WO2014112165A1 - Heat-curable composition and laminated structure - Google Patents

Abstract

Provided are: a heat-curable composition having an excellent adhesion property and excellent storage stability; and a laminated structure produced using the composition. A heat-curable composition characterized by comprising (A) a blocked isocyanate which has been blocked with at least two types of block agents, (B) a curing catalyst and (C) a hydroxy-group-containing resin having a glass transition temperature (Tg) of 25˚C or lower; and a laminated structure produced using the composition.

Description

Thermosetting composition and laminated structure

The present invention relates to a thermosetting composition and a laminated structure, and more particularly to a thermosetting composition excellent in adhesiveness and storage stability and a laminated structure obtained using the composition.

As one of the methods for producing a laminated structure, an adhesive has been used for bonding between layers. For example, in the manufacture of an IC card, an adhesive is applied between a sheet-like IC card circuit board made of insulating resin on which electronic components are mounted and a protective sheet made of plastic such as PET. A laminated structure in which the respective layers are firmly bonded can be formed (for example, Patent Documents 1 and 2).

JP 2004-318606 A JP 2006-072804 A

In recent years, with the diversification of objects to be bonded and their materials, further improvement in the adhesive properties of the adhesive is required. For example, in the case of a non-contact type IC card, an antenna circuit of an inlay (a sheet in which a non-contact IC module composed of an antenna circuit, an IC chip, etc. is provided on a base material) is attached to the base material surface with an adhesive. There is a technique of forming the formed aluminum by etching. In that case, since the adhesive for sticking aluminum remains on the surface of the base material, the conventional adhesive may not be able to sufficiently bond the inlay and other layers such as the core sheet. In addition, a two-component adhesive, that is, a component that is stored separately so as not to harden, and an adhesive that is mixed at the time of use tends to have better adhesiveness than a one-component adhesive. In addition, since the pot life after mixing is short, an adhesive having excellent adhesiveness and excellent storage stability as a one-component type has been demanded.

Therefore, an object of the present invention is to provide a thermosetting composition excellent in adhesiveness and storage stability and a laminated structure obtained using the composition.

As a result of intensive studies to solve the above-mentioned problems, the present inventors formulated a blocked isocyanate blocked with at least two types of blocking agents, a curing catalyst, and a hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.

That is, the thermosetting composition of the present invention comprises (A) a blocked isocyanate blocked with at least two types of blocking agents, (B) a curing catalyst, and (C) a glass transition temperature (Tg) of 25 ° C. or less. A hydroxyl group-containing resin.

In the thermosetting composition of the present invention, it is preferable that the blocking agent of blocked isocyanate blocked with (A) at least two types of blocking agents is a secondary amine blocking agent and an active methylene blocking agent.

In the thermosetting composition of the present invention, the (B) curing catalyst is preferably a salt of a basic compound and an organic acid.

The thermosetting composition of the present invention preferably further contains a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C.

In the thermosetting composition of the present invention, the hydroxyl group-containing resin (C) having a glass transition temperature (Tg) of 25 ° C. or less is preferably a polyester polyol.

The thermosetting composition of the present invention is preferably for an adhesive used in the production of an IC card.

The laminated structure of the present invention is obtained by using the thermosetting composition described above.

According to the present invention, it is possible to provide a thermosetting composition excellent in adhesiveness and storage stability and a laminated structure obtained using the composition by adopting the above configuration.

Since the thermosetting composition of the present invention is excellent in storage stability as described above, it can be made into a one-component thermosetting composition. In the present specification, one-component means that all components can be stored together.
Hereinafter, each component of the thermosetting composition of this invention is explained in full detail.

[(A) Blocked isocyanate blocked with at least two types of blocking agents]
The thermosetting composition of the present invention contains a blocked isocyanate blocked with at least two types of blocking agents as the component (A). A blocked isocyanate is a compound having a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When the isocyanate is heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group. Generated. Component (A) is a blocked isocyanate in which at least two types of blocking agents are added in one molecule. For example, an addition reaction between a compound having a plurality of isocyanate groups in one molecule and two or more types of blocking agents. However, it is not limited to this, and any known one can be used.

