Curable resin composition, adhesive, and bonding method

Abstract

To provide a curable resin composition with excellent stringiness, adhesion, and morphological stability.SOLUTION: A curable resin composition contains (A) a curable resin, (B) calcium carbonate with a BET specific surface area of 5 m2 / g or more, and (C) a curing agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, an adhesive, and an adhesion method. [Background technology]

[0002] Curable resin compositions are used in a variety of applications. For example, in the manufacture of electronic devices such as camera modules, curable resin compositions are sometimes used to bond multiple components together. Such curable resin compositions are usually used by coating.

[0003] When applying a resin composition, stable and good application is required. In relation to this point, Patent Document 1 (JP 2002-177843 A) discloses a dispenser device having a specific configuration that is capable of stable and good application even when applying a paste with high viscosity and high thixotropy. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-177843 Summary of the Invention [Problem to be solved by the invention]

[0005] In some cases, a curable resin composition used as an adhesive or the like needs to contain a high-viscosity curable resin or a solid curable resin in order to impart properties such as toughness, high heat resistance, and high reliability.

[0006] However, when a high-viscosity or solid curable resin is blended, the resin composition becomes viscous. As a result, the applicability may deteriorate. For example, when the resin composition is discharged through a nozzle during application, stringiness is likely to occur. In other words, the thread breakage is worsened. As a result, the takt time tends to be long. In addition, the resin composition is likely to adhere to areas other than the target area. Adding an inorganic filler to improve thread breakage resistance is also an option. However, this can lead to reduced adhesion to the bonded object. Thixotropy can also be reduced. This means that the shape stability (shape retention) of the resin composition after application is reduced, and the applied area is more likely to spread after application. Therefore, it has been difficult to achieve a good balance between thread breakage resistance, adhesion, and shape stability.

[0007] Therefore, an object of the present invention is to provide a curable resin composition that has an improved balance of resistance to thread breakage, adhesion, and shape stability. [Means for solving the problem]

[0008] As a result of investigations, the present inventors have found that the above problems can be solved by the following means. [1] (A) Curable resin and (B) BET specific surface area 5m 2 / g or more of calcium carbonate, (C) a curing agent. [2] The curable resin composition according to [1], wherein the (A) curable resin contains at least one resin selected from a high-viscosity curable resin, which is a resin having a viscosity of 100 Pa s or more as measured at 25°C and 1 rpm with an E-type viscometer, and a solid curable resin, which is a resin that is solid at 25°C. [3] The curable resin composition according to [2], wherein the high-viscosity curable resin and the solid curable resin are contained in an amount of 5 to 100 parts by mass per 100 parts by mass of the (A) curable resin. [4] The curable resin composition according to any one of [1] to [3], which has a viscosity of 10 to 500 Pa·s as measured at 25°C and 1 rpm using an E-type viscometer. [5] The curable resin composition according to any one of [1] to [4], wherein V1 is the viscosity measured with an E-type viscometer at 25°C and 1 rpm, and V2 is the viscosity measured with an E-type viscometer at 25°C and 10 rpm, and the ratio of the viscosity V1 to the viscosity V2 of the curable resin composition (V1 / V2) is 1.5 to 6.0; or V3 is the viscosity measured with an E-type viscometer at 25°C and 2 rpm, and V4 is the viscosity measured with an E-type viscometer at 25°C and 20 rpm, and the ratio of the viscosity V3 to the viscosity V4 of the curable resin composition (V3 / V4) is 1.5 to 6.0. [6] The curable resin composition according to any one of [1] to [5], wherein the (A) curable resin contains at least one selected from the group consisting of epoxy resins and compounds having a (meth)acryloyl group. [7] The curable resin composition according to any one of [1] to [6], wherein the component (A) contains an epoxy resin. [8] The BET specific surface area of ​​the (B) calcium carbonate is 5 m 2 / g or more 50m 2 The curable resin composition according to any one of [1] to [7], wherein the curable resin composition has a viscosity of 1000 MPa or less. [9] The curable resin composition according to any one of [1] to [8], wherein the (C) curing agent contains a polythiol compound having two or more mercapto groups in one molecule.

[10] The curable resin composition according to any one of [1] to [9], wherein the (A) curable resin is contained in an amount of 5 to 80 parts by mass per 100 parts by mass of non-volatile components of the curable resin composition.

[11] The curable resin composition according to any one of [1] to

[10] , wherein the (B) calcium carbonate is 3 to 80 parts by mass per 100 parts by mass of non-volatile components of the curable resin composition.

[12] The curable resin composition according to any one of [1] to

[11] , wherein the amount of the (C) curing agent is 5 to 80 parts by mass per 100 parts by mass of the non-volatile components of the curable resin composition.

[13] The curable resin composition according to any one of [1] to

[12] , which is applied by being discharged from a nozzle.

