WO2013146801A1 - Composition de résine durcissable pour la formation d'une couche adhésive et procédé d'intégration d'une base et base devant être liée - Google Patents

Composition de résine durcissable pour la formation d'une couche adhésive et procédé d'intégration d'une base et base devant être liée Download PDF

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WO2013146801A1
WO2013146801A1 PCT/JP2013/058830 JP2013058830W WO2013146801A1 WO 2013146801 A1 WO2013146801 A1 WO 2013146801A1 JP 2013058830 W JP2013058830 W JP 2013058830W WO 2013146801 A1 WO2013146801 A1 WO 2013146801A1
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adhesive layer
group
resin composition
forming
curable resin
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PCT/JP2013/058830
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English (en)
Japanese (ja)
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健敬 小島
枡田　一明
英行 佐藤
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日本ペイント株式会社
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Publication of WO2013146801A1 publication Critical patent/WO2013146801A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive

Definitions

  • the present invention relates to a curable resin composition for forming an adhesive layer and a method for integrating a substrate and an adherend substrate using the same.
  • substrates with various functions such as engineering plastics have begun to be used in the automobile and electronic / electrical industries in order to achieve miniaturization, weight reduction and high performance.
  • These base materials are generally difficult to adhere to other materials by applying an adhesive, and are called hard-to-adhere base materials. This is considered to be because it is difficult to form a chemical bond because there are few reactive functional groups in the structure of the substrate.
  • Patent Document 1 discloses aminoalkyl groups and alkoxy groups as primers having excellent adhesion and durability to PPS (polyphenylene sulfide) such as adhesives and paints made of various resins.
  • a primer for polyphenylene sulfide comprising an organosilicon compound having an oxirane ring and a compound having an oxirane ring is disclosed.
  • organosilicon compounds have poor compatibility with other resins, and the resulting coating film tends to be inhomogeneous.
  • by-products are generated due to decomposition and condensation of the organosilicon compound, which may impair adhesion.
  • a primer composition for engineering plastics having excellent adhesion to engineering plastics is selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, adipic acid and sebacic acid. And a polyester polyol (A) having a number average molecular weight of 15,000 or less and a polyisocyanate (B) are disclosed.
  • this composition has poor storage stability in a one-component type without a solvent, and in the case of a two-component type, the uniformity during mixing may be reduced.
  • a composition having a solid content of 5 to 20 Wt% is disclosed, but in this case, if sufficient solvent is not distilled off after coating, there is a possibility that the adhesion to the substrate or the directly overlying material may be lowered. is there.
  • This invention makes it a subject to solve the problem of the said prior art. If it specifies more specifically, this invention makes it a subject to provide the curable resin composition for contact bonding layer formation which can adhere
  • the present invention For forming an adhesive layer comprising a combination of a resin having at least one thermosetting functional group and a curing agent having a thermosetting functional group capable of undergoing a thermosetting reaction with the thermosetting functional group of the resin.
  • a curable resin composition comprising: (I) No detachment is generated by the thermosetting reaction, (Ii) a nitrogen element is included as an element constituting at least one of the thermosetting functional groups of the resin and the curing agent, (Iii) The concentration of the thermosetting functional group in which the nitrogen element is a constituent element in the resin solid content of the curable resin composition for forming an adhesive layer is 0.03 to 2.4 mmol / g.
  • a curable resin composition (1) for forming an adhesive layer is provided, which solves the above problems.
  • the present invention also provides A photopolymerizable monomer component containing a monomer having at least one thermosetting functional group, and a thermosetting function capable of thermosetting reaction with the thermosetting functional group of the photopolymerizable monomer component.
  • a curable resin composition for forming an adhesive layer containing a curing agent having a group (I) No detachment is generated by the thermosetting reaction, (Ii) a nitrogen element is included as an element constituting at least one thermosetting functional group of the photopolymerizable monomer component and the thermosetting functional group of the curing agent; (Iii)
  • the concentration of the thermosetting functional group in which the nitrogen element is a constituent element in the resin solid content of the curable resin composition for forming an adhesive layer is 0.03 to 2.4 mmol / g.
  • a curable resin composition (2) for forming an adhesive layer is also provided.
  • thermosetting functional group in which the nitrogen element is a constituent element is more preferably at least one selected from the group consisting of a carbodiimide group, an oxazoline group, an isocyanate group, and an amino group.
  • the present invention also provides A method of laminating a substrate and an adherend substrate to integrate the substrate and the adherend substrate, wherein the method includes the following steps: Applying an adhesive layer-forming curable resin composition (1) to a substrate to form an adhesive layer; The step of bonding the surface of the obtained adhesive layer and the adherend substrate, and after bonding, the adhesive layer is cured by heating, and the substrate and the adherend substrate are integrated.
  • Process, Including A method for integrating the substrate and the adherend substrate is also provided.
  • the present invention also provides A method of laminating a substrate and an adherend substrate to integrate the substrate and the adherend substrate, wherein the method includes the following steps: A process of forming an adhesive layer by irradiating with light after applying the curable resin composition for forming an adhesive layer (2) to a substrate; The step of bonding the surface of the obtained adhesive layer and the adherend substrate, and after bonding, the adhesive layer is cured by heating, and the substrate and the adherend substrate are integrated. Process, Including A method for integrating the substrate and the adherend substrate is also provided.
  • the curable resin composition for forming an adhesive layer of the present invention can firmly bond a substrate and an adherend substrate. This originates from the fact that the adhesive force does not decrease due to the generation of the desorbed material accompanying the curing of the composition.
  • Curing for forming an adhesive layer including a combination of a resin having at least one thermosetting functional group and a curing agent having a thermosetting functional group capable of undergoing a thermosetting reaction with the thermosetting functional group of the resin Curable resin composition (1), a photopolymerizable monomer component containing a monomer having at least one thermosetting functional group, and a thermosetting functional group possessed by the photopolymerizable monomer component;
  • a curable resin composition for forming an adhesive layer (2) comprising a curing agent having a thermosetting functional group capable of thermosetting reaction;
  • thermosetting reaction that no desorbed material is generated by the thermosetting reaction;
  • a nitrogen element is included as an element constituting at least one thermosetting functional group of the thermosetting functional group of the resin or photopolymerizable monomer component and the curing agent,
  • the functional group of the resin or photopolymerizable monomer component and the curing agent includes a thermosetting functional group in which nitrogen element is a constituent element,
  • concentration of the thermosetting functional group in which the nitrogen element is a constituent element in the resin solid content of the curable resin composition for forming an adhesive layer is 0.03 to 2.4 mmol / g, In common.