As the compound having a plurality of isocyanate groups, that is, a polyisocyanate compound, for example, aromatic polyisocyanate or alicyclic aliphatic polyisocyanate may be used. Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate. In addition, adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds can be used. (A) The blocked isocyanate blocked with at least two types of blocking agents is either a blocked isocyanate in which the isocyanate group of hexamethylene diisocyanate polyisocyanate is blocked with a blocking agent, or any of its adducts, burettes and isocyanurates. It is preferable that The number of functional groups is preferably 2 or more.

Examples of the blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate, acetylacetone and diethylmalonate; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol Monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone Alcohol-based blocking agents such as coal, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, Mercaptan block agents such as thiophenol, methylthiophenol, ethylthiophenol; acid amide block agents such as acetic acid amide and benzamide; imide block agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine Primary amine blocking agents such as pyrazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole, 3-methylpyrazole, 3-isobutyl-5 -Pyrazoles such as t-butyl-pyrazole, 3-isobutyl-5-methyl-pyrazole and 3,5-di-t-butyl-pyrazole, imidazoles such as imidazole and 2-ethylimidazole, 1,2,4 triazole And secondary amine blocking agents such as triazols such as 3,5-dimethyltriazole and pyrazoline and pyrazolinone described in Australian Published Patent Application No. AU-81721 / 94; such as methyleneimine and propyleneimine Examples include imine block agents.

(A) The blocking agent of blocked isocyanate blocked with at least two kinds of blocking agents is preferably a blocking agent that can be dissociated at 80 to 130 ° C. This is because if a blocked isocyanate blocked with such a blocking agent is used, the adhesion treatment can be performed even at a relatively low temperature. In that case, even if the object to be bonded is made of a material having low heat resistance such as polyethylene terephthalate (PET) or polyvinyl chloride (PVC), the bonding process can be performed. The component (A) is preferably a secondary amine block agent and an active methylene block agent, more preferably a pyrazole block agent and an active methylene block agent, from the viewpoint of adhesiveness. More preferably, 5-dimethylpyrazole and diethyl malonate. Although the detailed mechanism is not necessarily clear, it is considered that these blocking agents do not evaporate in the dissociation temperature range after dissociation, and thus good adhesiveness can be obtained.

(A) The blocked isocyanate blocked with at least two kinds of blocking agents may be commercially available, for example, TRIXENE BI-7992 [HDI (hexamethylene diisocyanate) -based trimer manufactured by Baxenden; 5-dimethylpyrazole and diethyl malonate] and the like.

(A) The blocked isocyanate blocked with at least two types of blocking agents is an equivalent ratio of the blocked isocyanate group to the hydroxyl group of the hydroxyl group-containing resin contained in the thermosetting composition of the present invention (block isocyanate group / hydroxyl group). , Preferably 0.01 to 100, more preferably 0.1 to 10. When the equivalent ratio is 0.01 or more, the curing reaction proceeds sufficiently so that high adhesive strength can be obtained. When the equivalent ratio is 100 or less, the strength of the composition is improved. (A) A component can be used individually by 1 type or in combination of 2 or more types. Further, other blocked isocyanates may be blended within a range not impairing the effects of the present invention.

[(B) Curing catalyst]
The thermosetting composition of the present invention contains a curing catalyst as the component (B). (B) The curing catalyst is preferably a urethanization catalyst. (B) As the curing catalyst, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), Triethylamine, triethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2-dimethylimidazole Basic compounds such as amine compounds such as: salts of the basic compounds with organic acids such as formic acid, acetic acid, acetoacetic acid, citric acid, phthalic acid, benzenesulfonic acid, sulfamic acid; stannous octoate, dibutyltin Tin catalysts such as organic tin compounds such as dilaurate and inorganic tin compounds; tetra-isopropyl-titanate, tetra-butyl-titanium Titanium-based catalysts such as carbonates; metal chlorides made of Cr, Mn, Co, Ni, Fe, Cu or Al, such as cobalt chloride, ferrous chloride, ferric chloride; cobalt acetylacetonate, nickel acetyl Metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al such as acetonate and iron acetylacetonate; Metal made of Cr, Mn, Co, Ni, Fe, Cu or Al such as copper sulfate Examples thereof include sulfates.

