initiator examples include acetophenone o-benzoyloxime, nifedipine, 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4,4,0] deca- 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate, 1,2 -Dicyclohexyl-4,4,5,5-tetramethylbiguanidinium, n-butyltriphenylborate and the like.
  • the amine compound as component (D) include monofunctional amines and polyamines having a weight average molecular weight of 90 to 700, preferably 100 to 690, more preferably 110 to 680, and a plurality of amino groups.
  • the weight average molecular weight of the amine compound is less than 90, not only the volatility of the amine is increased, causing odor and void, but also the amine concentration at the time of heat curing is lowered, so that the crosslinking reaction is difficult to proceed and the adhesion is improved. It tends to decrease.
  • the weight average molecular weight of an amine compound exceeds 700, water resistance will become low and adhesiveness will fall easily.
  • Monofunctional amines include primary amines, secondary amines, and tertiary amines.
  • polyamines include primary amines, secondary amines, tertiary amines, and complex amines.
  • a complex amine is an amine having two or more of a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such complex amines include imidazoline compounds, imidazole compounds, N-substituted piperazine compounds, and N, N-dimethylurea derivatives.
  • an amine compound can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.
  • the amine compound may form a salt with an organic acid in advance in order to adjust the catalytic activity.
  • organic acid to be reacted in advance with the amine compound include aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 20 carbon atoms and 1 to 5 carboxyl groups in the molecule, and carboxyl groups having 1 to 20 carbon atoms.
  • aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 1 to 10 groups in the molecule, or isocyanuric acid.
  • imidazole compounds with high basicity are suitable for curing at the lowest temperature. Further, an imidazole compound coated with a phenol resin or the like can also be used.
  • the imidazole compound is a compound represented by the following formula 6.
  • R 9 is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom.
  • R 8 , R 10 and R 11 are each a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and R 8 to R 11 are bonded to form a ring. If it is, it is a hydrocarbon group having 2 to 8 carbon atoms.
  • the curable resin composition has a mass ratio ((A) / (B)) of (A) a thioether-containing (meth) acrylate derivative and (B) a polyfunctional (meth) acrylate of 0.05 to 30.
  • Blend “(A) / (B)” is a value obtained by dividing the mass of (A) the thioether-containing (meth) acrylate derivative by the mass of (B) polyfunctional (meth) acrylate.
  • (A) / (B) is less than 0.05 or more than 30, the adhesion tends to decrease.
  • the optimum value of (A) / (B) varies depending on the characteristics required for the curable resin composition, the type of (A) thioether-containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate.
  • the characteristics after curing the curable resin composition are the values of (number of thiol groups) / (number of (meth) acryloxy groups) (hereinafter referred to as thiol / ene ratio) in the unit weight of the curable resin composition. to be influenced. For example, when the thiol / ene ratio is in the range of 0.5 to 1.5, it is easy to form dense crosslinks and to become a tough cured product.
  • the thiol / ene ratio is 0.1 or more and less than 0.5 or more than 1.5 and 2.0 or less, a flexible and sticky cured product can be obtained. If the thiol / ene ratio is less than 0.1 or exceeds 2.0, gelation is difficult and adhesion tends to decrease.
  • curable resin composition is (C) with respect to 100 mass parts of total mass ((A) + (B)) of (A) thioether containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate (C).
  • the photopolymerization initiator is blended in an amount of 0.01 to 10 parts by mass.
  • the blending amount of the component (C) is less than 0.01 parts by mass with respect to 100 parts by mass of ((A) + (B))
  • a large amount of integrated light is required for the reaction of the thiol group and the (meth) acryloxy group to proceed Is required, and if it exceeds 10 parts by mass, the crosslink density may be lowered and the adhesion may be lowered.
  • the total weight of (A) thioether-containing (meth) acrylate derivative and (B) polyfunctional (meth) acrylate ((A) + (B)) 100 parts by mass of (D) the amine compound is blended in an amount of 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass.
  • the blending amount of the component (D) is less than 0.01 with respect to ((A) + (B))
  • the function as a catalyst becomes insufficient, the curing is not accelerated by heating, and the amount exceeds 50 parts by mass.
  • the storage stability of the curable resin composition is lowered.
  • the curable resin composition can form a cured film by coating on a substrate and curing.
  • the curable resin composition exhibits adhesion to the substrate due to the thioether group of the (A) thioether-containing (meth) acrylate derivative. Therefore, as a base material, a base material that forms a chemical bond with a thioether group (high chemical affinity), such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, etc.
  • an organic substrate such as an inorganic substrate, an organic substance having an unsaturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone.
  • the inorganic base material include glass, silicon, and various metals.
  • PET polyethylene terephthalate
  • PET polyethylene terephthalate
  • PET polybutylene terephthalate
  • polycarbonate resins polyimide resins
  • polyolefins such as polyethylene and polypropylene
  • Preferable examples include resin, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride resin, and polyacetal.
  • curable resin composition a cured film is excellent in a softness
  • the curable resin composition can be cured by irradiating light.
