JP7014998B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition.

Epoxy resin compositions using a polythiol compound as a curing agent have good low-temperature curability and quick-curing properties, and are therefore used in various applications such as adhesives, encapsulants, and coating agents. Among the polythiol compounds, the ester structure-containing polythiol compound is often used because it is easy to synthesize and can be produced at low cost (Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 11-256013

However, since the ester structure of the ester structure-containing polythiol compound is susceptible to hydrolysis, there is room for improvement in moisture resistance even in the epoxy resin composition containing the ester structure-containing polythiol compound. Therefore, an object of the present invention is to provide an epoxy resin composition containing an ester structure-containing polythiol compound, which has excellent moisture resistance.

In order to solve the above problems, the present invention includes the following matters.
[1] (A) Epoxy resin,
A resin composition containing (B) an ester structure-containing polythiol compound and (C) a carbodiimide having a molecular weight of 150 to 13000.
[2] The resin composition according to the above [1], wherein the content of the carbodiimide in the resin composition is 0.01 to 50% by mass when the non-volatile component of the resin composition is 100% by mass. thing.
[3] The resin composition according to the above [1] or [2], further comprising (E) an inorganic filler.
[4] The resin composition according to the above [3], wherein the content of the inorganic filler is 1 to 70 parts by mass when the non-volatile component in the resin composition is 100 parts by mass.
[5] The resin composition according to the above [3] or [4], wherein the inorganic filler contains at least one selected from the group consisting of silica, calcium carbonate, talc and mica.
[6] The item according to any one of [1] to [5] above, wherein the equivalent ratio (epoxide group / thiol group) of the epoxy group and the thiol group in the resin composition is 0.50 to 10.0. Resin composition.
[7] The resin composition according to any one of [1] to [6] above, further comprising (D) a curing accelerator.
[8] The resin composition according to the above [7], wherein the curing accelerator is a latent curing accelerator.
[9] The latent curing accelerator is at least one selected from the group consisting of an epoxy adduct of an amine compound, a urea adduct of an amine compound, and a compound obtained by adding an isocyanato compound to a hydroxyl group of the epoxy adduct. The resin composition according to the above [8].
[10] The resin composition according to any one of [1] to [9] above, which is a one-component resin composition.
[11] An adhesive containing the resin composition according to any one of the above [1] to [10].
[12] The adhesive according to the above [11], which is used for bonding between components of a camera module.
[13] A sealing agent containing the resin composition according to any one of the above [1] to [10].
[14] A coating agent containing the resin composition according to any one of the above [1] to [10].
[15] A cured product obtained by thermally curing the resin composition according to any one of the above [1] to [10].
[16] An electronic component containing the cured product according to the above [15].

According to the present invention, there is provided an epoxy resin composition containing an ester structure-containing thiol, which is excellent in storage stability, low temperature curability, and moisture resistance.

The resin composition according to the embodiment of the present invention contains (A) an epoxy resin, (B) an ester structure-containing polythiol compound, and (C) a carbodiimide having a molecular weight of 150 to 13000.
According to this embodiment, by using a carbodiimide having a molecular weight of 150 to 13000, a resin composition having excellent moisture resistance can be obtained even when an inexpensive ester structure-containing polythiol compound is used as a curing agent. Obtainable. That is, it is possible to obtain a resin composition having excellent moisture resistance while using an ester structure-containing thiol.

The resin composition according to this embodiment is preferably a "one-component" resin composition. The "one-component" resin composition means a composition in which a curing agent and an epoxy resin are mixed in advance and has a property of being cured by applying heat.

Hereinafter, each component (A) to (C) will be described in detail.

[(A): Epoxy resin]
The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule. Preferably, as the epoxy resin, a resin having two or more epoxy groups per molecule on average is used.
As the epoxy resin, for example, a polyglycidyl ether obtained by reacting a polyhydric phenol such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin; p. -Glysidyl ether ester obtained by reacting hydroxycarboxylic acids such as hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polycarboxylic acids such as phthalic acid and terephthalic acid and epichlorohydrin. Polyglycidyl esters obtained by reaction; further, epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cyclic aliphatic epoxy resin, other urethane-modified epoxy resin; and the like are limited to these. It's not a thing.

Among these, the epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, and phenol aralkyl type from the viewpoint of maintaining high heat resistance and low moisture permeability. At least one selected from the group consisting of an epoxy resin, an aromatic glycidylamine type epoxy resin, and an epoxy resin having a dicyclopentadiene structure is preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and At least one selected from the group consisting of epoxy resins having a dicyclopentadiene structure is more preferable.

The epoxy resin may be liquid or solid, and both liquid resin and solid resin may be used. Here, "liquid" and "solid" are the states of the epoxy resin at 25 ° C. From the viewpoint of coatability, processability, and adhesiveness, it is preferable that at least 10% by mass or more of the entire epoxy resin used is liquid.