  • the curable resin composition for forming an adhesive layer in the present invention has the above feature (i), the adhesion force does not decrease due to the generation of a desorbed substance accompanying the curing of the composition. Thereby, it became possible to bond a base material and a to-be-adhered base material firmly. Moreover, by having the characteristics of (ii) and (iii) above, the wettability (affinity) of the curable resin composition with respect to the substrate and the adherend substrate becomes extremely good, and the substrate and the adherend substrate A strong bonding with is achieved.
  • the curable resin compositions (1) and (2) for forming the adhesive layer will be described in detail.
  • Curable resin composition for forming an adhesive layer (1) is: A resin having at least one thermosetting functional group, and a curing agent having a thermosetting functional group capable of undergoing a thermosetting reaction with the thermosetting functional group of the resin, including.
  • (1-1) an embodiment comprising a carboxyl group-containing resin (A) and a carbodiimide group-containing curing agent (D)
  • (1-2) an embodiment comprising a carboxyl group-containing resin (A) and an oxazoline group-containing curing agent (E)
  • (1-3) an embodiment comprising a hydroxyl group-containing resin (B) and an isocyanate group-containing curing agent (F)
  • (1-4) an embodiment containing a glycidyl group-containing resin (C) and an amino group-containing curing agent (G)
  • (1-5) an embodiment in which the above (1-1) and (1-2) are mixed
  • (1-6) a mode in which the above (1-1) and / or (1-2) and (1-3) are mixed
  • thermosetting reaction of the composition no desorbed material is generated by the thermosetting reaction of the composition.
  • the desorbed material include low molecular weight compounds such as water and alcohol generated by a polymerization reaction or a condensation reaction that is a thermosetting reaction.
  • Carboxyl group-containing resin (A) examples include a carboxyl group-containing acrylic resin, a carboxyl group-containing polyester resin, and a carboxyl group-containing alkyd resin.
  • carboxyl group-containing acrylic resin is a monomer mixture containing a carboxyl group-containing acrylic monomer and, if necessary, another monomer copolymerizable with the carboxyl group-containing acrylic monomer.
  • carboxyl group-containing acrylic resin is a monomer mixture containing a carboxyl group-containing acrylic monomer and, if necessary, another monomer copolymerizable with the carboxyl group-containing acrylic monomer.
  • Can be obtained by well-known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and high-temperature pressure continuous polymerization.
  • carboxyl group-containing acrylic monomer examples include (meth) acrylic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, itaconic acid, maleic acid, and fumaric acid.
  • Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • esters of alkyl alcohols such as lauryl (meth) acrylate and (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, diethylene glycol (meth) acrylate, caprolactone Hydroxyl group-containing acrylic monomers such as modified hydroxy (meth) acrylate and N-methylolacrylamide; styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, - methylstyrene, p-tert-butylstyrene, itaconic acid esters such as dimethyl itaconate, maleic acid esters such as dimethyl maleate, fumaric acid esters such as dimethyl fumarate, vinyl acetate; and the like.
  • Carboxyl group-containing polyester resin and carboxyl group-containing alkyd resin The carboxyl group-containing polyester resin can be obtained by half-esterifying a polyester polyol having three or more hydroxyl groups and an acid anhydride. Moreover, it can also obtain by condensing a polybasic acid component and a polyhydric alcohol component by a conventional method.
  • polyester polyol having 3 or more hydroxyl groups examples include low molecular polyhydric alcohols having 3 to 16 carbon atoms and having at least 3 hydroxyl groups.
  • these low molecular weight polyhydric alcohols can be synthesized by adding a lactone compound such as ⁇ -caprolactone to extend the chain.
  • Examples of the low molecular weight polyhydric alcohol used include trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin and a mixture thereof.
  • acid anhydrides used for preparing carboxyl group-containing polyester resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trimellitic anhydride, succinic anhydride, and the like. It is done.
  • the half-esterification reaction between a polyester polyol having three or more hydroxyl groups and an acid anhydride can be carried out under ordinary reaction conditions such as room temperature to 150 ° C. and normal pressure. However, it is not necessary to modify all the hydroxyl groups of the polyester polyol to carboxyl groups, and the hydroxyl groups may remain.
  • polybasic acid component examples include, in addition to the above acid anhydrides, for example, aromatic polyvalent carboxylic acids such as isophthalic acid and terephthalic acid, and alicyclic groups such as 1,4- and 1,3-cyclohexanedicarboxylic acid.
  • aromatic polyvalent carboxylic acids such as isophthalic acid and terephthalic acid
  • alicyclic groups such as 1,4- and 1,3-cyclohexanedicarboxylic acid.
  • examples thereof include aliphatic polycarboxylic acids such as polycarboxylic acids, fumaric acid, adipic acid, sebacic acid and azelaic acid.
  • a monobasic acid such as benzoic acid or t-butylbenzoic acid may be used in combination.
  • polyhydric alcohol component examples include, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2, 2-diethyl-1,3-propanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanediol, hydroxypivalic acid neopentyl glycol ester, 2-butyl-2-ethyl-1,3-propane Diols such as diol, 3-methyl-1,5-pentanediol, 2,2,4-trimethylpentanediol and hydrogenated bisphenol A, and trivalent or more such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol Polyols 2,2-dimethyl,
  • the carboxyl group-containing alkyd resin is prepared by ester condensation reaction of a polybasic acid component and a polyhydric alcohol component, and esterifying a fatty acid such as an unsaturated fatty acid to the hydroxyl group of the resulting ester condensation product. can do.
  • Unsaturated fatty acids such as linseed oil, safflower oil, soybean oil, sesame oil, poppy oil, eno oil, corn oil, tall oil, sunflower oil, cottonseed oil, kiri oil, dehydrated castor oil and semi-dry oil Fatty acids, and synthetic unsaturated fatty acids represented by high-diene fatty acids.
  • the carboxyl group-containing resin (A) preferably has a solid resin acid value in the range of 10 to 200 mgKOH / g.
  • the carboxyl group-containing resin (A) may contain a hydroxyl group.
  • Hydroxyl-containing resin (B) examples include a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, and a hydroxyl group-containing alkyd resin.
  • the hydroxyl group-containing acrylic resin is a solution polymerization of a monomer mixture containing a hydroxyl group-containing acrylic monomer and, if necessary, another monomer copolymerizable with the hydroxyl group-containing acrylic monomer. , Suspension polymerization, emulsion polymerization, high temperature and pressure continuous polymerization, and the like.
  • hydroxyl group-containing acrylic monomer those described for the carboxyl group-containing acrylic resin can be used.
  • Other monomers copolymerizable with a hydroxyl group-containing acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Esters of alkyl alcohols such as 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate and (meth) acrylic acid; styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene , P-tert-butylstyrene, itaconate such as dimethyl itaconate, maleate such as dimethyl maleate, fumarate such as dimethyl fumarate, vinyl acetate, and the like.
