TW201936775A - Resin composition which is excellent in moisture resistance, preservation stability and low-temperature curability - Google Patents

Abstract

Disclosed is an epoxy resin composition which is excellent in moisture resistance, wherein the epoxy resin composition contains thiol having an ester structure. A resin composition comprises an epoxy resin, an ester structure-containing polythiol compound, and a carbodiimide having a molecular weight of 150 to 13,000.

Description

Resin composition

The present invention relates to a resin composition.

The epoxy resin composition using a polythiol compound as a curing agent has good low-temperature curing properties and fast curing properties, and is therefore used for various applications such as adhesives, sealants, and coating agents. Among the polythiol compounds, polythiol compounds having an ester-containing structure can be easily synthesized and produced inexpensively, and therefore they are often used (Patent Document 1).
[Prior technical literature]
[Patent Literature]

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

[Problems to be Solved by the Invention]

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

[Means to solve the problem]

In order to solve the above problems, the present invention includes the following matters.
[1] A resin composition comprising:
(A) epoxy resin,
(B) a polythiol compound containing an ester structure, and
(C) A carbodiimide having a molecular weight of 150 to 13,000.
[2] The resin composition according to the above [1], wherein when the non-volatile content of the resin composition is set to 100% by mass, the content of the carbodiimide in the resin composition is 0.01 to 50% by mass .
[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 when the non-volatile component in the resin composition is 100 parts by mass, the content of the inorganic filler is 1 to 70 parts by mass.
[5] The resin composition according to the above [3] or [4], wherein the inorganic filler includes at least one selected from the group consisting of silicon dioxide, calcium carbonate, talc, and mica.
[6] The resin composition according to any one of the above [1] to [5], wherein the equivalent ratio (epoxy group / mercapto group) of the epoxy group to the mercapto group in the resin composition is 0.50 to 10.0.
[7] The resin composition according to any one of [1] to [6], further including (D) a hardening accelerator.
[8] The resin composition according to the aforementioned [7], wherein the hardening accelerator is a latent hardening accelerator.
[9] The resin composition as described in the above [8], wherein the aforementioned latent hardening accelerator comprises a hydroxyl group and an isocyanate selected from the group consisting of an epoxy adduct of an amine compound, a urea adduct of an amine compound, and an epoxy adduct. At least one group of compounds in which a cyano compound is subjected to an addition reaction.
[10] The resin composition according to any one of the above [1] to [9], which is a single-liquid type resin composition.
[11] An adhesive comprising the resin composition according to any one of the above [1] to [10].
[12] The adhesive as described in [11] above, which is used for adhering between the constituent members of the photographic module.
[13] A sealant comprising the resin composition according to any one of the above [1] to [10].
[14] A coating agent comprising the resin composition according to any one of the aforementioned [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 comprising a hardened body as described in [15] above.

[Effect of the invention]

The present invention provides an epoxy resin composition excellent in storage stability, low-temperature hardening property, and moisture resistance, which contains an thiol having an ester-containing structure.

The resin composition according to the embodiment of the present invention contains (A) an epoxy resin, (B) a polythiol compound containing an ester structure, and (C) a carbodiimide having a molecular weight of 150 to 13,000.
According to this embodiment, by using a carbodiimide having a molecular weight of 150 to 13,000, a resin composition having excellent moisture resistance can be obtained even when a polythiol compound having an inexpensive ester-containing structure is used as a hardener. That is, even if a mercaptan having an ester-containing structure is used, a resin composition having excellent moisture resistance can be obtained.

The resin composition of this embodiment is preferably a "single-liquid" resin composition. The "single-liquid type" resin composition refers to a composition in which a curing agent and an epoxy resin have been mixed in advance, and has a property of being cured by heating.

The components (A) to (C) will be described in detail below.

[(A): Epoxy resin]
The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule. As the epoxy resin, a resin having an average of two or more epoxy groups per molecule is preferably used.
Examples of the epoxy resin include polyphenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerol or polyethylene glycol, and a table. Polyepoxypropyl ether obtained by reaction of chlorohydrin; Epoxypropyl ether ester obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; Polyepoxypropyl ester obtained by reacting phthalic acid, terephthalic acid-like polycarboxylic acid with epichlorohydrin; and epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, cyclic Type aliphatic epoxy resins, other urethane-modified epoxy resins, and the like, but are not limited thereto.

Among these, as the epoxy resin, from the viewpoint of maintaining high heat resistance and low moisture permeability, etc., it is selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, At least one of a group consisting of a biphenyl aralkyl type epoxy resin, a phenol aralkyl type epoxy resin, an aromatic epoxypropylamine type epoxy resin, and an epoxy resin having a dicyclopentadiene structure. Preferably, at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and epoxy resin having a dicyclopentadiene structure is preferred. .