(B) Since the curing catalyst is excellent in storage stability as a one-part thermosetting composition, it is preferably a salt of the basic compound and the organic acid. When a basic compound is blended as it is as a curing catalyst for the purpose of improving adhesiveness, when the hydroxyl group-containing resin contained in the thermosetting composition of the present invention is a polyol having an ester bond, the hydrolysis reaction of the ester is accelerated. This is because the viscosity decreases with time. In addition, since basic compounds are highly dangerous to the human body, they are difficult to handle as they are. In the present invention, by adding a salt of a basic compound and an organic acid as a curing catalyst (B) as a curing catalyst, better adhesion and storage stability as a one-component thermosetting composition can be obtained. Obtainable. As a salt of a basic compound and an organic acid, any known salt can be used.

The salt of the basic compound and the organic acid is preferably a salt of an amine compound and an organic acid, more preferably a salt of a cyclic amine compound and an organic acid, and 1,8-diazabicyclo [5.4.0] undeca A salt of -7-ene and an organic acid or a salt of 1,5-diazabicyclo [4.3.0] non-5-ene and an organic acid is more preferable. The above 1,8-diazabicyclo [5.4.0] undec-7-ene has the following structural formula (1), and the above 1,5-diazabicyclo [4.3.0] non-5-ene has the following structural formula. It is represented by (2).

(B) The curing catalyst is an equivalent ratio of the chemical equivalent of the curing catalyst to the hydroxyl equivalent of the hydroxyl group-containing resin contained in the thermosetting composition of the present invention (chemical equivalent of the curing catalyst / hydroxyl equivalent), preferably 0.01. To 100, more preferably 0.1 to 10. (B) A component can be used individually by 1 type or in combination of 2 or more types.

Even when a salt of a basic compound and an organic acid is used as the component (B), the equivalent ratio of the chemical equivalent of the basic compound to the hydroxyl equivalent of the hydroxyl group-containing resin contained in the thermosetting composition of the present invention ( The chemical equivalent of the basic compound / hydroxyl equivalent) is preferably 0.01 to 100, more preferably 0.1 to 10. When the equivalent ratio is 0.01 or more, the dissociation reaction of the blocked isocyanate proceeds efficiently, and good adhesiveness is obtained. When the equivalent ratio is 100 or less, the strength of the composition is improved.

[(C) Hydroxyl-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower]
The thermosetting composition of the present invention contains a hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower as the component (C). Since the component (C) has a hydroxyl group, it reacts with an isocyanate group generated from the component (A) by dissociation of the blocking agent. In the present invention, excellent adhesion can be obtained by using a hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower. Any known hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower can be used. In addition, the glass transition temperature (Tg) as used in the field of this invention is measured by the differential scanning calorimeter (DSC) according to the method described in “5.17.5 DSC method” of JIS C6481: 1996 ( Tg).

The hydroxyl group-containing resin in component (C) is a resin having a hydroxyl group in one molecule, and is usually a resin having a hydroxyl value of 0.01 to 1000 mgKOH / g, preferably 0.1 to 500 mgKOH / g. Specific examples of the hydroxyl group-containing resin include polyester polyol, polyether polyol, polyurethane polyol, polycarbonate polyol, polycaprolactone polyol, and polyacryl polyol. The hydroxyl group-containing resin in component (C) is preferably a polyester polyol.

(C) A hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower may be a commercially available product. For example, Byron 500 manufactured by Toyobo Co., Ltd. (polyester polyol, Tg = 4 ° C.), Byron 550 (polyester polyol, Tg = −15 ° C.), Byron 560 (polyester polyol, Tg = 7 ° C.), Byron 630 (polyester polyol, Tg = 7 ° C.), Byron 670 (polyester polyol, Tg = 7 ° C.), Nippon Synthetic Chemical Polyester TP290 (polyester polyol, Tg = 10 ° C.), Polyester LP035 (polyester polyol, Tg = 20 ° C.), Polyester LP033 (polyester polyol, Tg = 15 ° C.), Polyester LP050 (polyester polyol, Tg = 10 ° C.), Polyester LP0 1 (polyester polyol, Tg = 4 ° C.), Polyester LP022 (polyester polyol, Tg = −15 ° C.), ARUFON UH-2000 (polyacryl polyol, Tg = −55 ° C.) manufactured by Toagosei Co., Ltd., ARUFON UH-2032 ( Polyacryl polyol, Tg = −60 ° C.), ARUFON UH-2041 (polyacryl polyol, Tg = −50 ° C.), ARUFON UHE-2012 (polyacryl polyol, Tg = 20 ° C.) and the like.
The glass transition temperature (Tg) may be 25 ° C. or less, preferably −70 ° C. or more and 25 ° C. or less, more preferably −65 ° C. or more and 20 ° C. or less.