  • the hydroxyl group-containing polyester resin includes an oil-free polyester resin obtained by condensing the polybasic acid component and the polyhydric alcohol component, and a modified polyester obtained by modifying the polyester resin obtained above. Examples thereof include resins. Moreover, the polyester resin which grafted acrylic resin and / or vinyl resin can also be used. Furthermore, a urethane-modified polyester resin obtained by reacting a polyisocyanate compound with a polyester resin obtained by reacting a polybasic acid component and a polyhydric alcohol component can also be used.
  • monohydric alcohol monoepoxide compound such as Cardura E (trade name: manufactured by Ciel Chemical)
  • lactones ⁇ -propiolactone, dimethylpropiolactone, Butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, crotolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
  • monohydric alcohol monoepoxide compound such as Cardura E (trade name: manufactured by Ciel Chemical)
  • lactones ⁇ -propiolactone, dimethylpropiolactone, Butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, crotolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
  • the hydroxyl group-containing resin (B) preferably has a solid resin hydroxyl value in the range of 10 to 200 mgKOH / g.
  • the hydroxyl value exceeds 200 mgKOH / g, the viscosity of the resin composition is increased and workability may be deteriorated, and the water resistance of the resulting adhesive layer may be lowered.
  • the hydroxyl value is less than 10 mgKOH / g, the curability of the resin composition is lowered, and the solvent resistance, chemical resistance and water resistance of the resulting adhesive layer may be insufficient.
  • the said hydroxyl-containing resin (B) may contain the carboxyl group.
  • Glycidyl group-containing resin (C) examples include glycidyl group-containing acrylic resins and bisphenol-type epoxy resins.
  • a glycidyl group-containing acrylic resin is preferred from the viewpoint of the viscosity of the resin.
  • the glycidyl group-containing acrylic resin is a solution polymerization of a monomer mixture containing a glycidyl group-containing acrylic monomer and, if necessary, another monomer copolymerizable with the glycidyl group-containing acrylic monomer. It can be obtained by well-known polymerization methods such as suspension polymerization, emulsion polymerization, and high-temperature and pressure continuous polymerization.
  • glycidyl group-containing acrylic monomer examples include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexanyl (meth) acrylate, and the like.
  • Examples of other monomers copolymerizable with glycidyl group-containing acrylic monomers include, for example, the above-mentioned hydroxyl group-containing acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- Esters of alkyl alcohol and (meth) acrylic acid such as butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate; styrene, ⁇ -methylstyrene, o-methyl Styrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, itaconate such as dimethyl itaconate, maleate such as dimethyl maleate, fumarate such as dimethyl fumarate, vinyl acetate ;
  • the glycidyl group-containing resin (C) preferably has an epoxy equivalent in the range of 140 to 5,610.
  • the epoxy equivalent exceeds 5,610, the curability of the resin composition becomes low, and the solvent resistance, chemical resistance and water resistance of the resulting adhesive layer may be insufficient.
  • the epoxy equivalent is less than 140, the viscosity of the resin composition is increased, the workability may be deteriorated, and the water resistance of the resulting adhesive layer may be decreased.
  • the number average molecular weight of the carboxyl group-containing resin (A), the hydroxyl group-containing resin (B) and the glycidyl group-containing resin (C) is preferably 3,000 to 15,000, and preferably 4,000 to 10,000. More preferably.
  • the number average molecular weight in this specification can be measured by styrene homopolymer conversion using gel permeation chromatography.
  • the glass transition temperature of the carboxyl group-containing resin (A), the hydroxyl group-containing resin (B), and the glycidyl group-containing resin (C) is preferably 30 ° C. or less, and more preferably 20 ° C. or less.
  • the glass transition temperature can be measured by DSC (differential scanning calorimeter) or TMA (thermomechanical analyzer), and can be calculated from the amount of the monomer as a design value.
  • the solvent removal treatment is performed, and the obtained carboxyl group-containing resin (A), hydroxyl group-containing resin (B), and glycidyl group-containing resin (C) are used. It is preferable to distill off the solvent contained in advance. By sticking off the solvent in advance, a strong bonding can be achieved.
  • Carbodiimide group-containing curing agent (D) is a compound containing at least two carbodiimide groups in one molecule. From the viewpoint of reactivity, it is preferable to have a carbodiimide group at both ends.
  • a method for producing the carbodiimide group-containing curing agent a method well known to those skilled in the art, for example, a condensation reaction involving decarbonization of an organic diisocyanate can be used.
  • organic diisocyanate examples include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof.
  • aromatic diisocyanates 4,4- Diphenylmethane diisocyanate, 4,4-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate
  • isophorone diisocyanate dicyclohexylmeta 4,4-diisocyanate, and the like methylcyclohexane diisocyanate
  • a carbodiimidization catalyst is usually used.
  • the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3- Examples include methyl-1-phenyl-2-phospholene-1-oxide and phospholene oxides such as 3-phospholene isomers. From the viewpoint of reactivity, 3-methyl-1-phenyl-2 -Phosphorene-1-oxide is preferred.
  • the carbodiimide group-containing curing agent (D) preferably has a weight average molecular weight of 300 to 15,000, more preferably 500 to 10,000.
  • the weight average molecular weight in this specification can be measured by styrene homopolymer conversion using gel permeation chromatography.
  • the carbodiimide group-containing curing agent (D) preferably has a carbodiimide equivalent in the range of 200 to 1,000.
  • the carbodiimide equivalent exceeds 1,000, the curability of the resin composition becomes low, and the solvent resistance, chemical resistance and water resistance of the resulting adhesive layer may be insufficient.
  • the carbodiimide equivalent is less than 200, the viscosity of the resin composition is increased, the workability may be deteriorated, and the water resistance of the resulting adhesive layer may be decreased.
  • carbodiimide group-containing curing agent (D) Commercially available products may be used as the carbodiimide group-containing curing agent (D).
  • Examples of commercially available carbodiimide group-containing curing agents (D) include carbodilite V-01, V-03, V-05, V-07, V-09 (manufactured by Nisshinbo Chemical Co., Ltd.).
  • Oxazoline group-containing curing agent (E) As the oxazoline group-containing curing agent (E), a monomer mixture containing an oxazoline group-containing monomer and another monomer copolymerizable with the oxazoline group-containing monomer is subjected to solution polymerization, suspension polymerization, emulsion polymerization, high-temperature and pressure continuous polymerization. It can be prepared by polymerizing by a known polymerization method.
  • oxazoline group-containing monomers examples include 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-vinyl-2-oxazoline , 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and monomers having a substituent on the oxazoline group of these oxazoline group-containing monomers.
  • substituent of the oxazoline group include an alkyl group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an aromatic group having 5 to 10 carbon atoms. These oxazoline group-containing monomers may be used alone or in combination of two or more.
  • the other monomer copolymerizable with the oxazoline group-containing monomer is not particularly limited as long as it is copolymerizable with the monomer having an oxazoline group.