[14] An adhesive comprising the curable resin composition according to any one of [1] to

[13] .

[15] The adhesive according to

[14] , which is for bonding components of a camera module.

[16] A bonding method, comprising a step of discharging the curable resin composition according to any one of [1] to

[13] from a nozzle. [Effects of the Invention]

[0009] According to the present invention, there is provided a curable resin composition which has an improved balance of resistance to thread breakage, adhesion, and shape stability. DETAILED DESCRIPTION OF THE INVENTION

[0010] The curable resin composition according to this embodiment comprises (A) a curable resin and (B) a curable resin having a BET specific surface area of ​​5 m 2 / g or more, and (C) a hardener. 2 / g or more of calcium carbonate is blended, which allows for a balanced improvement in thread breakage resistance, adhesion, and shape stability.

[0011] Each component will be described in detail below.

[0012] (A) Curing resin The curable resin is not particularly limited as long as it has the function of being cured by heat, ultraviolet light, or the like.

[0013] The content of the (A) curable resin in the curable resin composition is, for example, 5 to 80 parts by mass, preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass, per 100 parts by mass of the nonvolatile components of the curable resin composition.

[0014] Examples of the curable resin include one or more selected from epoxy resins, compounds having a (meth)acryloyl group, silicone resins, phenolic resins, melamine resins, and unsaturated polyester resins. Preferably, the curable resin includes an epoxy resin or a compound having a (meth)acryloyl group, and particularly preferably includes an epoxy resin.

[0015] Examples of epoxy resins include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; and further, epoxidized phenol novolac resins, epoxidized cresol novolac resins, epoxidized polyolefins, alicyclic epoxy resins, and other urethane-modified epoxy resins.

[0016] The term "(meth)acryloyl group" refers to either or both of an acryloyl group and a methacryloyl group. Examples of the compound having a (meth)acryloyl group include β-carboxyethyl (meth)acrylate, isobornyl (meth)acrylate, octyl / decyl (meth)acrylate, ethoxylated phenyl (meth)acrylate, EO-modified phenol (meth)acrylate, EO-modified o-phenylphenol (meth)acrylate, EO-modified para-cumylphenol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, N-(meth)acryloyloxyethyl hexahydrophthalimide, ω-carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, dipropylene glycol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, EO-modified isocyanuric acid di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate, polyurethane having (meth)acryloyl group, polyester having (meth)acryloyl group, trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, EO-modified isocyanuric acid (tri)(meth)acrylate, pentaerythritol Examples of the epoxy acrylate include (tri / tetra)(meth)acrylate, glycerin propoxytri(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol (penta / hexa)(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified diglycerin tetra(meth)acrylate, and epoxy acrylate. Epoxy acrylate can also be considered an epoxy resin.

[0017] Preferably, the curable resin includes at least one resin selected from a high-viscosity curable resin and a solid curable resin.

[0018] A "high-viscosity curable resin" is a resin with a viscosity of 100 Pa·s or more as measured at 25°C and 1 rpm with an E-type viscometer. The viscosity of the high-viscosity curable resin (E-type viscometer, 25°C, 1 rpm) is preferably 100 to 2000 Pa·s, and more preferably 120 to 1500 Pa·s. The "high-viscosity curable resin" is preferably an epoxy resin. When the high-viscosity curable resin is an epoxy resin, its epoxy equivalent is, for example, 50 to 700 g / eq, preferably 50 to 500 g / eq, more preferably 100 to 450 g / eq, and even more preferably 150 to 450 g / eq. The epoxy equivalent is the mass of the epoxy resin per epoxy group, and can be measured in accordance with JIS K 7236 (2009). Specific examples of such high viscosity curable resins include "EXA-4816" (manufactured by DIC Corporation), "MX-135" (manufactured by Kaneka Corporation), and "EA-1010N" (manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0019] A "solid curable resin" is a curable resin that is solid at 25°C. In a preferred embodiment, the curable resin includes a solid curable resin that is an epoxy resin. When the solid curable resin is an epoxy resin, the epoxy equivalent is, for example, 800 to 1200 g / eq, preferably 850 to 1100 g / eq, and more preferably 900 to 1000 g / eq. A specific example of such a solid curable resin is "1004AF" (manufactured by Mitsubishi Chemical Corporation).

[0020] The inclusion of a high-viscosity curable resin or a solid curable resin can improve performance such as toughness, high heat resistance, and high reliability. On the other hand, the inclusion of such a resin increases the viscosity of the resin composition, which generally worsens thread breakage. However, according to this embodiment, the calcium carbonate solves the thread breakage problem. Therefore, a curable resin with excellent thread breakage resistance can be realized even while containing a high-viscosity curable resin or a solid curable resin. The content (total amount) of the high-viscosity curable resin and the solid curable resin is, for example, 5 to 100 parts by mass relative to 100 parts by mass of the curable resin.