The epoxy resin may be used in a liquid state or a solid state, and both of a liquid resin and a solid resin may be used. Here, "liquid state" and "solid state" refer to the state 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 refers to the mass of the epoxy resin per one equivalent of the epoxy group, and it can be measured in accordance with JIS K7236 (2009).

Specific examples of the liquid epoxy resin include bisphenol A type epoxy resin ("jER828EL", "jER827", manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy resin ("jER807" manufactured by Mitsubishi Chemical Corporation). Phenolic novolac epoxy resin ("jER152" manufactured by Mitsubishi Chemical Corporation) naphthalene bifunctional epoxy resin ("HP-4032", "HP-4032D" manufactured by DIC), bisphenol A epoxy resin / bisphenol Type F epoxy resin ("ZX-1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), epoxy resin with hydrogenated structure ("YX-8000" manufactured by Mitsubishi Chemical Corporation), and epoxy resin with butadiene structure ( "PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.). Among them, "jER828EL", "jER827", "jER807", and "ZX-1059" made by Mitsubishi Chemical Corporation, which has high heat resistance and low viscosity, are more 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), and dicyclopentadiene-type polyfunctional epoxy resin ("HP manufactured by DIC Corporation"). -7200 "), naphthol type epoxy resin (" ESN-475V "manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), epoxy resin with biphenyl structure (" NC-3000H "manufactured by Nippon Kayaku Co., Ltd.," NC-3000L "," YX-4000 "manufactured by Mitsubishi Chemical Corporation), etc.

Examples of suitable epoxy resins include bisphenol A type epoxy resin / bisphenol F type epoxy resin mixture ("ZX-1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and phenol novolac type epoxy resin (Mitsubishi Chemical company "jER152"), and dicyclopentadiene type multifunctional epoxy resin ("HP-7200" by DIC).

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

[(B): Polythiol compound with ester structure]
The polythiol compound having an ester structure is not particularly limited as long as it is a compound having an ester structure in the molecule and two or more mercapto groups.
The polythiol compound having an ester structure is preferably a trifunctional to 6 functional compound (a compound having 3 to 6 thiol groups in one molecule).

The ester-containing polythiol compound is preferably contained so that the equivalent ratio (epoxy group / mercapto group) of the epoxy group to the mercapto group in the resin composition becomes 0.50 to 10.0. The equivalent ratio (epoxy group / mercapto group) is preferably 0.75 to 5.0, and more preferably 0.80 to 2.0.
In addition, the equivalent weight of a mercapto group means the mass of the polythiol compound containing an ester structure with 1 equivalent of a mercapto group.

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

Examples of the polythiol compound having an ester-containing structure include a partial ester and a full ester of a polyalcohol and a mercapto organic acid. Here, a partial ester means an ester of a polyalcohol with a carboxylic acid and a part of hydroxyl groups of the polyalcohol forms an ester bond, and a complete ester means a person whose hydroxyl groups of a polyalcohol form an ester bond. Examples of the polyalcohol include ethylene glycol, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the mercapto organic acid include mercaptoacetic acid, mercaptopropionic acid (example: 3-mercaptopropionic acid), mercaptobutyric acid (example: 3-mercaptobutyric acid, 4-mercaptobutyric acid), and the like. Monocarboxylic acids; esters containing thiol and carboxyl groups obtained by esterification of hydroxy acids and mercapto organic acids; thiol fats such as thiosuccinic acid and dimercaptosuccinic acid (eg, 2,3-dimercaptosuccinic acid) Group dicarboxylic acids; mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid (eg, 4-mercaptobenzoic acid) and the like. The carbon number of the aforementioned mercapto aliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among the aforementioned mercapto organic acids, a mercapto aliphatic monocarboxylic acid having 2 to 8 carbon atoms is preferred, and mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and 4-mercaptobutyric acid are more preferred, and 3 -Mercaptopropionic acid is more preferred.

Specific examples of partial esters of a polyhydric alcohol and a mercapto organic acid include trimethylolpropane bis (mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), and trimethylol Propane bis (3-mercaptobutyrate), trimethylolpropane bis (4-mercaptobutyrate), pentaerythritol ginseng (mercaptoacetate), pentaerythritol ginseng (3-mercaptopropionate), pentaerythritol ginseng (3 -Mercaptobutyrate), pentaerythritol (4-mercaptobutyrate), dipentaerythritol (mercaptoacetate), dipentaerythritol (3-mercaptopropionate), dipentaerythritol (3-mercaptobutyrate) ), Dipentaerythritol (4-mercaptobutyrate) and the like.