  • Acrylic esters or methacrylates such as ethyl, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, unsaturated nitriles such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide ,
  • Unsaturated amides such as N-methylolacrylamide and N-methylolmethacrylamide
  • vinyl esters such as vinyl acetate and vinyl propionate
  • vinyl ethers such as methyl vinyl ether and ethyl vinyl ether Le
  • ethylene, olefins such as propylene
  • Preferred examples of the oxazoline group-containing curing agent (E) include a copolymer of styrene and 2-isopropenyl-2-oxazoline.
  • the oxazoline group-containing curing agent (E) preferably has an oxazoline equivalent in the range of 200 to 1,000.
  • the oxazoline equivalent exceeds 1,000, the curability of the resin composition becomes low, and the solvent resistance, chemical resistance and water resistance of the resulting adhesive layer may be insufficient.
  • an oxazoline equivalent is less than 200, the viscosity of a resin composition becomes high, there exists a possibility that workability
  • oxazoline group-containing curing agent (E) Commercial products may be used as the oxazoline group-containing curing agent (E).
  • examples of commercially available oxazoline group-containing curing agents (E) include Epocross RPS-1005 (manufactured by Nippon Shokubai Co., Ltd.).
  • the oxazoline group of the oxazoline group-containing curing agent (E) reacts with the carboxyl group of the carboxyl group-containing resin (A) to generate an amide ester bond or an amide ether bond to form a crosslinked structure.
  • This reaction is a reaction that proceeds well even at low temperatures, and no desorbed product is produced by this reaction. Therefore, there exists an advantage that a base material and a to-be-adhered base material can be bonded together firmly.
  • the isocyanate group-containing curing agent (F) is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule. Specifically, 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4- Aromatic polyisocyanates such as phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI); hexamethylene diisocyanate (HDI), trimethylhexa Methylene diisocyanate (HDI), trimethylhexa Methylene diiso
  • the weight average molecular weight of the isocyanate group-containing curing agent (F) is preferably 200 to 10,000, and more preferably 300 to 5,000.
  • the isocyanate group-containing curing agent (F) preferably has an isocyanate concentration in the curing agent in the range of 12 to 60% by mass.
  • the isocyanate concentration exceeds 60% by mass, the viscosity of the resin composition is increased, workability may be deteriorated, and the water resistance of the resulting adhesive layer may be decreased.
  • the isocyanate concentration is less than 12% by mass, the curability of the resin composition is lowered, and the resulting adhesive layer may have insufficient solvent resistance, chemical resistance, water resistance, and the like.
  • isocyanate group-containing curing agent F
  • examples of such commercially available products include Takenate D-102 and 170N, Takenate 500 (manufactured by Mitsui Chemicals), T1890 (manufactured by Degussa), Desmodur L, HL, Sumidur N-7, N-3300, N3500, N3200-90CX (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate THA-100, 24A-90PX (manufactured by Asahi Kasei Chemicals), Coronate 2030, FH, 341 (manufactured by Nippon Polyurethane Co., Ltd.), Isonate 143L (manufactured by Mitsubishi Chemical), Bernock D -750, 800, Crisbon NX (manufactured by DIC), VESTANAT T1890 / 100 (manufactured by Degussa Huls) and the like
  • the amino group-containing curing agent (G) preferably has a weight average molecular weight of 100 to 15,000, more preferably 200 to 10,000.
  • weight average molecular weight of the carbodiimide group-containing curing agent (G) is in the above range, there is an advantage that more excellent adhesion and storage stability can be obtained.
  • the amino group-containing curing agent (G) preferably has an amine equivalent in the range of 280 to 5,610.
  • the amine equivalent exceeds 5,610, the curability of the resin composition becomes low, and the solvent resistance, chemical resistance and water resistance of the resulting adhesive layer may be insufficient.
  • the amine equivalent is less than 280, the viscosity of the resin composition is increased, the workability may be deteriorated, and the water resistance of the resulting adhesive layer may be decreased.
  • Curable resin compositions for forming an adhesive layer (1-1) to (1-6) are embodiments of the curable resin composition (1) for forming an adhesive layer of the present invention, a carboxyl group-containing resin (A), a hydroxyl group-containing resin (B), and glycidyl
  • the group-containing resin (C) corresponds to a resin having at least one thermosetting functional group, and includes a carbodiimide group-containing curing agent (D), an oxazoline group-containing curing agent (E), and an isocyanate group-containing curing agent (F).
  • the amino group-containing curing agent (G) corresponds to a curing agent having a thermosetting functional group capable of undergoing a thermosetting reaction with the thermosetting functional group of the resin.
  • the carboxyl group-containing resin (A) may contain a hydroxyl group
  • the hydroxyl group-containing resin (B) may contain a carboxyl group. That is, in the embodiment of (1-6), when (1-1) and / or (1-2) and (1-3) are mixed, the resin includes a carboxyl group-containing resin (A) and a hydroxyl group-containing resin. (B) may be used, or a hydroxyl group-containing resin (A) containing a hydroxyl group or a hydroxyl group-containing resin (B) containing a carboxyl group may be used.
  • the carbodiimide group-containing curing agent (D), the oxazoline group-containing curing agent (E), the isocyanate group-containing curing agent (F), and the amino group-containing curing agent (G) are the elements constituting the thermosetting functional group. Nitrogen atoms are included. That is, the thermosetting functional group in which the nitrogen element is a constituent element includes a carbodiimide group that the carbodiimide group-containing curing agent (D) has, an oxazoline group that the oxazoline group-containing curing agent (E) has, and an isocyanate group-containing curing agent (F). Is an amino group possessed by the isocyanate group and amino group-containing curing agent (G).
  • thermosetting functional group containing nitrogen element is preferably at least one selected from the group consisting of a carbodiimide group, an oxazoline group, an isocyanate group, and an amino group.
  • the concentration of the thermosetting functional group in which the nitrogen element is a constituent element in the resin solid content of the curable resin composition for forming the adhesive layer is 0.00. It is 03 to 2.4 mmol / g, preferably 0.17 to 2.4 mmol / g, more preferably 0.25 to 2.4 mmol / g, and still more preferably 0.4 to 2.4 mmol / g.
  • concentration of the thermosetting functional group in which this nitrogen element is a constituent element is less than 0.03 mmol / g, problems such as insufficient adhesion of the resulting adhesive layer occur.
  • the “resin solid content of the curable resin composition for forming an adhesive layer” in the curable resin composition for forming an adhesive layer (1) refers to the above components (A) to (G) and other resins as required. It means the total solid content of the component.
  • the amount of the thermosetting functional group possessed by the resin exceeds the above range, the curability of the resin composition becomes low, and the durability of the resulting adhesive layer may be insufficient.