The epoxy equivalent of the epoxy resin is, for example, 50 to 1000 g / eq, preferably 100 to 500 g / eq, and more preferably 150 to 300 g / eq. Here, the epoxy equivalent is the mass of the epoxy resin per equivalent of the epoxy group, and can be measured according to JIS K7236 (2009).

Specific examples of the liquid epoxy resin include bisphenol A type epoxy resin ("jER828EL" and "jER827" manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resin ("jER807" manufactured by Mitsubishi Chemical Co., Ltd.), and phenol novolac type epoxy resin (Mitsubishi). Chemical's "jER152") Naphthalene type bifunctional epoxy resin (DIC's "HP-4032", "HP-4032D"), bisphenol A type epoxy resin / bisphenol F type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ZX-" 1059 ”), an epoxy resin having a hydrogenated structure (“YX-8000” manufactured by Mitsubishi Chemical Co., Ltd.), and an epoxy resin having a butadiene structure (“PB-3600” manufactured by Daicel Chemical Industry Co., Ltd.). Among them, "jER828EL", "jER827", "jER807" and "ZX-1059" manufactured by Mitsubishi Chemical Corporation, which have high heat resistance and low viscosity, are preferable, and "jER828EL" is more preferable. Specific examples of the solid epoxy resin include naphthalene-type tetrafunctional epoxy resin (“HP-4700” manufactured by DIC Corporation), dicyclopentadiene-type polyfunctional epoxy resin (“HP-7200” manufactured by DIC Corporation), and naphthol-type epoxy resin. ("ESN-475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), epoxy resin having a biphenyl structure ("NC-3000H", "NC-3000L" manufactured by Nippon Kayaku Co., Ltd., "YX-4000" manufactured by Mitsubishi Chemical Corporation), etc. Be done.

Suitable epoxy resins include bisphenol A type epoxy resin / bisphenol F type epoxy resin mixture (“ZX-1059” manufactured by Nippon Steel & Sumitomo Metal Corporation), phenol novolac type epoxy resin (“jER152” manufactured by Mitsubishi Chemical Co., Ltd.), and dicyclopentadiene. Examples thereof include a type polyfunctional epoxy resin (“HP-7200” manufactured by DIC).

The content of the epoxy resin as the component (A) in the resin composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 10% by mass, when the non-volatile component of the resin composition is 100% by mass. 20% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, particularly preferably 75% by mass or less, most preferably 70% by mass. % Or less.

[(B): Ester structure-containing polythiol compound]
The ester structure-containing polythiol compound is not particularly limited as long as it is a compound containing an ester structure and two or more thiol groups in the molecule.
The ester structure-containing polythiol compound is preferably a trifunctional to hexafunctional compound (a compound in which the number of thiol groups in one molecule is 3 to 6).

The ester structure-containing polythiol compound is preferably contained in an amount such that the equivalent ratio of the epoxy group to the thiol group (epoxide group / thiol group) in the resin composition is 0.50 to 10.0. More preferably, the equivalent ratio (epoxide group / thiol group) is 0.75 to 5.0, more preferably 0.80 to 2.0.
The equivalent of the thiol group is the mass of the ester structure-containing polythiol compound per one equivalent of the thiol group.

When the content of the epoxy resin as the component (A) is 100 parts by mass, the content of the ester structure-containing polythiol compound as the component (B) is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass. , More preferably 50 to 100 parts by mass.

Examples of the ester structure-containing polythiol compound include a partial ester of a polyol and a mercapto organic acid, and a complete ester. Here, the partial ester is an ester of a polyol and a carboxylic acid in which a part of the hydroxy groups of the polyol forms an ester bond, and the complete ester is an ester in which all the hydroxy groups of the polyol have an ester bond. It means what is being formed. Examples of the polyol include ethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (eg, 3-mercaptopropionic acid), and mercaptobutyric acid (eg, 3-mercaptobutyric acid, 4-mercaptobutyric acid); hydroxy. Esters containing thiol groups and carboxy groups obtained by esterification reaction of acid with mercapto organic acid; mercapto aliphatic dicarboxylic acid such as mercaptosuccinic acid, dimercaptosuccinic acid (eg 2,3-dimercaptosuccinic acid) Examples include mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (eg 4-mercaptobenzoic acid); and the like. The carbon number of the mercaptoaliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among the mercapto organic acids, mercapto aliphatic monocarboxylic acids having 2 to 8 carbon atoms are preferable, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferable, and 3-mercaptopropion. Acids are more preferred.

Specific examples of the partial ester of the polyol and the mercapto organic acid include trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane bis (3-mercaptobutyrate), and tri. Methylolpropane bis (4-mercaptobutyrate), pentaerythritol tris (mercaptoacetate), pentaerythritol tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), pentaerythritol tris (4-mercaptobutyrate) Lat), dipentaerythritol tetrakis (mercaptoacetate), dipentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol tetrakis (4-mercaptobutyrate), etc. Can be mentioned.