(C) Hydroxyl-containing resins having a glass transition temperature (Tg) of 25 ° C. or lower can be used singly or in combination of two or more. Moreover, other hydroxyl-containing resin may be mix | blended in the range which does not impair the effect of this invention.

[Hydroxyl-containing resin with glass transition temperature (Tg) exceeding 25 ° C.]
The thermosetting composition of the present invention preferably further contains a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. Thereby, it is easy to finely adjust the shift of the position when bonding the objects to be bonded, and it is difficult for dust to be attached, so that a thermosetting composition excellent in workability can be obtained. Any known hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. can be used.

The hydroxyl group-containing resin in the hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. is a resin having a hydroxyl group in one molecule. Specific examples of the hydroxyl group-containing resin include the same resins as the component (C).

The hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. may be a commercially available one. For example, Byron 103 (polyester polyol, Tg = 47 ° C.) manufactured by Toyobo Co., Ltd., Byron 200 (polyester polyol, Tg = 67) ° C), Byron 220 (polyester polyol, Tg = 53 ° C.), Byron 226 (polyester polyol, Tg = 65 ° C.), Byron 240 (polyester polyol, Tg = 60 ° C.), Byron 245 (polyester polyol, Tg = 60 ° C.) Byron 270 (polyester polyol, Tg = 67 ° C.), Byron 280 (polyester polyol, Tg = 68 ° C.), Byron 290 (polyester polyol, Tg = 72 ° C.), Byron 296 (polyester polyol, Tg = 71 ° C.), Byron 00 (polyester polyol, Tg = 47 ° C.), Byron 660 (polyester polyol, Tg = 55 ° C.), Byron 802 (polyester polyol, Tg = 60 ° C.), Byron 822 (polyester polyol, Tg = 68 ° C.), Byron 885 ( Polyester polyol, Tg = 79 ° C., Nippon Synthetic Chemical Co., Ltd. Polyester TP220 (polyester polyol, Tg = 70 ° C.), Polyester TP217 (polyester polyol, Tg = 40 ° C.), Polyester TP249 (polyester polyol, Tg = 36) ° C), polyester TP235 (polyester polyol, Tg = 65 ° C), polyester TP236 (polyester polyol, Tg = 60 ° C), polyester TP270 (polyester polyol, Tg = 40) ), Polyester TP220 (polyester polyol, Tg = 70 ° C.), manufactured by Toagosei Co., Ltd. ARUFON UH-2170 (polyacrylic polyol, Tg = 60 ° C.), and the like.
Although glass transition temperature (Tg) should just exceed 25 degreeC, Preferably, it is 90 degreeC or less larger than 25 degreeC, More preferably, it is 30 degreeC or more and 85 degrees C or less.

The compounding amount when a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. is calculated in terms of solid content with respect to 100 parts by mass of the hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or less. And preferably 1 to 10000 parts by mass, more preferably 10 to 1000 parts by mass, and still more preferably 50 to 200 parts by mass. In the case of 1 part by mass or more, it is easy to adjust the position shift when bonding the objects to be bonded, and it is possible to suppress the adhesion of dust. In the case of 10,000 parts by mass or less, the adhesive strength is improved. The hydroxyl group-containing resin component having a glass transition temperature (Tg) exceeding 25 ° C. can be used alone or in combination of two or more.

(solvent)
The thermosetting composition of the present invention may contain an organic solvent in order to adjust the viscosity of the composition. Any known solvent can be used as long as it can dissolve the components (A) to (C). For example, toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol Examples thereof include monomethyl ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, and butyl carbitol acetate. A solvent can be appropriately selected according to the printing method. Two or more of them may be included as necessary.