  • curing agent has exceeds the said range there exists a possibility that the water resistance of the contact bonding layer obtained may fall with the unreacted remaining hardening
  • the curable resin composition for forming an adhesive layer (1) at least one of the components constituting the composition preferably has a cyclic structure portion.
  • the cyclic structure portion include an aliphatic hydrocarbon ring such as cyclohexane, an aromatic hydrocarbon ring such as a benzene ring, a heterocyclic ring such as an isocyanurate ring, and an oxazoline ring.
  • an engineering plastic generally a PPS or the like, which is generally referred to as a difficult-to-adhere substrate, is used. In the case of bonding, there is an advantage that better adhesion can be obtained.
  • Curable resin composition for forming an adhesive layer (2) is: A photopolymerizable monomer component containing a monomer having at least one thermosetting functional group, and a thermosetting agent capable of undergoing a thermosetting reaction with the thermosetting functional group of the photopolymerizable monomer component A curing agent having a group, including.
  • the curable resin composition for forming an adhesive layer (2) is first irradiated with light after being applied, whereby the photopolymerizable monomer component is polymerized and becomes a resin component that undergoes a thermosetting reaction with the curing agent. Next, by heating, the resin component formed by polymerization of the photopolymerizable monomer component and the curing agent are thermally reacted, and the adhesive layer is cured.
  • the components (A) to (G) are the same components as the above-described curable resin composition for forming an adhesive layer (1).
  • the photopolymerizable monomer component that becomes the carboxyl group-containing resin (A) by photopolymerization includes a carboxyl group-containing monomer.
  • the carboxyl group-containing monomer corresponds to “a monomer having a thermosetting functional group”.
  • the carboxyl group-containing monomer for example, in addition to the carboxyl group-containing acrylic monomer described in the carboxyl group-containing resin (A), a commercially available product, monohydroxyethyl phthalate, which is sold as Aronix series manufactured by Toagosei Co., Ltd.
  • carboxyl group-containing monomers such as acrylate, ⁇ -carboxy-polycaprolactone monoacrylate, polybasic acid-modified acrylic oligomer, and polyester acrylate.
  • monomers other than a carboxyl group-containing monomer contained in the said monomer monomers other than the carboxyl group-containing acrylic monomer described in the carboxyl group-containing resin (A) are mentioned, for example.
  • photopolymerizing such a photopolymerizable monomer component containing a carboxyl group-containing monomer the carboxyl group-containing resin (A) is obtained.
  • the photopolymerizable monomer component that becomes the hydroxyl group-containing resin (B) by photopolymerization includes a hydroxyl group-containing monomer.
  • the hydroxyl group-containing monomer corresponds to “a monomer having a thermosetting functional group”.
  • the hydroxyl group-containing monomer contained in the hydroxyl group-containing monomer and the monomer for example, in addition to the hydroxyl group-containing acrylic monomer described in the carboxyl group-containing acrylic resin (A) as in the hydroxyl group-containing resin (B), Mention may be made of long-chain hydroxyl group-containing monomers such as isocyanuric acid-ethylene oxide-modified diacrylate and 2-hydroxy-3-phenoxypropyl acrylate, which are commercially available and sold as Aronix series manufactured by Toagosei Co., Ltd.
  • the monomer other than the hydroxyl group-containing monomer include monomers other than the hydroxyl group-containing acrylic monomer described in the hydroxyl group-containing resin (B).
  • the photopolymerizable monomer component that becomes the glycidyl group-containing resin (C) by photopolymerization includes a glycidyl group-containing monomer.
  • the glycidyl group-containing monomer corresponds to “a monomer having a thermosetting functional group”.
  • Examples of the monomer other than the glycidyl group-containing monomer and the glycidyl group-containing monomer contained in the glycidyl group-containing monomer and the above monomer include those described in the glycidyl group-containing resin (C).
  • the photopolymerizable monomer component contained in the composition is photopolymerized by light irradiation after the composition is applied, and the component (A) ) To (C). Therefore, it is preferable that the curable resin composition (2) for forming an adhesive layer contains a photopolymerization initiator.
  • the photopolymerizable monomer component that becomes a carboxyl group-containing resin (A) by photopolymerization may contain a hydroxyl group-containing monomer, and the photopolymerizable monomer component that becomes a hydroxyl group-containing resin (B) by photopolymerization. May contain a carboxyl group-containing monomer.
  • the resin obtained by photopolymerization is a carboxyl group-containing resin ( A) and the hydroxyl group-containing resin (B) may be mixed, or may be a carboxyl group-containing resin (A) containing a hydroxyl group or a hydroxyl group-containing resin (B) containing a carboxyl group.
  • Examples of the photopolymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
  • Examples of radical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-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-methylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] Al
  • Examples of the cationic polymerization initiator include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-ditertiarybutyldiphenyliodonium, 3,3′-dinitrodiphenyliodonium.
  • the amount of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the resin solid content of the curable resin composition for forming an adhesive layer (2). It is more preferable that If the amount of the photopolymerization initiator is outside the above range, the curability of the curable resin composition may be lowered.
  • the (meth) acryloyl group concentration of the curable resin composition for forming an adhesive layer (2) is preferably 0.1 to 5.0 mmol / g, and preferably 0.15 to 4.0 mmol / g. Is more preferable.
  • (meth) acryloyl group concentration (mmol / g) is included in 1 g of the photopolymerizable monomer component contained in the adhesive layer forming curable resin composition (2). The calculated value of the number of (meth) acryloyl groups.
  • the concentration of the thermosetting functional group in which the nitrogen element is a constituent element in the resin solid content of the curable resin composition for forming the adhesive layer is 0.00. It is 03 to 2.4 mmol / g, preferably 0.17 to 2.4 mmol / g, more preferably 0.25 to 2.4 mmol / g, and still more preferably 0.4 to 2.4 mmol / g.
  • concentration of the thermosetting functional group in which this nitrogen element is a constituent element is less than 0.03 mmol / g, problems such as insufficient adhesion of the resulting adhesive layer occur.
  • the concentration of the thermosetting functional group in which nitrogen element is a constituent element exceeds 2.4 mmol / g, the viscosity of the resin composition may increase and workability may deteriorate, and the resulting adhesive layer may be obtained. There is a risk of problems such as a decrease in water resistance.
  • the “resin solid content of the curable resin composition for forming an adhesive layer” in the curable resin composition for forming an adhesive layer (2) is a photopolymerizable monomer component and the above components (D) to (G). And the total solid content of other resin components as required.
  • the ratio of the thermosetting functional group of the photopolymerizable monomer component to the thermosetting functional group of the curing agent is the photopolymerizable monomer.
  • the quantity of the thermosetting functional group which a photopolymerizable monomer component has exceeds the said range there exists a possibility that the adhesive force of the contact bonding layer obtained may become inadequate.