Specific examples of the complete ester of the polyol and the mercapto organic acid include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), and ethylene glycol bis (3-mercapentaerythritoltetrakis (3-mercapto). Propionate) Tobutyrate), Ethylene Glycol Bis (4-mercaptobutyrate), Trimethylol Propane Tris (Mercaptoacetate), Trimethylol Propane Tris (3-Mercaptopropionate), Trimethylol Propane Tris (3-Mercapto Butyrate) ), Trimethylol Propane Tris (4-Mercaptobutyrate), Pentaerythritol Tetrakiss (Mercaptoacetate), Pentaerythritol Tetrakiss (3-Mercaptopropionate), Pentaerythritol Tetrakiss (3-Mercaptobutyrate), Pentaerythritol Tetrakiss (4) -Mercaptobutyrate), Dipentaerythritol Hexakis (Mercaptoacetate), Dipentaerythritol Hexakis (3-Mercaptopropionate), Dipentaerythritol Hexakis (3-Mercaptobutyrate), Dipentaerythritol Hexakis (4-Mercaptobutyrate) ) Etc. can be mentioned. Preferred are pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate) and trimethylolpropane tris (3-mercaptopropionate). ) Is at least one selected from the group.

Examples of the ester structure-containing polythiol compound include tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate and 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine. -2,4,6 (1H, 3H, 5H) -Trione and the like can also be used.

[(C) Carbodiimide]
The carbodiimide (C component) is not particularly limited as long as it is a compound having a molecular weight of 150 to 13000 and having an "-N = C = N-" structure in the molecule.
The molecular weight of carbodiimide is preferably 170 or more, more preferably 185 or more, still more preferably 200 or more. Within such a range, good storage stability can be obtained in addition to the improvement of moisture resistance.
The molecular weight of carbodiimide is preferably 8000 or less, preferably 6000 or less, more preferably 5000 or less, and further preferably 4000 or less. Within such a range, better moisture resistance can be obtained.
In the present specification, when carbodiimide is a polymer, the molecular weight of carbodiimide means "mass average molecular weight".
Here, the mass average molecular weight of carbodiimide is a polystyrene-equivalent mass average molecular weight measured by a gel permeation chromatography (GPC) method, and specifically, the polystyrene-equivalent mass average molecular weight of carbodiimide is used as a measuring device. Using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as a column, and chloroform or the like as a mobile phase, the column temperature is 40 ° C. It can be measured by and calculated using the calibration curve of standard polystyrene.

As the carbodiimide, any of monocarbodiimide, polycarbodiimide and cyclic carbodiimide can be used, but polycarbodiimide is more preferable. The mass average molecular weight of carbodiimide is a polystyrene-equivalent mass average molecular weight measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent mass average molecular weight of carbodiimide is used as a measuring device. Measured at a column temperature of 40 ° C. using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and chloroform or the like as a mobile phase. However, it can be calculated using the calibration curve of standard polystyrene.

As the monocarbodiimide, for example, a compound represented by the following formula (I) can be used.
(Equation I) _RA -N = _C = N-RB
In the formula, _RA and RB independently represent a _{C 1} to C ₁₈ alkyl group, a C ₅ to C ₁₈ cycloalkyl group, or an aryl group. The aryl group may be substituted with at least one substituent selected from the group consisting of C ₁ to C ₁₈ alkyl groups, nitro groups, amino groups and hydroxy groups.
Specific examples of the monocarbodiimide include N, N'-di-o-toluyl carbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N, N'-bis ( 2,6-diisopropylphenyl) carbodiimide, N, N'-bis (propylphenyl) carbodiimide, N, N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,2 -Di-tert-butylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'- Examples thereof include di-p-hydroxyphenylcarbodiimide, N, N'-dicyclohexylcarbodiimide, and N, N'-di-p-toluylcarbodiimide. Of these, N, N'-dicyclohexylcarbodiimide, N, N'-bis (propylphenyl) carbodiimide and bis (dipropylphenyl) carbodiimide are preferable.

As the polycarbodiimide, for example, the compound described in Japanese Patent No. 5693799 can be used. Specifically, the compound described in the document is a carbodiimide compound represented by the following formula.
(Equation): R ^2- (-N = C = N-R ^1- ) _m -R ³
In the above formula, in the formula, R ¹ represents a divalent aromatic group and / or an aliphatic group, which is the same or different.

When R ¹ is an aromatic group, R ¹ may be substituted with an aliphatic substituent and / or an alicyclic substituent and / or an aromatic substituent having at least one carbon atom. Here, these substituents may have a heteroatom, and these substituents may be substituted at at least one ortho position of the aromatic group to which the carbodiimide group is attached.

R ² is C ₁ to C ₁₈ alkyl, C ₅ to C ₁₈ cycloalkyl, aryl, C ₇ to C ₁₈ aralkyl, -R ⁴ -NH-COS-R ⁵ , -R ⁴ COOR ⁵ , -R ⁴ -OR. ⁵ , -R ⁴ -N (R ⁵ ) ₂ , -R ⁴ -SR ⁵ , -R ⁴ -OH, R ⁴ -NH ₂ , -R ⁴ -NHR ⁵ , -R ⁴ -Epoxy, -R ⁴ -NCO , -R ⁴ -NHCONHR ⁵ , -R ⁴ -NHCONR ⁵ R ⁶ or -R ⁴ -NHCOOR ⁷ .