Specific examples of the complete ester of a polyol and a mercapto organic acid include ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), and ethylene glycol bis (3-mercaptopropionate). Mercaptopentaerythritol (3-mercaptopropionate butyrate), ethylene glycol bis (4-mercaptobutyrate), trimethylolpropane (mercaptoacetate), trimethylolpropane (3 -Mercaptopropionate), trimethylolpropane (3-mercaptobutyrate), trimethylolpropane (4-mercaptobutyrate), pentaerythritol (mercaptoacetate), pentaerythritol (3 -Mercaptopropionate), pentaerythritol (3-mercaptobutyrate), pentaerythritol (4-mercaptobutyrate), dipentaerythritol (mercaptoacetate), dipentaerythritol (3-mercaptopropionate) , Dipentaerythritol (3-mercaptobutyrate), dipentaerythritol (4-mercaptobutyrate), and the like. Selected from the group consisting of pentaerythritol (3-mercaptopropionate), pentaerythritol (3-mercaptobutyrate), dipentaerythritol (3-mercaptopropionate), and trimethylolpropane (3-mercaptopropionate) ) At least one of the groups is preferred.

As the polythiol compound having an ester-containing structure, for example, ginseng [(3-mercaptopropionyloxy) -ethyl] -isotricyanate, 1,3,5-ginseng (3- Mercaptobutoxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

[(C) carbodiimide]
The carbodiimide (component C) is not particularly limited as long as it is a compound having a molecular weight of 150 to 13,000 and a structure of "-N = C = N-" in the molecule.
The molecular weight of carbodiimide is preferably 170 or more, more preferably 185 or more, and still more preferably 200 or more. If it is in this range, in addition to improving moisture resistance, good storage stability can also be obtained.
The molecular weight of the carbodiimide is preferably 8,000 or less, more preferably 6,000 or less, more preferably 5,000 or less, and even more preferably 4,000 or less. Within this range, more excellent moisture resistance can be obtained.
In addition, in this specification, when a carbodiimide is a polymer, the molecular weight of a carbodiimide means the "mass average molecular weight".
Here, the mass average molecular weight of the carbodiimide is a mass average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method. Specifically, the carbodiimide is in terms of polystyrene. For mass average molecular weight, LC-9A / RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation is used as a column. Chloroform is used. As a transfer phase, measurement was performed at a column temperature of 40 ° C, and calculation was performed using a calibration curve of standard polystyrene.

As the carbodiimide, any of monocarbodiimide, polycarbodiimide, and cyclic carbodiimide can be used, but polycarbodiimide is preferred. The mass average molecular weight of carbodiimide is a mass average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method. Specifically, the mass of carbodiimide in terms of polystyrene The average molecular weight can be measured 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 transfer The phase was measured at a column temperature of 40 ° C and was calculated using a calibration curve of standard polystyrene.

As the monocarbodiimide, for example, a compound represented by the following formula (I) can be used.
(Formula I) R _A -N = C = NR _B
In the formula, R _A and R _B independently represent a C ₁ to C ₁₈ alkyl group, a C ₅ to C ₁₈ cycloalkyl group, or an aryl group. The aryl system may be substituted with at least one kind of substituent selected from the group consisting of a C ₁ to C ₁₈ alkyl group, a nitro group, an amine group, and a hydroxyl group.
Specific examples of the monocarbodiimide include N, N'-di-o-tolylcarbodiimide, N, N'-diphenylcarbodiimide, and N, N'-di-2 , 6-dimethylphenylcarbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-bis (propylphenyl) carbodiimide Imine, N, N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,2-di-tert-butyl Phenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-amine Phenylphenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-dicyclohexylcarbodiimide, and N, N'-di-p-tolyl Carbodiimide, etc. Moreover, among these are N, N'-dicyclohexylcarbodiimide, N, N'-bis (propylphenyl) carbodiimide and bis (dipropylphenyl) carbodiimide Better.

As the polycarbodiimide, for example, a compound described in Japanese Patent No. 5693799 can be used. Specifically, the compound described in this document refers to a carbodiimide compound represented by the following formula.
(Formula): R ² -(-N = C = NR ^1- ) _m -R ³
In the above formula, in the formula, R ¹ represents a divalent aromatic group and / or an aliphatic group which are 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 hetero atom, and these substituents may be substituted at ortho positions of at least one of the aromatic groups to which the carbodiimide group is bonded.

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 group, -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 group, -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 ~ C ₂₀ alkyl, C ₃ ~ C ₂₀ cycloalkyl, C ₇ ~ C ₁₈ aralkyl, oligo / polyethylene glycols and / or oligo / poly Propylene glycols.