  • the amount of the thermosetting functional group possessed by the curing agent exceeds the above range, the viscosity of the resin composition may be increased and workability may be deteriorated, and the water resistance of the obtained adhesive layer is decreased. There is a case.
  • the curable resin composition for forming an adhesive layer (2) at least one of the components constituting the composition preferably has a cyclic structure portion.
  • the cyclic structure portion include an aliphatic hydrocarbon ring such as cyclohexane, an aromatic hydrocarbon ring such as a benzene ring, a heterocyclic ring such as an isocyanurate ring, and an oxazoline ring.
  • an engineering plastic which is generally referred to as a difficult-to-adhere substrate, particularly a substrate such as PPS, is used. In the case of bonding, there is an advantage that better adhesion can be obtained.
  • the adhesive layer forming curable resin compositions (1) and (2) of the present invention may contain other components than the resin component and the photopolymerization initiator, if necessary.
  • a filler is mentioned, for example.
  • fillers include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, and oxidation.
  • examples thereof include inorganic fillers such as magnesium, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide and ceramic, and organic fillers such as carbon and rubber fillers.
  • fillers can be appropriately selected according to the type and use of the substrate and the adherend substrate.
  • the metal filler can be added for the purpose of imparting conductivity, thermal conductivity, thixotropy and the like to the curable resin composition for forming an adhesive layer.
  • the inorganic filler can be added for the purpose of imparting thermal conductivity, low thermal expansibility, low hygroscopicity and the like to the adhesive layer.
  • the organic filler can be added for the purpose of imparting toughness to the adhesive layer.
  • These fillers may be used individually by 1 type, and may use 2 or more types together.
  • a silica filler is more preferable.
  • Silica filler has the advantages of high dispersibility with respect to the resin component and can provide good adhesion.
  • the number average particle diameter of the filler is preferably 0.001 to 30 ⁇ m. When the number average particle diameter of the filler is within the above range, there is an advantage that an effect of improving fracture toughness can be obtained.
  • Examples of the method for measuring the number average particle size of the filler include a method of measuring the particle size using a scanning electron microscope (SEM).
  • the content when the filler is included is in the range of 1 to 50 parts by mass of the filler with respect to 100 parts by mass of the resin component. Preferably there is.
  • the adhesive layer forming curable resin compositions (1) and (2) of the present invention may contain various coupling agents as required.
  • the coupling agent By including the coupling agent, the interface bonding performance with respect to the substrate and the adherend substrate can be improved.
  • the various coupling agents include silane-based, titanium-based, and aluminum-based coupling agents. Among these, silane coupling agents are particularly preferable.
  • the content is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin component.
  • the adhesive layer-forming curable resin compositions (1) and (2) of the present invention may contain an ion scavenger as necessary.
  • an ion scavenger By including the ion-trapping agent, there are advantages such that the ionic impurities are adsorbed and the insulating property under the condition that the adhesive layer absorbs moisture is improved.
  • the ion scavenger include inorganic ion adsorbents such as triazine thiol compounds, bisphenol reducing agents, zirconium compounds, and antimony bismuth magnesium aluminum compounds.
  • the content when an ion scavenger is used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin component.
  • the adhesive layer-forming curable resin compositions (1) and (2) of the present invention may contain a curing accelerator as necessary.
  • a curing accelerator can be used without particular limitation as long as it accelerates the thermal curing of the resin component.
  • the curing accelerator include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4. 0.0] undecene-7-tetraphenylborate.
  • the adhesive layer forming curable resin composition (1) comprises the above components (A) to (G) and other components as required. Can be prepared by mixing.
  • the adhesive layer-forming curable resin composition (2) is prepared by mixing the photopolymerizable monomer component, components (D) to (G), and a photopolymerization initiator and other components as required. Can be prepared. Mixing can be performed using a commonly used disperser such as a stirrer, a three-roller, or a ball mill.
  • the substrate and the adherend The substrate can be bonded well.
  • a method for integrating the substrate and the adherend substrate when using the curable resin composition (1) for forming an adhesive layer, Applying an adhesive layer-forming curable resin composition (1) to a substrate to form an adhesive layer; The step of bonding the surface of the obtained adhesive layer and the adherend substrate, and after bonding, the adhesive layer is cured by heating, and the substrate and the adherend substrate are integrated. Process, Is included.
  • the curable resin composition for forming an adhesive layer of the present invention can be suitably used for bonding components used in the automobile industry, the electronic and electrical equipment industry and the like.
  • the base material and the adherend base material constituting these parts for example, ABS (acrylonitrile-butadiene-styrene) resin, polycarbonate resin, nylon resin, polyester resin, polypropylene resin, polyethylene terephthalate resin, polyimide resin, polyetherimide resin , Plastics such as polyether naphthalate resin and methyl pentene resin and fiber reinforced products such as these polymer alloys, carbon fiber and glass fiber, thermosetting plastics such as epoxy resin and unsaturated polyester, silver, copper, magnesium, Examples thereof include metals such as aluminum, iron, tin, tin, and alloys thereof, and those whose materials are surface-treated or painted.
  • the curable resin composition for forming an adhesive layer of the present invention has an advantage that it can be particularly suitably used for bonding an engineering plastic represented by a PPS resin generally referred to
  • the method for applying the adhesive layer-forming curable resin composition (1) or (2) to the substrate is not particularly limited, and the adhesive layer-forming curable resin composition (1) or (2) can be applied by a method such as spraying, brushing, roller, or spin coating.
  • the adhesive layer is provided on the substrate.
  • the coating amount of the curable resin composition for forming an adhesive layer (1) or (2) can be appropriately adjusted according to the base material to be bonded and the use of the base material.
  • the base material and the adherend base material are bonded together without performing the light irradiation step.
  • adhesive layer forming curable resin composition (2) after apply
  • the light to be irradiated for example, light having an exposure amount of 0.1 to 3.0 J / cm 2 , preferably 0.3 to 1.5 J / cm 2 can be used.
  • the wavelength of irradiation light is not specifically limited, For example, the irradiation light etc. which have a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.
  • the irradiation time is not particularly limited and is, for example, 0.5 to 2 seconds.
  • volatile components such as an organic solvent or water that can be contained in the composition can be removed.
  • the adhesive layer is cured by heating.
  • a base material and a to-be-adhered base material are adhere
  • the heating temperature and heating time depend on the types of components (A) to (G) and / or photopolymerizable monomer components contained in the curable resin composition for forming an adhesive layer, and the material of the substrate and the substrate to be bonded. It can be suitably selected according to (heat-resistant temperature), shape and the like. Examples of the heating conditions include conditions of heating at 60 to 200 ° C. for 10 to 60 minutes.