R ³ is -N = C = N-aryl, -N = C = N-alkyl, -N = C = N-cycloalkyl, -N = C = N-aralkyl, -NCO, -NHCONHR ⁵ , -NHCONHR. ⁵ R ⁶ , -NHCOOR ⁷ , -NHCOS-R ⁵ , -COOR ⁵ , -OR ⁵ , Epoxy, -N (R ⁵ ) ₂ , -SR ⁵ , -OH, -NH ₂ , -NHR ⁵ .

R ⁴ represents a divalent aromatic group and / or an aliphatic group.

R ⁵ and R ⁶ are the same or different, C ₁ to C ₂₀ alkyl, C ₃ to C ₂₀ cycloalkyl, C ₇ to C ₁₈ aralkyl, oligo / polyethylene glycols and / or oligo / polypropylene glycol. Kind.

R ⁷ has one of the above definitions of R ⁵ , or is a polyester or polyamide group.

m is an integer of 2 or more.

Examples of polycarbodiimide include poly (4,4'-dicyclohexylmethanecarbodiimide), poly (N, N'-di-2,6-diisopropylphenylcarbodiimide), and poly (1,3,5-triisopropylphenylene-2,4). -Carbodiimide), etc. Of these, poly (1,3,5-triisopropylphenylene-2,4-carbodiimide) is preferable.
As the polycarbodiimide, a commercially available product may be used, for example, an aliphatic polycarbodiimide (“Elasto Stub H-01” manufactured by Nisshinbo Chemical Co., Ltd.), a carbodiimide-modified isocyanate (“Carbodilite V-05” manufactured by Nisshinbo Chemical Co., Ltd.), and the like. Can be mentioned. Of these, carbodiimide-modified isocyanate (“Carbodilite V-05” manufactured by Nisshinbo Chemical Co., Ltd.) is preferable.
Examples of the cyclic carbodiimide include the cyclic carbodiimide described in Japanese Patent No. 5856924.

The content of (C) carbodiimide in the resin composition is preferably 0.01 to 50% by mass, preferably 0.1 to 35% by mass, when the non-volatile component of the resin composition is 100% by mass. % Is more preferable.

[(D): Curing accelerator]
The resin composition according to the present embodiment preferably contains a curing accelerator.

As the curing accelerator, a latent curing accelerator is preferably used. The latent curing accelerator is an important component particularly in the case of making a one-component resin composition, and does not contribute to the curing of the epoxy resin at room temperature (20 ° C ± 15 ° C (JISZ8703)), and the epoxy resin during heating. It is an additive having a function of accelerating the curing of the resin.

As the latent curing accelerator, either a liquid latent curing accelerator or a solid dispersion type latent curing accelerator can be used, but a solid dispersion type latent curing accelerator is more preferably used.

The liquid latent curing accelerator is a liquid that is soluble in epoxy at room temperature and is not active at room temperature, but is a compound that functions as a curing accelerator for epoxy resin when heated.
Examples of the liquid latent curing accelerator include, but are not limited to, ionic liquids.
Examples of the cations constituting the ionic liquid include ammonium cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazonium ion, guanidinium ion and pyridinium ion; phosphonium cation such as tetraalkylphosphonium cation; triethylsulfonium. Examples thereof include sulfonium cations such as ions.
The anions constituting the ionic liquid include halide-based anions such as fluoride ion, chloride ion, bromide ion, and iodide ion: alkyl sulfate-based anions such as methanesulfon ion: trifluoromethanesulfonic acid ion, hexafluorophosphone. Fluoro-containing compound anions such as acid ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion: phenol ion, 2-methoxyphenol ion, Phenolic anions such as 2,6-di-tert-butylphenol ion: Acidic amino acid ions such as aspartate ion and glutamate ion: Neutral amino acid ions such as glycine ion, alanine ion and phenylalanine ion: N-benzoylalanine ion, N -N-acylamino acid ions such as acetylphenylalanine ion, N-acetylglycine ion, N-acetylglycine ion: carboxylic acids such as formate ion, lactate ion, tartrate ion, horse uric acid ion, N-methyl field uric acid, benzoate ion and the like. A system anion can be mentioned.

The solid-dispersed latent curing accelerator is a compound that is insoluble in an epoxy resin at room temperature, is solubilized by heating, and functions as a curing accelerator for the epoxy resin.

Examples of the solid-dispersed latent curing accelerator include, but are not limited to, an imidazole compound that is solid at room temperature and a solid-dispersed amine adduct-based latent curing accelerator.

Examples of the imidazole compound solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and the like. 2-Phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl-S-triazine, 2,4-diamino-6- (2') -Methylimidazolyl- (1)')-Ethyl-S-triazine isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole-trimethylate, 1-cyanoethyl-2-phenylimidazole-trimeritate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N'-(2-methylimidazolyl- (1) )-Ethyl) -aziboyldiamide and the like, but are not limited thereto.