R ⁷ is one of the aforementioned definitions of R ⁵ or a polyester group or a polyamido group.

m is an integer of 2 or more.

Examples of the polycarbodiimide include poly (4,4'-dicyclohexylmethanecarbodiimide) and poly (N, N'-di-2,6-diisopropylphenylcarbodiimide). Amine), poly (1,3,5-triisopropylphenylene-2,4-carbodiimide), and the like. Among these, poly (1,3,5-triisopropylphenylphenyl-2,4-carbodiimide) is preferred.
As the polycarbodiimide, a commercially available product can also be used, and examples thereof include aliphatic polycarbodiimide ("Elastostab H-01" manufactured by Nisshinbo Chemical Co., Ltd.), and carbodiimide-modified isocyanate (manufactured by Nisshinbo Chemical Co., Ltd.). "Carbodilite V-05") and so on. Among these, a carbodiimide-modified isocyanate ("Carbodilite V-05" manufactured by Nisshinbo Chemical Co., Ltd.) is preferred.
Examples of the cyclic carbodiimide include a cyclic carbodiimide described in Japanese Patent No. 5,856,924.

When the non-volatile content of the resin composition is 100% by mass, the content of (C) carbodiimide in the resin composition is preferably 0.01 to 50% by mass, and more preferably 0.1 to 35% by mass. .

[(D): Hardening accelerator]
The resin composition of this embodiment preferably contains a hardening accelerator.

As the hardening accelerator, a latent hardening accelerator is preferably used. The latent hardening accelerator is an important component especially when it is used as a single-liquid type resin composition. It does not impart hardening to the epoxy resin at normal temperature (20 ° C ± 15 ° C (JISZ8703)), and has an accelerating ring when heated. Additive for the hardening function of oxygen resin.

As the latent hardening accelerator, any of a liquid latent hardening accelerator and a solid-dispersed latent hardening accelerator can be used, but a solid-dispersed latent hardening accelerator is preferably used.

The liquid latent hardening accelerator refers to a compound that is soluble in epoxy at normal temperature and is not active at normal temperature, but has the function of a hardening accelerator for epoxy resin due to heating.
Examples of the liquid latent hardening accelerator include, but are not limited to, ionic liquids.
Examples of the cation constituting the ionic liquid include ammonium cations such as imidazolium cations, piperidinium cations, pyrrolidium cations, pyrazonium ions, guanidinium cations, and pyridinium cations; Sulfonium cations such as sulfonium cations; sulfonium cations such as triethylsulfonium ions.
Examples of the anion constituting the ionic liquid include halide-based anions such as fluoride ion, chloride ion, bromide ion, and iodide ion: alkylsulfate-based anions such as methanyl ion: trifluoromethanesulfonate Fluorine compounds such as acid ions, hexafluorophosphonic acid ions, trifluoroshen (pentafluoroethyl) phosphonic acid ions, bis (trifluoromethanesulfonyl) phosphonium imine ions, trifluoroacetic acid ions, tetrafluoroborate ions, etc. Anions: Phenol ions, 2-methoxyphenol ions, 2,6-di-tert-butylphenol ions, and other phenolic anions: aspartic acid ions, glutamic acid ions and other acidic amino acid ions: Neutral amino acid ions such as glycine ion, alanine ion, phenylalanine ion, etc .: N-benzylfluorenyl alanine ion, N-ethylamylphenylalanine ion, N-ethylammonium glycine N-fluorenylamino acid ions such as acid ions, N-acetylsulfuric acid ions: formic acid ion, lactic acid ion, tartaric acid ion, uric acid ion, N-methyl field uric acid, benzoic acid ion, etc. Department of anions.

The solid dispersion-type latent hardening accelerator refers to a compound that is insoluble in epoxy resin at room temperature and is soluble by heating and has a function as a hardening accelerator for epoxy resin.

Examples of the solid dispersion-type latent hardening accelerator include, for example, a solid imidazole compound and a solid dispersion-type amine adduct-based latent hardening accelerator at room temperature, but they are not limited thereto.

Examples of the solid imidazole compound at normal temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, and 2-phenyl-4- Methyl-5-hydroxymethylimidazole, 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, isotricyanic acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-partial Trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, N, N '-(2- Methylimidazolyl- (1) -ethyl) -hexamethylenediamine and the like are not limited thereto.

Suitable examples of the solid dispersion-type amine adduct-based latent hardening accelerator include, for example, an epoxy adduct of an amine compound, a urea adduct of an amine compound, and an epoxy adduct At least one group of compounds formed by the addition reaction of a hydroxyl group and an isocyanate compound.