  • the curable resin compositions (1) and (2) for forming an adhesive layer of the present invention are said to be adhesives such as various base materials constituting parts used in the automobile industry or the electronic and electrical equipment industry, particularly difficult-to-adhere base materials. It can be suitably used in the adhesion of the substrate. Moreover, the curable resin composition for forming an adhesive layer of the present invention can be used as a primer in adhesion or coating of various substrates in addition to the use of bonding a substrate and an adherend substrate. The curable resin composition for forming an adhesive layer of the present invention can also be used as a sealing material (filler).
  • the “adhesive layer” in the present specification includes forms such as “primer layer” and “sealing part (filling part)” in the case where the curable resin composition for forming an adhesive layer is used in the above applications.
  • the mixture was reacted at the same temperature for 1 hour, and an initiator solution consisting of 1.0 part of azobisisobutyronitrile and 20 parts of methyl ethyl ketone was added dropwise over 1 hour. After completion of the dropping, the reaction was continued at the same temperature for further 3 hours, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a carboxyl group-containing acrylic resin 1.
  • the number average molecular weight in terms of polystyrene was 4,600 as measured by a non-volatile content (solid content) of 100%, a solid content resin acid value of 30 mgKOH / g, and gel permeation chromatography (GPC) measurement.
  • Production Example 2 Production of the carboxyl group-containing acrylic resin 2
  • the monomer mixture was changed to 7.7 parts of methacrylic acid, 18.6 parts of methyl methacrylate and 73.7 parts of 2-ethylhexyl acrylate.
  • a carboxyl group-containing acrylic resin 2 was obtained.
  • the number average molecular weight in terms of polystyrene was 4,900 as measured by a non-volatile content (solid content) of 100%, a solid content resin acid value of 50 mgKOH / g, and gel permeation chromatography (GPC).
  • Production Example 3 Production Example 1 of the hydroxyl group-containing acrylic resin 1 was the same as Production Example 1 except that 25.5 parts of 2-hydroxyethyl methacrylate, 6.8 parts of methyl methacrylate, and 67.7 parts of 2-ethylhexyl acrylate were used. Similarly, a hydroxyl group-containing acrylic resin 1 having a nonvolatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 4,900, and the solid resin hydroxyl value was 110 mgKOH / g.
  • Production Example 4 Production Example 1 except that the production monomer mixture of hydroxyl group-containing acrylic resin 2 was changed to 9.3 parts of 2-hydroxyethyl methacrylate, 20.2 parts of methyl methacrylate, and 70.6 parts of 2-ethylhexyl acrylate. Similarly, a hydroxyl group-containing acrylic resin 2 having a nonvolatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 4,700, and the solid resin hydroxyl value was 40 mgKOH / g.
  • Production Example 5 Production Example 1 for hydroxyl group-containing acrylic resin 3 except that the monomer mixture was changed to 2.3 parts of 2-hydroxyethyl methacrylate, 25.9 parts of methyl methacrylate, and 71.8 parts of 2-ethylhexyl acrylate. Similarly, a hydroxyl group-containing acrylic resin 3 having a nonvolatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 5,000, and the solid resin hydroxyl value was 10 mgKOH / g.
  • Production of glycidyl group-containing acrylic resin 1 A monomer mixture was changed to 10.0 parts of glycidyl methacrylate, 20.2 parts of methyl methacrylate, and 69.8 parts of 2-ethylhexyl acrylate. Thus, a glycidyl group-containing acrylic resin 1 having a resin non-volatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 4,900, and the epoxy equivalent was 142.
  • Production Example 7 Production of glycidyl group-containing acrylic resin 2 The same as in Production Example 1, except that the monomer mixture was 30.0 parts of glycidyl methacrylate, 4.9 parts of methyl methacrylate, and 65.1 parts of 2-ethylhexyl acrylate. Thus, a glycidyl group-containing acrylic resin 2 having a resin non-volatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 4,700, and the epoxy equivalent was 188.
  • Production Example 9 Production of Oxidation Polymerizable Unsaturated Group-Containing Acrylic Resin Monomer mixed solution except that 10.0 parts of oleic acid adduct of glycidyl methacrylate, 20.0 parts of methyl methacrylate, 70.0 parts of 2-ethylhexyl acrylate Produced an oxidatively polymerizable unsaturated group-containing acrylic resin having a nonvolatile content (solid content) of 100% in the same manner as in Production Example 1. The number average molecular weight of the obtained resin was 4,000.
  • Production Example 10 Same as Production Example 1, except that the monomer mixture for producing the non-curable acrylic resin was 50.0 parts of n-butyl acrylate, 20.0 parts of methyl methacrylate, and 30.0 parts of 2-ethylhexyl acrylate. Thus, a non-curable acrylic resin having a nonvolatile content (solid content) of 100% was obtained. The number average molecular weight of the obtained resin was 4,200.
  • Examples 1 to 4 By mixing the carboxyl group-containing acrylic resins 1 and 2 obtained in Production Examples 1 and 2 and the carbodiimide group-containing curing agent at a solid mass shown in Table 1, respectively, a curable resin composition for forming an adhesive layer A product was prepared.
  • concentration of the thermosetting functional group in which the nitrogen atom is a constituent element in the resin solid content of the obtained curable resin composition for forming an adhesive layer was calculated according to the above formula (1), 0.35, 0.53, 0.78 and 0.35 mmol / g.
  • a curable resin composition for forming an adhesive layer is prepared by mixing the hydroxyl group-containing acrylic resins 1 to 3 obtained in Production Examples 3 to 5 and the isocyanate group-containing curing agent in solid masses shown in Table 1, respectively. Was prepared.
  • the concentration of the thermosetting functional group in which the nitrogen atom is a constituent element in the resin solid content of the obtained curable resin composition for forming an adhesive layer was calculated in the same manner as in Example 1. 1.04, 0.31 and 0.10 mmol / g.
  • Examples 9-11 Glycidyl group-containing acrylic resin 1 and glycidyl group-containing acrylic resin 2 obtained in Production Examples 6 and 7 and an amino group-containing curing agent are mixed at a solid mass shown in Table 1 to form an adhesive layer.
  • a curable resin composition was prepared. When the concentration of the thermosetting functional group in which the nitrogen atom is a constituent element in the resin solid content of the obtained adhesive layer forming curable resin composition was calculated in the same manner as in Example 1, 0.54, 0.25 and 1.60 mmol / g.
  • Comparative Example 3 A curable resin composition for forming an adhesive layer was prepared by mixing the alkoxysilyl group-containing acrylic resin obtained in Production Example 8 and dibutyltin dilaurate in solid masses shown in Table 2, respectively.
  • Comparative Example 4 A curable resin composition for forming an adhesive layer was prepared by mixing the oxidatively polymerizable unsaturated group-containing acrylic resin obtained in Production Example 9 and the oxidative polymerization dryer at solid masses shown in Table 2, respectively. .
  • Comparative Example 5 A composition was prepared using the non-curable acrylic resin obtained in Production Example 10.