(Other additives)
In the thermosetting composition of the present invention, components generally blended in the composition can be blended as long as the effects of the present invention are not impaired. Such components include binders, colorants, surface treatment agents, antifoaming agents, leveling agents, surface tension reducing agents, plasticizers, fillers, coupling agents, thixotropic agents, stabilizers, antioxidants, A dispersing agent etc. are mentioned. Moreover, the touch-drying property (tack property) of the thermosetting composition of this invention can also be improved by mix | blending a filler.

The thermosetting composition of the present invention can be used as an adhesive. The bonding method is not particularly limited. For example, the composition is applied on at least one adhesion target by a printing method or the like and dried, and the adhesion target is positioned so that the applied composition is positioned between the adhesion targets. The objects to be bonded can be bonded by bonding and curing the composition while thermocompression bonding. When the composition is applied using a printing method, any printing method may be used. For example, the composition may be applied by a screen printing method, an offset printing method, a gravure printing method, a die coating method, or the like. Among these, the screen printing method is preferably used because the film thickness can be easily controlled by selecting the plate and printing conditions. The temperature of thermocompression bonding needs to be a temperature at which the object to be bonded is not deformed. For example, it is preferably set to 140 ° C. or less for a PET substrate.

The object to be bonded is not particularly limited, but a sheet formed of a plastic such as PET, PET-G (polyethylene terephthalate copolymerized with cyclohexanedimethanol), PVC, polycarbonate, or the like; formed of an adhesive such as polyethylene or polyurethane Adhesive layer: It can be suitably used for adhesion of metals such as aluminum and copper.

The adhesive using the thermosetting composition of the present invention can be used for producing a laminated structure such as an IC card. For example, in the case of an IC card, it can be used for adhesion between a circuit board (or inlay), a sheet-like base material formed of PET or the like, and an adhesive layer formed thereon. According to the present invention, after the thermosetting composition is applied to the substrate and dried, the substrate and the circuit board (or inlay) are applied to the substrate and dried via the thermosetting composition. A laminated IC card can be provided by bonding and curing the thermosetting composition while thermocompression bonding the base material to the circuit board (or inlay).

The thermosetting composition of the present invention can be used as a paint by adding colorants such as pigments, dyes, and pigments. The kind of colorant to be added is not particularly limited as long as it can be dispersed in the composition.
As the colorant, conventionally known colorants such as red, blue, green, yellow, white, black, purple, orange, brown can be used, and any of pigments, dyes, and pigments may be used. As a specific example, a color index (CI; issued by The Society of Dyers and Colorists) number is given.

Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone compounds.
Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds.
Examples of the green colorant include metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based compounds.
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone compounds.
Examples of the black colorant include carbon black.
Examples of the white colorant include rutile type or anatase type titanium oxide, zinc oxide, basic lead carbonate, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, and barium sulfate.
Titanium oxide is preferably rutile titanium oxide because it has little influence on the deterioration of the resin and can suppress an increase in the viscosity of the composition. Titanium oxide is not limited by a production method such as a chlorine method or a sulfuric acid method. Moreover, what gave surface treatments, such as an alumina process and a silica process, can be used suitably.
The blending amount of the white colorant is preferably 100 to 350 parts by mass, more preferably 150 to 300 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing resin (C) having a glass transition temperature (Tg) of 25 ° C. or less.
The blending amount of the colorant other than white is not particularly limited, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing resin (C) having a glass transition temperature (Tg) of 25 ° C. or less. Particularly preferred is 0.1 to 5 parts by mass.