Preferable examples of the solid-dispersed amine adduct-based latent curing accelerator include an epoxy adduct of an amine compound, a urea adduct of an amine compound, and a compound obtained by adding an isocyanato compound to a hydroxyl group of the epoxy adduct. At least one selected may be mentioned.

Examples of the epoxy compound used as one of the raw materials for producing the epoxy adduct of the amine compound include polyhydric phenols such as bisphenol A, bisphenol F, catechol and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol and epichloro. Polyglycidyl ether obtained by reacting with hydrin; glycidyl ether ester obtained by reacting hydroxycarboxylic acid such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; phthalic acid, terephthalic acid. Polyglycidyl ester obtained by reacting a polycarboxylic acid such as an acid with epichlorohydrin; glycidylamine obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol, etc. with epichlorohydrin. Compounds; further include polyfunctional epoxy compounds such as epoxidized phenol novolac resin, epoxidized cresol novolak resin, and epoxidized polyolefin, and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate; and the like. Is not limited to these.

The amine compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator has at least one active hydrogen in the molecule capable of an addition reaction with an epoxy group, and has a primary amino group and a secondary amino group. And it is sufficient that it has at least one functional group selected from the tertiary amino groups in the molecule. Examples of such amine compounds include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; Aromatic amine compounds such as 4,4'-diaminodiphenylmethane, 2-methylaniline; nitrogen such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazolin, piperidine, piperazin and the like. Examples include, but are not limited to, heterocyclic compounds containing atoms;

Further, among these, a compound having a tertiary amino group in the molecule is a raw material for giving a latent curing accelerator having an excellent curing promoting ability, and examples of such a compound include, for example, dimethylaminopropyl. Amine compounds such as amines, diethylaminopropylamines, di-n-propylaminopropylamines, dibutylaminopropylamines, dimethylaminoethylamines, diethylaminoethylamines, N-methylpiperazines, 2-methylimidazoles, 2-ethylimidazoles, 2- Primary or secondary amines with a tertiary amino group in the molecule, such as imidazole compounds such as ethyl-4-methylimidazole, 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylamino Ethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1-( 2-Hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl)- 2-Ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylamino) Methyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzoimidazole, 2-mercaptobenzoimidazole, 2 -Mercaptbenzothiazole, 4-mercaptopyridine, N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N, N-dimethylglycine hydrazide, N, N-dimethylpropion Examples thereof include alcohols, phenols, thiols, carboxylic acids and hydrazides having a tertiary amino group in the molecule, such as acid hydrazide, nicotinic acid hydrazide, isonicotinic acid hydrazide and the like.

When the above-mentioned epoxy compound and amine compound are subjected to an addition reaction to produce a latent curing accelerator, an active hydrogen compound having two or more active hydrogens in the molecule can be further added. Examples of such active hydrogen compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolak resin, polyhydric alcohols such as trimethylolpropane, and adipic acid. , Polyvalent carboxylic acids such as phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranylic acid, lactic acid and the like. Not limited.

Examples of the isocyanate compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; hexamethylene diisocyanate and tolui. Polyfunctional isocyanates such as range isocyanate, 1,5-naphthalenediocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylenedi isocyanate, 1,3,6-hexamethylenetriisocyanate, bicycloheptanetriisocyanate Compounds; Further, terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds; and the like can also be used. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol. Examples thereof include, but are not limited to, additional compounds having.

Further, examples of the urea compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator include, but are not limited to, urea and thiourea.

The solid dispersion type latent curing accelerator may be, for example, appropriately mixed with the above-mentioned production raw materials, reacted at a temperature of room temperature to 200 ° C., cooled and solidified, and then pulverized, or methyl ethyl ketone, dioxane, tetrahydrofuran, etc. It can be easily obtained by reacting in the same solvent as above, removing the solvent, and then pulverizing the solid content.

Typical examples commercially available as a solid-dispersed latent curing accelerator include "PN-23" (manufactured by Ajinomoto Fine-Techno) and "Amicure" as an amine-epoxy adduct system (amine adduct system). "PN-H" (manufactured by Ajinomoto Fine Techno Co., Ltd.), "Hardner X-3661S" (manufactured by ACR), "Hardner X-3670S" (manufactured by ACR), etc. Examples of the urea type adduct system include "FXR-1081" (manufactured by T & K TOKA), "Fujicure FXR-1000" (manufactured by T & K TOKA), and "Fujicure FXR-1030" (manufactured by T & K TOKA). Further, "Novacure HX-3721" (manufactured by Asahi Kasei Co., Ltd.), "HX-3722" (manufactured by Asahi Kasei Co., Ltd.), and "Novacure HX-3742" (manufactured by Asahi Kasei Co., Ltd.), which are imidazole-modified microcapsules, can also be mentioned.