  • the light to be irradiated include active energy rays such as UV (ultraviolet rays) and EB (electron beams).
  • the curable resin composition comprises a component (C)
  • curable resin composition contains (D) component
  • hardening at about 80 degreeC low temperature is attained.
  • the curable resin composition contains the component (C) and the component (D)
  • it can be cured through a two-stage process including a curing process by light irradiation and a curing process by heating.
  • the curable resin composition may be diluted with an organic solvent to make the reaction system uniform and facilitate coating.
  • organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents, ether ester solvents, ketone solvents, and phosphate ester solvents. These organic solvents are preferably suppressed to a blending amount of less than 10000 parts by mass with respect to 100 parts by mass of the curable resin composition, but basically the solvent is volatilized at the time of becoming a cured film. It does not have a big influence on the physical properties.
  • the curable resin composition may be blended with a viscosity modifier such as silica powder for the purpose of adjusting the viscosity.
  • a viscosity modifier such as silica powder for the purpose of adjusting the viscosity.
  • These viscosity modifiers are preferably suppressed to a blending amount of less than 300 parts by mass with respect to 100 parts by mass of the curable resin composition. When the blending amount of the viscosity modifier exceeds 300 parts by mass, the adhesion may be lowered.
  • the curable resin composition may be added with various additives such as those used in ordinary paints and adhesives.
  • additives such as those used in ordinary paints and adhesives.
  • examples of such an additive include a surfactant for smoothing the coated surface, and an aluminum salt for increasing the usable time.
  • These additives are preferably suppressed to a blending amount of less than 80 parts by mass with respect to 100 parts by mass of the curable resin composition. When the compounding amount of these additives exceeds 80 parts by mass, the adhesion may be lowered.
  • ⁇ (B) component polyfunctional (meth) acrylate> (B-1, Mw: 5000) (N is an average of 13) (B-2, Mw: 246) (B-3, Mw: 352) (B-4, Mw: 22000)
  • B-1, Mw: 5000 N is an average of 13
  • B-2, Mw: 246 B-3, Mw: 352
  • B-4, Mw: 22000 A polymer obtained by adding equimolar amounts of methacrylic acid to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using the following D-3 as a catalyst (a white solid obtained by reprecipitation of a 50 wt% methyl isobutyl ketone solution with hexane).
  • ⁇ (C) component photopolymerization initiator> (C-1, Mw: 204) 1-hydroxy-cyclohexyl-phenyl-ketone (C-2, Mw: 348) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (C-3, Mw: 407) 2- (9-Oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] dec-5-ene
  • ⁇ (D) component amine compound> (D-1, Mw: 110) (D-2, Mw: 102) N, N-dimethyl-1,3-propanediamine (D-3, Mw: 680) (N1, n2, n3 are integers of 1 to 5, and the average is 3.5)
  • the components (A) to (D) were mixed at the blending ratios shown in Tables 1 to 4, respectively, and stirred with a spatula until uniform, to obtain samples of the curable resin compositions of Examples and Comparative Examples.
  • the following adhesiveness 1 room temperature adhesiveness
  • adhesiveness 2 cold region adhesiveness
  • flexibility flexibility
  • storage stability were evaluated for the samples of the curable resin compositions obtained in Examples and Comparative Examples. went. The results are shown in Tables 1 to 4.
  • Test pieces for evaluation of adhesion 1, adhesion 2, and flexibility were obtained as follows. Each sample of the curable resin composition was coated on a 25 mm wide PET film with a die coater to a thickness of 100 microns, and another PET film was stacked thereon, and then the curing conditions shown in Tables 1 to 4 were applied. A test piece for evaluation was obtained by curing. Note that Lumirror U46-100 manufactured by Toray Industries, Inc. was used as the PET film. For the light irradiation, a UV lamp system “Light Hammer 6” manufactured by Heraeus Noble Light Fusion Ubuy Co., Ltd. was used, and an H bulb was used as the lamp bulb.
  • Adhesion 1 room temperature adhesion
  • the test piece for evaluation was allowed to stand at 25 ° C. for 24 hours, and was measured within 5 minutes by the T-type peeling method defined in JIS K6854-3, and evaluated as follows.
  • the curable resin compositions of Examples 1-1 to 1-13 were confirmed to have high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability.
  • the curable compositions of Examples 2-1 to 2-5 were cured with a small amount of light irradiation, and high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability were confirmed.
  • the curable compositions of Examples 3-1 to 3-5 were cured by low light irradiation and low-temperature heating, and high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability were confirmed. It was.
  • Comparative Example 1-1 in which component (A) is too small relative to component (B) and Comparative Example 1-2 in which component (A) is excessive relative to component (B) Adhesion was poor even at room temperature.
  • Comparative Examples 1-3 to 1-7 in which the compound having the structure of the above formula 1 was used as the component (A), the adhesion under cold conditions was inferior.

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

Abstract

L'invention concerne une composition de résine durcissable contenant (A) un dérivé de (méth)acrylate contenant un thioéther ayant une structure spécifique, et (B) un (méth)acrylate polyfonctionnel ayant un poids moléculaire moyen en poids de 200-50 000. Le rapport de masse ((A)/(B)) entre le composant (A) et le composant (B) est de 0,05 à 30.
PCT/JP2016/050454 2015-01-20 2016-01-08 Composition de résine durcissable WO2016117385A1 (fr)

Priority Applications (4)

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KR1020177004380A KR101850257B1 (ko) 2015-01-20 2016-01-08 경화성 수지 조성물
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