The thermosetting composition of the present invention can be used as a conductive adhesive, a conductive paint, or an anisotropic conductive adhesive by adding conductive particles. The conductive particles are not particularly limited as long as they can be dispersed in the composition.
As conductive fine particles, silver (Ag), gold (Au), nickel (Ni), copper (Cu), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe) , Metals such as platinum (Pt), iridium (Ir), osmium (Os), palladium (Pd), rhodium (Rh), ruthenium (Ru), tungsten (W), molybdenum (Mo) and their alloys, Examples thereof include metal oxides such as tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), and indium tin oxide (ITO), and carbon black. These may be used alone or in combination of two or more. It can be used as a powder. Moreover, in order to prevent the conductive fine particles from being oxidized and to improve the dispersibility in the composition, those treated with a fatty acid are preferred. Among the fatty acids, particularly low-carbon carboxylic acids having 6 to 8 carbon atoms, specifically hexanoic acid, heptanoic acid, octanoic acid, sorbic acid, benzoic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid. It is preferable that the length is about.
As the conductive fine particles, Cu, Ag, and Al are preferable, and Ag is more preferable.

Various shapes such as a spherical shape, a flake shape, and a dendrite shape can be used as the shape of the conductive fine particles. In the thermosetting composition of the present invention, the primary particle size of the conductive fine particles is less than 1 μm. Is more preferably 300 nm or less, still more preferably 100 nm or less, particularly preferably 60 nm or less, and most preferably 20 nm or less.
The primary particle diameter of the conductive fine particles is an average particle diameter calculated from 10 random conductive fine particles observed with an electron microscope.

The blending amount of the conductive fine particles is appropriately in a proportion of 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 15 to 90% by mass, based on the solid content. When the amount of the conductive fine particles is 5 to 90% by mass, the line width shrinkage and disconnection of the electrode circuit can be suppressed, and a stable good dispersion (paste) can be easily produced.

(Laminated structure)
The laminated structure of the present invention is obtained using the thermosetting composition of the present invention. In this specification, a laminated structure means a structure in which a member to be bonded and an adhesive member are bonded via a cured product of a thermosetting composition pattern on the member to be bonded. As said to-be-adhered member and an adhesive member, members of arbitrary properties according to a use, such as various insulating members, various conductive members, various transparent or translucent members, or colored members, can be used. Moreover, as a to-be-adhered member and an adhesive member, the molded article, plate-shaped molded article, sheet | seat, etc. which were produced from various materials, such as glass, ceramics, a metal, a plastics, paper, etc. can be used, according to a desired use. Various members can be used. Specific examples of the laminated structure include an IC card and a printed wiring board.
In addition, the thermosetting composition of this invention is applicable also as coating material uses, such as adhesion | attachment uses, such as a logo, and an interlayer insulation material.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

Each component described in Tables 1 and 2 below was mixed and stirred to prepare a composition. The unit of the blending amount in the table is part by mass.

(Adhesive strength A)
The composition of the example and the comparative example was applied to a white PET film having a thickness of 250 μm (Tetron film U2 manufactured by Teijin DuPont Films Co., Ltd.) by a screen printing method using a 100-mesh polyester bias plate with a film thickness of 20 μm on the entire surface. Printing was done. This was dried in a hot air circulating drying oven at 50 ° C. for 30 minutes. By chemically etching the surface aluminum layer of the aluminum foil type raw fabric of the non-contact IC Card / IC Tag antenna film (inlay) manufactured by Nippon Graphite Industry Co., Ltd. using an acidic chemical solution mainly composed of hydrochloric acid. All the adhesive layers made of an adhesive for affixing aluminum were exposed. The exposed adhesive layer was placed on the composition application surface on a white PET film and thermocompression bonded at 140 ° C. with a press pressure of 0.2 MPa for 60 minutes. A specimen of a laminated structure was obtained by naturally cooling to room temperature and cutting to a required size. After the test piece of this laminated structure was left at room temperature for one day, the adhesive strength was evaluated according to the JISX6305-1 delamination test method.

(Adhesive strength B)
The composition of the example and the comparative example was solid-printed with a film thickness of 20 μm on the entire surface of a copper plate having a thickness of 200 μm by a screen printing method using a 100 mesh polyester bias plate. This was dried in a hot air circulating drying oven at 50 ° C. for 30 minutes. A 200 μm-thick transparent polycarbonate film (Iupilon FE2000 manufactured by Mitsubishi Gas Chemical Company) was placed on the composition coated surface on the copper plate, and thermocompression bonded at 180 ° C. with a press pressure of 0.5 MPa for 10 seconds. A specimen of a laminated structure was obtained by naturally cooling to room temperature and cutting to a required size. After the test piece of this laminated structure was left at room temperature for one day, the adhesive strength was evaluated according to the JISX6305-1 delamination test method.