When the content of the epoxy resin as the component (A) is 100 parts by mass, the content of the curing accelerator as the component (D) is preferably 0.1 to 100 parts by mass, and 0.5 to 50 parts by mass. It is more preferably parts by mass, and even more preferably 1.0 to 30 parts by mass.

[(E): Inorganic filler]
The resin composition according to the present embodiment preferably contains an inorganic filler. Moisture resistance can be further improved by using an inorganic filler.

The content of the inorganic filler (E) component is, for example, 1 to 70 parts by mass, more preferably 5 to 60 parts by mass, and further preferably 10 to 50 parts when the non-volatile content in the resin composition is 100 parts by mass. It is a mass part.

The average particle size of the inorganic filler is, for example, 0.1 to 100 μm, preferably 0.5 to 40 μm, and more preferably 1.0 to 30 μm.
The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis by a laser diffraction type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, LA-500 manufactured by HORIBA, Ltd. or the like can be used.

The inorganic filler is not particularly limited, but for example, silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, etc. At least one selected from the group consisting of aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate can be mentioned.
The inorganic filler preferably contains at least one selected from the group consisting of silica, calcium carbonate, talc, and mica, and more preferably contains silica.

[(F): Others]
Further, the resin composition according to the present embodiment further has a borate ester compound, a titanium acid ester compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid, and an acid anhydride in order to realize excellent storage stability. It is preferable to contain one or more selected from the compound and the mercapto organic acid.

Examples of the borate compound include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, tri-n-butylborate, tripentylborate, triallylborate, trihexylborate, and tricyclohexylborate. Trioctylborate, Trinonylborate, Tridecylbolate, Tridodecylbolate, Trihexadecylbolate, Trioctadecylbolate, Tris (2-ethylhexyloxy) borate, Bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borate, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m-trill Examples thereof include borate and triethanolamine borate.

Examples of the titanium acid ester compound include tetraethyl titanate, tetrapropyl titanate, tetraisoproprutitanate, tetrabutyl titanate, and tetraoctyl titanate.

Examples of the aluminate compound include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate and 2,6-dimethylphenyl isocyanate. , 2,4-Toluene diisocyanate, toluylene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalenedi isocyanate, diphenylmethane-4,4'-diisocyanate, trizine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylenedi isocyanate, bicyclo Examples thereof include heptane triisocyanate.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid and capric acid, unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid and crotonic acid, and monochloro acid. Halogenized fatty acids such as acetic acid and dichloroacetic acid, monobasic oxy acids such as glycolic acid and lactic acid, aliphatic aldehyde acids such as glyoxal acid and grape acid, and ketone acids, oxalic acids, malonic acids, succinic acids and maleic acids. Examples thereof include aromatic monobasic acids such as aliphatic polybasic acid, benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid and mandelic acid, and aromatic polybasic acids such as phthalic acid and trimesic acid. ..

Examples of the acid anhydride include succinic anhydride, dodecynyls succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydroanhydride, methyltetrahydrophthalic anhydride and the like. Examples thereof include aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyrrolimellitic anhydride such as basic acid anhydride.

The mercapto organic acid is obtained by, for example, an esterification reaction between a mercapto aliphatic monocarboxylic acid such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, dimercaptosuccinic acid, a hydroxy organic acid and a mercapto organic acid. Examples thereof include mercapto aliphatic monocarboxylic acids such as mercapto aliphatic monocarboxylic acids and mercapto aromatic monocarboxylic acids such as mercapto benzoic acid.

Of these, as the component (F), a borate ester compound is preferable from the viewpoint of high versatility and safety and improvement of storage stability, and triethylborate, tri-n-propylborate, triisopropylborate, and tri. -N-Butyl borate is more preferred, and triethyl borate is even more preferred. The content of the component (F) is not particularly limited as long as the storage stability of the resin is enhanced, but when the content of the epoxy resin of the component (A) is 100 parts by mass, the content of the component (F) is It is preferably 0.001 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.1 to 10 parts by mass.

The resin composition according to the present embodiment described above can be carried out according to a conventionally known method. That is, for example, the resin composition according to the present embodiment can be prepared by mixing each component with various mixers.

When the resin composition according to the present embodiment is a one-component resin composition, a conventionally known method can be used as the curing method thereof. For example, it can be cured by heating the resin composition. The heating is carried out, for example, at a temperature of 60 to 150 ° C., preferably 70 to 120 ° C., more preferably 80 to 100 ° C., for example, 1 to 120 minutes, preferably 3 to 60 minutes, more preferably 5 to 40. It is appropriate to do it for a minute.

The resin composition according to the present embodiment may contain, if necessary, a filler, a diluent, a solvent, a pigment, a flexibility-imparting agent, a coupling agent, an antioxidant, and thixotropy, which are commonly used in the field of the present invention. Various additives such as sex-imparting agents and dispersants can be added.