Examples of the epoxy compound used as one of the raw materials for producing the epoxy adduct of the amine compound include polyphenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or Polyglycidyl ether obtained by reacting a polyhydric alcohol like glycerol or polyethylene glycol with epichlorohydrin; such as p-hydroxybenzoic acid, hydroxycarboxylic acid of β-hydroxynaphthoic acid and epichlorohydrin Glycidyl ether ester obtained by reaction; polyglycidyl ester obtained by reacting polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin; 4,4'-diamine Epoxypropylamine compounds obtained by reacting diphenylmethane or m-aminophenol with epichlorohydrin; and polyfunctional epoxidized phenol novolac resin, epoxidized cresol novolac resin, epoxidized polyolefin, etc. Although it is not limited to these epoxy compounds or monofunctional epoxy compounds such as butylglycidyl ether, phenylglycidyl ether, glycidyl methacrylate, and the like.

An amine compound that is used as a raw material for the production of the aforementioned solid dispersion-type amine adduct-type latent hardening accelerator, as long as it has at least one active hydrogen capable of undergoing an addition reaction with an epoxy group in the molecule and at least less than the molecule It is sufficient to have one or more functional groups selected from among primary amine groups, secondary amine groups, and tertiary amine groups. Examples of such an amine compound include diethylene glycol triamine, triethylene glycol tetraamine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamine Amine-dicyclohexylmethane-like aliphatic amines; 4,4'-diaminodiphenylmethane, 2-methylaniline and other aromatic amine compounds; 2-ethyl-4-methylimidazole, Nitrogen atom-containing heterocyclic compounds such as 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, piperazine, and the like are not limited thereto.

Among them, a compound having a tertiary amine group in particular is a raw material for imparting a potential hardening accelerator having excellent hardening promoting ability. Examples of such a compound include dimethylaminopropyl group. Diamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine , N-methylpiperazine and other amine compounds, or 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole compounds Grade 1 or Grade 2 amines with 3 amine groups; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethyl Aminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methyl Imidazole, 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-butoxy (Propyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4,6-ginseng (dimethylaminomethyl) phenol, N-β-hydroxyethyl Phthaloline, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N, N-dimethyl Aminoaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, topicodic acid, N, N-dimethylglycine hydrazine, N, N-dimethylpropane Acid hydrazine, nicotinic acid hydrazine, isonicotinic acid hydrazine, etc. are alcohols, phenols, thiols, carboxylic acids, and hydrazines having tertiary amine groups in the molecule.

When the latent curing accelerator is produced by an addition reaction of the aforementioned epoxy compound and amine compound, an active hydrogen compound having two or more active hydrogens in the molecule may be further added. Examples of such active hydrogen compounds include polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenol novolac resin, and the like. Polyvalent alcohols such as methylolpropane, polycarboxylic acids such as adipic acid, phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2 -Propanol, mercaptoacetic acid, anthranilic acid, lactic acid, etc., but not limited to these.

As the isocyanate compound used as a raw material for the production of the above-mentioned solid dispersion-type amine adduct-based latent hardening accelerator, for example, n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, and the like can be used. Functional isocyanate compounds; hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, stub base Difunctional isocyanate compounds such as diisocyanate, p-phenylene diisocyanate, 1,3,6-hexamethylenetriisocyanate, dicycloheptane triisocyanate, and the like; and, by using these polyfunctional isocyanate compounds and Compounds containing terminal isocyanate groups obtained by the reaction of hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by the reaction of toluene diisocyanate and trimethylolpropane, and a reaction of toluene diisocyanate and pentaerythritol. The obtained addition compound having a terminal isocyanate group is not limited to these.

Examples of the urea compound used as a raw material for the production of the solid dispersion-type amine adduct-based latent hardening accelerator include, for example, urea and thiourea, but they are not limited to these.

The solid dispersion-type latent hardening accelerator is suitably mixed with the above-mentioned production raw materials, reacted at a temperature from normal temperature to 200 ° C, and then pulverized after cooling and solidification, or in methyl ethyl ketone and dioxin. It is made to react in a solvent, such as an alkane, tetrahydrofuran, etc., and it can be obtained easily by pulverizing a solid content after solvent removal.

As a representative example of a commercially available solid dispersion-type latent hardening accelerator, for example, as an amine-epoxy addition system (amine addition system), for example, "PN-23" (Ajinomoto Precision Technology company), "Amicure PN-H" (manufactured by Ajinomoto Precision Technology Co., Ltd.), "Hardener X-3661S" (manufactured by ACR company), "Hardener X-3670S" (manufactured by ACR company), etc. Examples of the type addition 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).
In addition, examples include "Novacure HX-3721" (manufactured by Asahi Kasei Corporation), "HX-3722" (manufactured by Asahi Kasei Corporation), and "Novacure HX-3742" (manufactured by Asahi Kasei Corporation), which are denatured microcapsules.