(Thickening rate)
0.2 ml of the composition of Examples and Comparative Examples was sampled, and the initial viscosity was measured using a cone plate viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the conditions of 25 ° C. and 5 rpm. Next, 200 g of each of the compositions of Examples and Comparative Examples was placed in a sealed container and stored in a constant temperature bath at 20 ° C. for 48 hours. 0.2 ml of the composition after storage was collected, and the viscosity after storage was measured using a cone plate viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 25 ° C. and at a rotation speed of 5 rpm. The thickening rate Δ% was calculated using the following formula.
Viscosity increase Δ% = (viscosity after 48 hours storage−initial viscosity) / initial viscosity × 100

(Workability)
The composition of the example and the comparative example was printed on a white PET film (Tetron film U2 manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 250 μm using a 100-mesh polyester bias plate with a thickness of 20 μm on the entire surface by screen printing. Went. This was dried in a hot air circulating drying oven at 50 ° C. for 30 minutes. After cooling to room temperature, a Toray Lumirror T-60 was placed on the composition-coated surface of the white PET film, and a load of 10 g / cm ² was applied. After standing at room temperature for 24 hours, the adhesion of the white PET film and Lumirror T-60 was evaluated.
○: Good workability (no sticking)
Δ: Slight workability (slightly sticking)
×: Workability failure (with a large amount of sticking)

(chemical resistance)
The compositions of Examples and Comparative Examples were solid-printed with a film thickness of 20 μm on the entire surface using a 100-mesh polyester bias plate by screen printing on Lumirror T-60 manufactured by Toray Industries, Inc. This was dried in a hot air circulating drying oven at 50 ° C. for 30 minutes. After cooling to room temperature, it hardened | cured on 140 degreeC on the conditions for 30 minutes, and produced the test piece for chemical-resistance evaluation. The prepared test piece was immersed in PMA (propylene glycol monomethyl ether acetate) at room temperature for 1 hour and then air-dried, and a cross-cut cello tape (registered trademark) peel test was performed based on JIS: K5600-5-6. Sex was evaluated. The evaluation criteria are as follows.
○: No peeling △: Partial peeling ×: Overall peeling

(Specific resistance)
The compositions of Examples and Comparative Examples were printed with a 1 mm width and a 40 mm length evaluation pattern on a Toray Lumirror T-60 by screen printing, and dried in a hot air circulation drying oven at 50 ° C. for 30 minutes. It was. After cooling to room temperature, it hardened | cured on 140 degreeC on the conditions for 30 minutes, and produced the resistance value measurement pattern. The line width, line length, and thickness of the prepared pattern were measured to determine the specific resistance (volume resistivity).

※１：東洋紡社製バイロン５６０（ポリエステルポリオール、固形分：１００％、Ｔｇ＝７℃、水酸基価＝８ｍｇＫＯＨ／ｇ）
※２：東亞合成社製ＡＲＵＦＯＮ　ＵＨ２０００（ポリアクリルポリオール、固形分：１００％、Ｔｇ＝－５５℃、水酸基価＝２０ｍｇＫＯＨ／ｇ）
※３：東洋紡社製バイロン２００（ポリエステルポリオール、固形分：１００％、Ｔｇ＝６７℃、水酸基価＝６ｍｇＫＯＨ／ｇ）
※４：バクセンデン社製ＢＩ－７９９２［３，５－ジメチルピラゾールとジエチルマロネートで封鎖されたブロックイソシアネート、ＨＤＩ（ヘキサメチレンジアミン）系のトリイソシアネートのイソシアヌレート体］、固形分：７０％、ブロックイソシアネート当量：４５７
※５：バクセンデン社製ＢＩ－７８８２［３，５－ジメチルピラゾールで封鎖されたブロックイソシアネート；ＨＤＩ（ヘキサメチレンジアミン）系のトリイソシアネートのイソシアヌレート体］、固形分：７０％、ブロックイソシアネート当量：４１２
※６：旭化成ケミカルズ社製デュラネート２１Ｓ－７５Ｅ［イソシアネート；ＨＤＩ（ヘキサメチレンジアミン）系のトリイソシアネートのビウレット体］、固形分：７５％、イソシアネート当量：２７１
※７：ＤＢＵ（１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン）とギ酸の塩、固形分：１００％、化学当量：１９８
※８：ＤＢＮ（１，５－ジアザビシクロ［４．３．０］ノナ－５－エン）とギ酸の塩、固形分：１００％、化学当量：１７０
※９：ＰＭＡ（プロピレングリコールモノメチルエーテルアセテート）
※１０：銀粉末（フレーク状、平均粒径４～５μｍ）