The resin composition according to this embodiment can be used, for example, in a functional product. Examples of the functional product include an adhesive, a casting agent, a sealing agent, a sealing agent, a fiber-reinforced resin, a coating agent, a paint and the like.
Preferably, the resin composition according to the present embodiment is preferably used as an adhesive used in the manufacture of electronic components such as CCMs, HDDs, semiconductor elements, and integrated circuits, and more preferably, a camera module. It is used as an adhesive for bonding between components. Examples of such components include metal members such as copper and nickel; plastic members such as LCP (liquid crystal polymer), polyamide and polycarbonate. The resin composition according to the present embodiment is suitable as an adhesive for adhering the same or different kinds of members selected from these metal members and plastic members.

According to the resin composition according to the present embodiment, for example, after being left in an environment of 121 ° C. and 100% RH for 24 hours, a shear adhesion strength retention rate of 30% or more can be obtained.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" in the following description means "part by mass".

1. 1. Raw materials [(A) component]
(A1) ZX-1059: Bisphenol A type epoxy resin / bisphenol F type epoxy resin mixture manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy equivalent (EPW) 165 g / eq
(A2) jER152: Phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation Epoxy equivalent (EPW) 177 g / eq
(A3) HP-7200: Dicyclopentadiene type epoxy resin manufactured by DIC Epoxy equivalent (EPW) 258 g / eq

[(B) component]
(B1) PE1: "Karensu MT" manufactured by Showa Denko Corporation Pentaerythritol tetrakis (3-mercaptobutylate), thiol equivalent 136 g / eq
(B2) PEMP: Pentaerythritol tetrakis (3-mercaptopropionate) manufactured by SC Organic Chemistry Co., Ltd., thiol equivalent 122 g / eq
(B3) DPMP: Dipentaerythritol hexakis (3-mercaptopropionate), thiol equivalent 131 g / eq
(B4) TMTP: Trimethylolpropanetris (3-mercaptopropionate), thiol equivalent 140 g / eq

[(C) component]
(C1) Stavaxol I powder: N, N'-bis (2,6-diisopropylphenyl) carbodiimide manufactured by LANXESS, molecular weight 360
(C2) Stavaxol P: Poly (1,3,5-triisopropylphenylene-2,4-carbodiimide) manufactured by LANXESS, mass average molecular weight 3000-4000
(C3) Carbodilite V-05: Carbodiimide-modified isocyanate manufactured by Nisshinbo Chemical Co., Ltd., mass average molecular weight 800
(C4) N, N'-dicyclohexylcarbodiimide: manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 206
(C5) Diisopropylcarbodiimide: manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 126
(C6) Stavaxol P100: Aromatic polycarbodiimide manufactured by LANXESS, mass average molecular weight of 15,000 or more

[(D) component]
(D1) PN-23: Ajinomoto Fine-Techno Co., Ltd. imidazole group-containing modified polyamine (solid)
(D2) FXR-1081: Urea bond-containing modified polyamine solid type manufactured by T & K TOKA (D3) HX-3722: Imidazole-modified microcapsule manufactured by Asahi Kasei Corporation

[(E) Inorganic filler]
(E1) SO-C5: Silica manufactured by Admatex Co., Ltd. Particle size 1.3 to 1.7 μm
(E2) Shiraishi B: Calcium carbonate average particle size 3.6 μm manufactured by Shiraishi Calcium Co., Ltd.
(E3) Talc MS: Manufactured by Japan Talc Talc average particle size 14.0 μm
(E4) Mica C-1000: Mica average particle size 26.0 μm manufactured by Imerys Mica Kings Mountain.

[(F) Others]
(F1) TEB: Triethyl borate manufactured by Junsei Chemical Co., Ltd.

2. 2. Evaluation test (1) Storage stability The resin composition to be measured was stored in a closed plastic container at 25 ° C. for 7 days. Before and after storage, the viscosity of the resin composition was measured at 25 ° C. and 20 rpm with an E-type viscometer RE-80U (Toki Sangyo Co., Ltd., rotor: 3 ° x R9.7), and the viscosity increase rate from the initial viscosity. Was calculated by viscosity / initial viscosity after 7 days.
<Evaluation criteria>
◎: Less than 2.0 times 〇: 2.0 times or more, less than 3.0 times ×: 3.0 times or more

(2) Low-temperature curability According to JIS C6521, the time during which the resin composition to be measured did not draw threads was measured at 90 ° C. using a hot plate type gelling tester GT-D (manufactured by Nissin Kagaku Co., Ltd.). Specifically, about 0.5 g of the composition was placed on a hot plate gelling tester preheated to 90 ° C., the stopwatch was started, and a spatula with a tip width of 5 mm was used to perform osculating circle motion. Repeatedly, the time until gelation was measured.
<Evaluation criteria>
◎: Less than 10 minutes 〇: 10 minutes or more, less than 30 minutes ×: 30 minutes or more

(3) Shear Adhesion Test According to JIS K-6850, the resin composition to be measured was cured in a heat circulation oven at 90 ° C. for 30 minutes to prepare a test piece adhered by the resin composition. As the test piece, a mild steel plate (SPCC, manufactured by Daiyu Kikai Co., Ltd.) was degreased with acetone and polished with an endless belt # 120. The shear adhesive strength of the obtained test piece was measured using a universal testing machine (AC-50KN-CM, manufactured by TSE) (measurement environment: temperature 25 ° C./humidity 60%, tensile speed; 5 mm). / Min).