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

[(E): Inorganic filler]
The resin composition of the present embodiment preferably contains an inorganic filler. By using an inorganic filler, moisture resistance can be further improved.

When the nonvolatile content in the resin composition is 100 parts by mass, the content of the inorganic filler (E) component is, for example, 1 to 70 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass. Serving.

The average particle diameter 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 diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction type particle size distribution measurement device, and the average diameter can be measured by setting the median diameter. As the measurement sample, it is preferable to use an ultrasonic dispersing inorganic filler in water. As a laser diffraction scattering type particle size distribution measuring device, LA-500 manufactured by HORIBA, etc. can be used.

The inorganic filler is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and oxidation. At least one of the group consisting of magnesium, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
The inorganic filler preferably contains at least one selected from the group consisting of silicon dioxide, calcium carbonate, talc, and mica, and more preferably contains silicon dioxide.

[(F): Other]
Furthermore, in order to achieve more excellent storage stability, the resin composition of this embodiment contains a material selected from the group consisting of a borate compound, a titanate compound, an aluminate compound, a zirconate compound, an isocyanate compound, a carboxylic acid and an anhydride And one or more mercapto organic acids are preferred.

Examples of the borate compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl. Borates, Tripentyl Borates, Triallyl Borates, Trihexyl Borates, Tricyclohexyl Borates, Trioctyl Borates, Trinonyl Borates, Tridecyl Boron Acid esters, ginsyl dodecyl borates, hexadecyl borates, octadecyl borates, ginseng (2-ethylhexyloxy) borane, bis (1,4,7,10- Tetraoxaundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzylborate, tris Phenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like.

Examples of the titanate compound include, for example, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and the like.

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, and the like. 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenyl Methane-4,4'-diisocyanate, ditoluidine diisocyanate, isophorone diisocyanate, stubyl diisocyanate, p-phenylene diisocyanate, dicycloheptane triisocyanate, etc.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, and octanoic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; Halogenated fatty acids such as chloroacetic acid and dichloroacetic acid, monobasic oxo acids such as glycolic acid, lactic acid, etc., fatty uronic acids such as glyoxalic acid, racemic acid, keto acid, and oxalic acid , Polybasic acids such as malonic acid, succinic acid, maleic acid, benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, mandelic acid, etc. Aromatic polybasic acids such as trimesic acid.

Examples of the acid anhydride include anhydrous succinic acid, anhydrous dodecenyl succinic acid, anhydrous maleic acid, an adduct of methylcyclopentadiene and anhydrous maleic acid, hexahydroanhydrophthalic acid, Methyltetrahydroanhydrous phthalic acid and other aliphatic or aliphatic polyacid anhydrides, etc., anhydrous phthalic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid and other aromatic polybasic acid anhydrides.

Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid, and esters of hydroxyorganic acids and mercaptoorganic acids. Mercapto aliphatic monocarboxylic acid obtained by chemical reaction, mercapto aromatic monocarboxylic acid such as mercaptobenzoic acid and the like.

As the component (F), among these, from the viewpoints of general versatility and safety and improved storage stability, borate ester compounds are preferred, and triethylborate and tri-n are preferred. -Propyl borate, triisopropyl borate, and tri-n-butyl borate are preferred, and triethyl borate is more preferred. The content of the (F) component is not particularly limited as long as the storage stability of the resin is improved. When the content of the epoxy resin of the (A) component is 100 parts by mass, the content of the (F) component is 0.001 to 50 mass Parts is better, 0.05 to 30 parts by mass is more preferred, and 0.1 to 10 parts by mass is more preferred.

The resin composition of the embodiment described above can be implemented by a conventionally known method. That is, for example, the resin composition of this embodiment can be prepared by mixing the components with various mixers.

When the resin composition of the present embodiment is a one-liquid type resin composition, a conventionally known method can be used as the curing method. For example, hardening can be performed by heating a resin composition. The heating system is suitably, for example, at 60 to 150 ° C, preferably at 70 to 120 ° C, and more preferably at a temperature of 80 to 100 ° C, for example, 1 to 120 minutes, preferably 3 to 60 minutes, and more preferably 5 ~ 40 minutes.

If necessary, fillers, diluents, solvents, pigments, flexibility imparting agents, coupling agents, antioxidants, thixotropy imparting agents, dispersing agents, etc. that are commonly used in the field of the present invention can be added to the resin composition of this embodiment. Of various additives.