* 1: Byron 560 manufactured by Toyobo Co., Ltd. (polyester polyol, solid content: 100%, Tg = 7 ° C., hydroxyl value = 8 mgKOH / g)
* 2: ARUFON UH2000 manufactured by Toagosei Co., Ltd. (polyacryl polyol, solid content: 100%, Tg = −55 ° C., hydroxyl value = 20 mgKOH / g)
* 3: Byron 200 manufactured by Toyobo Co., Ltd. (polyester polyol, solid content: 100%, Tg = 67 ° C., hydroxyl value = 6 mgKOH / g)
* 4: BI-7992 (block isocyanate blocked with 3,5-dimethylpyrazole and diethylmalonate, isocyanurate of HDI (hexamethylenediamine) triisocyanate), solid content: 70%, block Isocyanate equivalent: 457
* 5: BI-7882 manufactured by Baxenden [Block isocyanate blocked with 3,5-dimethylpyrazole; isocyanurate of HDI (hexamethylenediamine) triisocyanate], solid content: 70%, blocked isocyanate equivalent: 412
* 6: Duranate 21S-75E manufactured by Asahi Kasei Chemicals Co., Ltd. [isocyanate; biuret of HDI (hexamethylenediamine) triisocyanate], solid content: 75%, isocyanate equivalent: 271
* 7: DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) and formic acid salt, solid content: 100%, chemical equivalent: 198
* 8: DBN (1,5-diazabicyclo [4.3.0] non-5-ene) and formic acid salt, solid content: 100%, chemical equivalent: 170
* 9: PMA (propylene glycol monomethyl ether acetate)
* 10: Silver powder (flakes, average particle size 4-5μm)

As shown in Tables 1 and 2, the adhesives of Examples 1 to 9 containing the components (A) to (C) showed high adhesive strength. Moreover, the viscosity did not increase even after mixing each component, and a one-part thermosetting composition excellent in storage stability could be obtained. Further, the adhesives of Examples 3 to 7 containing a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. were excellent in workability. On the other hand, instead of the component (A), the adhesive of Comparative Example 1 containing a blocked isocyanate blocked with only one type of blocking agent had low adhesive strength and poor workability. Although the adhesive of Comparative Example 2 containing an isocyanate not blocked with a blocking agent instead of the component (A) is excellent in adhesive strength, the viscosity increases when each component is mixed. As a liquid adhesive, it was inferior in storage stability. The adhesive of Comparative Example 3 containing no component (B) had low adhesive strength and was inferior in workability. In Comparative Example 4 using a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. instead of the component (C), the adhesive strength was low.

Claims (7)

(A) blocked isocyanate blocked with at least two types of blocking agents,
(B) a curing catalyst, and (C) a hydroxyl group-containing resin having a glass transition temperature (Tg) of 25 ° C. or lower,
A thermosetting composition comprising: 2. The thermosetting composition according to claim 1, wherein the blocking agent of blocked isocyanate blocked with (A) at least two types of blocking agents is a secondary amine blocking agent and an active methylene blocking agent. . The thermosetting composition according to claim 1 or 2, wherein the (B) curing catalyst is a salt of a basic compound and an organic acid. The thermosetting composition according to any one of claims 1 to 3, further comprising a hydroxyl group-containing resin having a glass transition temperature (Tg) exceeding 25 ° C. The thermosetting composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing resin (C) having a glass transition temperature (Tg) of 25 ° C or lower is a polyester polyol. The thermosetting composition according to any one of claims 1 to 5, which is used for an adhesive used in the production of an IC card. A laminated structure obtained by using the thermosetting composition according to any one of claims 1 to 6.