(4) Moisture resistance test A test piece is prepared by the same procedure as in (3), and the test piece is left in an advanced accelerated life test device (manufactured by ESPEC) set under the conditions of 121 ° C. and 100% RH for 24 hours. After the moisture resistance test, the shear bond strength of the obtained test piece was measured with a universal testing machine.
Furthermore, in order to evaluate the effect of high temperature and high humidity environment on the adhesive strength, the adhesive strength maintenance rate was calculated. The adhesive strength retention rate was calculated as follows from the values of the initial shear adhesive strength and the shear adhesive strength after the moisture resistance test.
[Adhesive strength maintenance rate (%)] = [Shear adhesive strength after moisture resistance test] / [Initial shear adhesive strength] x 100
<Evaluation criteria>
◎: 30% or more 〇: 15% or more, less than 30% ×: less than 15%

3. 3. Examples and Comparative Examples The resin compositions according to Examples 1 to 22 and Comparative Examples 1 to 5 were prepared by mixing each component with the formulations shown in the upper columns of Tables 1 to 4.

In Examples 1 to 22, the component (A), the component (C), and the component (E) are mixed by a three-roll mill, the components (D) and (F) are added thereto, and further by a mixer. The mixture was mixed, the component (B) was added thereto, and the mixture was sufficiently dispersed by a mixer, and then statically defoamed to prepare the mixture. The preparation work was performed at 25 ° C., and the total mixing time was 30 minutes.

Comparative Examples 1 to 5 were similarly adjusted based on the formulations shown in Tables 1 to 4.

The results of subjecting the resin compositions of Examples 1 to 22 and Comparative Examples 1 to 5 to the above-mentioned evaluation test are shown in Tables 1 to 4.

From Tables 1 to 4, as shown in the results of Examples 1 to 22, it can be seen that the resin composition of the present invention has excellent low temperature curability, good storage stability, and further excellent moisture resistance. .. On the other hand, it can be seen that the resin compositions of Comparative Examples 1 to 5 do not have the high level of performance as the resin compositions of the present invention.
Further, when Comparative Example 1 and Comparative Example 2 are compared with Comparative Example 5, Comparative Example 1 and Comparative Example 2 are superior in low temperature curability, but inferior in moisture resistance (adhesive strength retention rate). That is, when (B) an ester structure-containing polythiol compound is used, excellent low-temperature curability can be obtained, but moisture resistance deteriorates.
On the other hand, when Examples 1 to 22 are compared with Comparative Example 1 and Comparative Example 2, the moisture resistance is improved. That is, it can be understood that the moisture resistance is improved by adding (C) carbodiimide.
Further, when Comparative Examples 3 and 4 are compared with Examples 1 to 22, it is understood that even when carbodiimide is added, the storage stability is improved by setting the molecular weight in the range of 150 to 10000. can.
Among Examples 1 to 22, Examples 17 and 22 had particularly good results from the viewpoint of storage stability, low temperature curability and moisture resistance.

Claims (16)

(A) Epoxy resin,
(B) A resin composition containing an ester structure-containing polythiol compound and (C) a carbodiimide having a molecular weight of 150 to 13000 (excluding conductive materials having solder) . The resin composition according to claim 1, wherein the content of the carbodiimide in the resin composition is 0.01 to 50% by mass when the non-volatile component of the resin composition is 100% by mass. The resin composition according to claim 1 or 2, further comprising (E) an inorganic filler. The resin composition according to claim 3, wherein the content of the inorganic filler is 1 to 70 parts by mass when the non-volatile component in the resin composition is 100 parts by mass. The resin composition according to claim 3 or 4, wherein the inorganic filler contains at least one selected from the group consisting of silica, calcium carbonate, talc and mica. The resin composition according to any one of claims 1 to 5, wherein the equivalent ratio of the epoxy group to the thiol group (epoxide group / thiol group) in the resin composition is 0.50 to 10.0. The resin composition according to any one of claims 1 to 6, further comprising (D) a curing accelerator. The resin composition according to claim 7, wherein the curing accelerator is a latent curing accelerator. The latent curing accelerator comprises at least one selected from the group consisting of an epoxy adduct of an amine compound, a urea adduct of an amine compound, and a compound obtained by adding an isocyanato compound to a hydroxyl group of the epoxy adduct. Item 8. The resin composition according to Item 8. The resin composition according to any one of claims 1 to 9, which is a one-component resin composition. An adhesive containing the resin composition according to any one of claims 1 to 10. 11. The adhesive according to claim 11, which is used for bonding between components of a camera module. A encapsulant containing the resin composition according to any one of claims 1 to 10. A coating agent containing the resin composition according to any one of claims 1 to 10. A cured product obtained by thermally curing the resin composition according to any one of claims 1 to 10. An electronic component comprising the cured product according to claim 15.