The resin composition of this embodiment can be used, for example, in a functional product. Examples of the functional product include an adhesive, a molding agent, a sealant, a sealant, a fiber-reinforced resin, a coating agent, and a coating material.
The resin composition suitable for this embodiment is suitable for use as an adhesive used in the production of electronic parts such as CCM, HDD, semiconductor elements, and integrated circuits, and is more suitable for use as an adhesive between constituent members of a photographic module. Examples of such constituent members include metal members such as copper and nickel; and plastic members such as LCP (liquid crystal polymer), polyamide, and polycarbonate. The resin composition of this embodiment is suitable as an adhesive for the same or different members selected from these metal members and plastic members.

According to the resin composition of this 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.

[Example]

Hereinafter, the present invention will be described more specifically 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 "mass part."

Raw materials
[(A) Ingredient]
(A1) ZX-1059: Epoxy equivalent (EPW) of bisphenol A type epoxy resin / bisphenol F type epoxy resin mixture made by Nippon Steel & Sumitomo Chemical Co., Ltd. 165 g / eq
(A2) jER152: Epoxy equivalent (EPW) of phenol novolac epoxy resin made by Mitsubishi Chemical Corporation 177 g / eq
(A3) HP-7200: Dicyclopentadiene epoxy resin epoxy equivalent (EPW) 258 g / eq.

[(B) Ingredient]
(B1) PE1: "Karenz MT" manufactured by Showa Denko Corporation Pentaerythritol (3-mercaptobutyrate), thiol equivalent 136 g / eq
(B2) PEMP: Pentaerythritol (3-mercaptopropionate), thiol equivalent 122 g / eq, manufactured by SC Organic Chemicals
(B3) DPMP: dipentaerythritol (3-mercaptopropionate), thiol equivalent 131 g / eq
(B4) TMTP: Trimethylolpropane ginseng (3-mercaptopropionate), thiol equivalent 140g / eq

[(C) component]
(C1) Stabaxol I powder: N, N'-bis (2,6-diisopropylphenyl) carbodiimide manufactured by LANXESS, molecular weight 360
(C2) Stabaxol 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) Stabaxol P100: aromatic polycarbodiimide manufactured by LANXESS, with a mass average molecular weight of 15,000 or more

[(D) component]
(D1) PN-23: Modified polyamine (solid) containing imidazole group manufactured by Ajinomoto Precision Technology Co., Ltd.
(D2) FXR-1081: T & K TOKA company's modified polyamine solid type containing urea bond
(D3) HX-3722: Imidazole denatured microcapsule manufactured by Asahi Kasei Corporation

[(E) Inorganic Filler]
(E1) SO-C5: Silicon dioxide particle size from 1.3 to 1.7 μm by Admatex
(E2) Whiton B: average particle diameter of calcium carbonate manufactured by Shiraishi Calcium Corporation 3.6 μm
(E3) Talc MS: The average particle diameter of talc made by Japan Talc Corporation is 14.0 μm
(E4) Mica C-1000: The average particle size of mica manufactured by Imerys Mica Kings Mountain is 26.0 μm

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

2. Evaluation test
(1) Storage stability The resin composition to be measured was stored in a plastic closed container at 25 ° C for 7 days. Before and after storage, the viscosity of the resin composition was measured with an E-type viscosity meter RE-80U (manufactured by Toki Sangyo Co., Ltd., rotor: 3˚ × R9.7) at 25 ° C and 20 rpm, and the viscosity after 7 days / The initial viscosity is used to calculate the viscosity increase rate from the initial viscosity.

＜ 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 hardenability According to JIS C6521, a heating plate type gel tester GT-D (manufactured by Nisshin Scientific Co., Ltd.) was used to measure the time when the resin composition to be measured did not become drawn at 90 ° C. Specifically, about 0.5g of the composition was placed on a heating plate type gelatinization tester which was heated to 90 ° C in advance, and the stopwatch was started. The circular movement was repeated with a spatula with a tip width of 5mm and the measurement was performed until gelation. Time.

＜ Evaluation criteria ＞
：: Less than 10 minutes 0: More than 10 minutes, less than 30 minutes ×: more than 30 minutes

(3) Shearing test According to JIS K-6850, the resin composition to be measured was hardened in a thermal cycle oven at 90 ° C for 30 minutes, and a test piece adhered to the resin composition was produced. As a test piece, a soft steel plate (SPCC, manufactured by Dayu Machinery Co., Ltd.) was degreased with acetone and polished with an endless belt # 120. Using a universal testing machine (manufactured by TSE, AC-50KN-CM) to measure (measurement environment: temperature 25 ° C / humidity 60%, tensile speed; 5mm / min) the shear adhesion strength of the test piece.