  • Comparative Example 6 A curable resin composition for forming an adhesive layer was prepared in the same manner as in Example 12 except that the oxazoline group-containing curing agent was not used.
  • Comparative Example 7 A curable resin composition for forming an adhesive layer was prepared in the same manner as in Example 1 except that the amount of the carbodiimide group-containing compound was 0.5 part.
  • concentration of the thermosetting functional group in which the nitrogen atom is a constituent element in the resin solid content of the obtained curable resin composition for forming an adhesive layer was calculated according to the above formula (1), it was 0.02 mmol / g.
  • Comparative Examples 8 and 9 A curable resin composition for forming an adhesive layer was prepared in the same manner as in Example 5 except that the isocyanate group-containing compound was changed to 0.2 part and 50 parts, respectively.
  • the concentration of the thermosetting functional group in which the nitrogen atom is a constituent element in the resin solid content of the obtained curable resin composition for forming an adhesive layer was calculated according to the above formula (1). It was 2.55 mmol / g.
  • Example 12 and 13 and Comparative Example 6 the composition was applied and then irradiated with light having a wavelength of 365 nm at 300 mJ / cm 2 for 1.2 seconds using a high-pressure mercury lamp.
  • a glass plate having a size of 100 mm ⁇ 25 mm and a thickness of 1.6 mm was bonded thereto, and the sample was heated at 180 ° C. for 1 hour while being fixed with a clip to obtain a test body having an interlayer thickness of 100 ⁇ m.
  • test specimens thus obtained were measured for tensile shear adhesion strength according to the method of JIS K6850 (1999), and the bonding property between glass and PPS was evaluated according to the following criteria.
  • the results are shown in Tables 1 and 2. 5 ⁇ 3N / mm 2 or more 4 ⁇ 2N / mm 2 or more 3N / mm 2 less than 3 ⁇ 1N / mm 2 or more 2N / mm 2 less than 2 ⁇ 0.5N / mm 2 or more 1N / Less than mm 2 1 ... less than 0.5 N / mm 2
  • Carboxyl group-containing unsaturated group-containing monomer manufactured by Toagosei Co., Ltd., Aronix M-5400 ⁇ Unsaturated group-containing monomer having no thermosetting functional group: pentaerythritol acrylate, Carbodiimide group-containing curing agent: Nisshinbo Co., Ltd., Carbodilite V-05, Isocyanate group-containing curing agent: Asahi Kasei Chemicals, Duranate 22A-100, Amino group-containing curing agent: Mitsui Chemical Fine, NBDA, Oxazoline group-containing curing agent: Nippon Shokubai Co., Ltd., Epocross RPS-1005, -Glycidyl group-containing curing agent: manufactured by Mitsubishi Chemical Corporation, jER828, -Etherified methylol group-containing curing agent: Cymel 303, manufactured by Nippon Cytec Industries, Ltd. ⁇ Aromatic sulfonic
  • the adhesive layer forming curable resin compositions obtained in Examples 1 to 13 have high adhesion to glass, steel plate and PPS substrates. Also, the bonding of different materials such as glass and PPS was good.
  • Comparative Example 1 is an example using a glycidyl group-containing curing agent that does not contain a nitrogen atom as an element constituting a thermosetting functional group.
  • the adhesion to PPS was particularly poor.
  • Comparative Example 2 is an example using an etherified methylol group-containing curing agent that does not contain a nitrogen atom as an element constituting a thermosetting functional group. Also in this example, the adhesion to PPS was particularly poor. In addition, in the bonding of different materials such as glass and PPS, the adhesion is greatly reduced.
  • Comparative Examples 3 and 4 are examples in which a curable resin is contained but no curing agent is contained, and the curable resin does not contain a nitrogen atom as an element constituting a thermosetting functional group. . Also in this example, the adhesion to PPS was particularly poor. In addition, in the bonding of different materials such as glass and PPS, the adhesion is greatly reduced.
  • Comparative Example 5 is an example in which no thermosetting functional group is contained.
  • the cured adhesive layer itself could not be obtained, and adhesion to any substrate could not be ensured.
  • Comparative Example 6 is an example in which a photopolymerizable monomer component is included but no curing agent is included. Also in this example, the adhesion to PPS was particularly poor. Moreover, in the bonding of different materials such as glass and PPS, the adhesion was greatly reduced.
  • Comparative Examples 7 and 8 each contain a carbodiimide group-containing curing agent and an isocyanate group-containing curing agent containing nitrogen atoms as elements constituting thermosetting functional groups, the nitrogen element in the resin solid content is included. This is an example in which the concentration of the functional group contained is less than the specified range. Also in this example, the adhesion to PPS was poor. Moreover, in the bonding of different materials such as glass and PPS, the adhesion was greatly reduced.
  • Comparative Examples 9 and 10 each contain an isocyanate group-containing curing agent and an amino group-containing curing agent containing a nitrogen atom as an element constituting each thermosetting functional group, but the nitrogen element in the resin solid content. This is an example in which the concentration of the functional group included exceeds the specified range. Also in this example, the adhesion to PPS was poor. Moreover, in the bonding of different materials such as glass and PPS, the adhesion was greatly reduced.
  • the curable resin composition for forming an adhesive layer of the present invention can firmly bond a base material and a base material to be bonded, particularly a hard-to-adhere base material or a different material, for example, machine tool parts and automotive parts. It can be used for drive system parts, electrical equipment parts, transmission system parts, and the like.

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Abstract

L'invention a pour but de proposer une composition de résine durcissable pour la formation d'une couche adhésive, qui est apte à lier de façon fiable une base qui est appelée une base légèrement adhésive. A cet effet, l'invention concerne une composition de résine durcissable pour la formation d'une couche adhésive, qui contient une combinaison d'une résine ayant au moins une sorte de groupe fonctionnel thermodurcissable et un agent durcisseur ayant un groupe fonctionnel thermodurcissable qui est apte à subir une réaction de thermodurcissement avec le groupe fonctionnel thermodurcissable de la résine. Cette composition de résine durcissable pour la formation d'une couche adhésive est caractérisée en ce que : (i) une matière désorbée n'est pas générée par la réaction de thermodurcissement ; (ii) l'élément azote est contenu comme élément qui constitue le groupe fonctionnel thermodurcissable de la résine et/ou le groupe fonctionnel thermodurcissable de l'agent durcisseur ; et (iii) la concentration du groupe fonctionnel thermodurcissable qui contient l'élément azote comme élément constitutif dans les matières solides de résine de la composition de résine durcissable pour la formation d'une couche adhésive est 0,03-2,4 mmol/g.
PCT/JP2013/058830 2012-03-27 2013-03-26 Composition de résine durcissable pour la formation d'une couche adhésive et procédé d'intégration d'une base et base devant être liée WO2013146801A1 (fr)

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JP2012-070836 2012-03-27

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