(4) The humidity resistance test is performed in the same procedure as in (3). A test piece is produced, and the test piece is placed in a highly accelerated life tester (manufactured by Espec) which has been set at 121 ° C and 100% RH for 24 hours. Then, the obtained test piece was measured for the shear adhesion after the moisture resistance test using a universal testing machine.
In addition, in order to evaluate the influence on the bonding strength in a high-temperature and high-humidity environment, the bonding strength maintenance rate was calculated. The subsequent strength maintenance ratio is the difference between the initial shear adhesion strength and the shear adhesion strength after the moisture resistance test, and is calculated by the following formula.
[Adhesion strength retention rate (%)] = [Shear adhesion strength after moisture resistance test] / [Initial shear adhesion strength] × 100

＜ Evaluation criteria ＞
◎: 30% or more 〇: 15% or more, less than 30%
×: 15%

3. Examples and Comparative Examples The ingredients shown in the upper column of Tables 1 to 4 were used to mix the components to prepare resin compositions of Examples 1 to 22 and Comparative Examples 1 to 5.

In addition, in Examples 1 to 22, the components (A), (C), and (E) were mixed by a three-roll mill, and the components (D) and (F) were added thereto, and then they were performed by a mixer. Mix, add (B) component to this, fully disperse | distribute by a mixer, and let it stand and defoam, and prepare. Moreover, the preparation operation was performed at 25 degreeC, and the total mixing time was 30 minutes.

Comparative Examples 1 to 5 are also modulated in the same manner according to the cooperation of Tables 1 to 4.

The resin compositions of Examples 1 to 22 and Comparative Examples 1 to 5 were provided to the aforementioned evaluation test, and the results are shown in Tables 1 to 4.

As can be seen from Tables 1 to 4, as shown in the results of Examples 1 to 22, the resin composition of the present invention is excellent in low-temperature curability, has good storage stability, and exhibits excellent moisture resistance. On the other hand, it can be seen that the resin compositions of Comparative Examples 1 to 5 do not have such high performance as the resin composition of the present invention.
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 curing properties, but have poor moisture resistance (adhesive strength retention). That is, when a polythiol compound having an ester-containing structure (B) is used, excellent low-temperature curability is preferred, but moisture resistance is deteriorated.
On the other hand, when compared with Comparative Example 1 and Comparative Example 2, the moisture resistance of Examples 1 to 22 was improved. That is, it is understood that by adding (C) carbodiimide, the moisture resistance is improved.
In addition, when Comparative Examples 3 and 4 are compared with Examples 1 to 22, it can be understood that even when carbodiimide is added, by setting the molecular weight in the range of 150 to 10,000, storage stability is improved. .
Furthermore, among Examples 1 to 22, from the viewpoints of storage stability, low-temperature hardening property, and moisture resistance, Examples 17 and 22 were particularly good results.

Claims (16)

A resin composition comprising: (A) epoxy resin, (B) a polythiol compound containing an ester structure, and (C) A carbodiimide having a molecular weight of 150 to 13,000. The resin composition according to claim 1, wherein when the non-volatile content of the resin composition is 100% by mass, the content of the carbodiimide in the resin composition is 0.01 to 50% by mass. The resin composition as claimed in claim 1 or 2, further comprising (E) an inorganic filler. The resin composition according to claim 3, wherein when the non-volatile component in the resin composition is 100 parts by mass, the content of the inorganic filler is 1 to 70 parts by mass. The resin composition according to claim 3 or 4, wherein the inorganic filler comprises at least one selected from the group consisting of silicon dioxide, calcium carbonate, talc, and mica. The resin composition according to any one of claims 1 to 5, wherein the equivalent ratio (epoxy group / mercapto group) of the epoxy group to the mercapto 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 hardening accelerator. The resin composition according to claim 7, wherein the hardening accelerator is a latent hardening accelerator. The resin composition according to claim 8, wherein the aforementioned latent hardening accelerator comprises an epoxy adduct of an amine compound, a urea adduct of an amine compound, and a hydroxyl group and an isocyanate group of the epoxy adduct. At least one group of compounds in which a compound is subjected to an addition reaction. The resin composition according to any one of claims 1 to 9, which is a single-liquid type resin composition. An adhesive containing the resin composition according to any one of claims 1 to 10. If the adhesive of claim 11 is used, it is the adhesive between the constituent components of the photographic module. A sealant containing the resin composition according to any one of claims 1 to 10. A coating agent comprising 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 part comprising a hardened body as claimed in claim 15.