[0021] Furthermore, the curable resin may contain a low-viscosity curable resin in addition to the high-viscosity curable resin and / or the solid curable resin. A "low-viscosity curable resin" is a resin having a viscosity (E-type viscometer, 25°C, 1 rpm) of less than 100 Pa·s. The viscosity (E-type viscometer, 25°C, 1 rpm) of a "low-viscosity curable resin" is preferably 1 to 50 Pa·s, more preferably 5 to 30 Pa·s. By using a low-viscosity curable resin, the viscosity of the curable resin composition can be adjusted to a desired viscosity. The content of the low-viscosity curable resin is, for example, 5 to 90 parts by mass, and preferably 50 to 85 parts by mass, relative to 100 parts by mass of the curable resin.

[0022] In a preferred embodiment, the low-viscosity curable resin is an epoxy resin, in which case the epoxy equivalent is, for example, 150 to 300 g / eq, preferably 170 to 250 g / eq. A specific example of such a low viscosity curable resin is "YL-980" (manufactured by Mitsubishi Chemical Corporation).

[0023] (B) Calcium carbonate As mentioned above, calcium carbonate has a BET specific surface area of ​​5m 2 / g or more is used. The BET specific surface area can be measured in accordance with Japanese Industrial Standard JIS Z 8830 "Method for measuring the specific surface area of ​​powders (solids) by gas adsorption." The BET specific surface area can be measured using an automatic specific surface area measuring device, and an example of such an automatic specific surface area measuring device is the "Macsorb HM-1210" manufactured by Mountech Co., Ltd. BET specific surface area 5m 2 By using calcium carbonate having a % or more of calcium carbonate, thread breakage resistance, shape stability, and adhesion can be improved in a balanced manner. In addition, the BET specific surface area is 5m 2 If it is less than 1 / g, it becomes difficult to obtain the desired shape stability, and the adhesiveness also decreases. Furthermore, when calcium carbonate foil or other inorganic fillers such as silica are used, it is not possible to improve thread breakage resistance, shape stability, and adhesion in a balanced manner.

[0024] The BET specific surface area of ​​calcium carbonate is 5m 2 / g or more, but preferably 6m 2 / g or more, more preferably 7m 2 / g or more, more preferably 8m 2 / g or more, particularly preferably 8m 2 / g or more. The BET specific surface area is preferably 50 m 2 / g or less, and more preferably 40m 2 / g or less, more preferably 35m 2 / g or less, particularly preferably 30m 2 / g or less.

[0025] The content of calcium carbonate is, for example, 3 to 80 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the nonvolatile components of the curable resin composition.

[0026] (C) Hardener The curing agent is a substance that has the function of curing the curable resin by heat and / or ultraviolet irradiation, etc. The curing agent is not particularly limited as long as it has the function of curing the curable resin.

[0027] Preferably, a thiol compound having a mercapto group is used as the curing agent. More preferably, the thiol compound is a polythiol compound having two or more mercapto groups in one molecule. That is, a polyfunctional thiol compound is preferably used. The use of a polyfunctional thiol compound makes it possible to quickly cure the curable resin composition at low temperatures. Furthermore, since the polyfunctional thiol compound has low viscosity, it is easy to reduce the viscosity of the entire resin composition even when a high-viscosity resin is used.

[0028] The number of mercapto groups in one molecule of the polythiol compound is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3.

[0029] Specific examples of polythiol compounds include partial esters of polyols and mercapto organic acids, and complete esters of polyols and mercapto organic acids. Here, the term "partial ester" refers to an ester of a polyol and a carboxylic acid in which some of the hydroxy groups of the polyol form ester bonds. The term "complete ester" refers to an ester in which all of the hydroxy groups of the polyol form ester bonds.

[0030] Examples of polyols include ethylene glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0031] Examples of mercapto organic acids include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid (e.g., 3-mercaptopropionic acid), and mercaptobutyric acid (e.g., 3-mercaptobutyric acid, 4-mercaptobutyric acid); esters containing a mercapto group and a carboxy group obtained by esterification of a hydroxy acid with a mercapto organic acid; mercaptoaliphatic dicarboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid (e.g., 2,3-dimercaptosuccinic acid); and mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid (e.g., 4-mercaptobenzoic acid). The number of carbon atoms in the mercaptoaliphatic monocarboxylic acid is preferably 2 to 8, more preferably 2 to 6, even 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 preferred, mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid are more preferred, and 3-mercaptopropionic acid is even more preferred.

[0032] Specific examples of partial esters of polyols and mercapto organic acids include trimethylolethane bis(mercaptoacetate), trimethylolethane bis(3-mercaptopropionate), trimethylolethane bis(3-mercaptobutyrate), trimethylolethane bis(4-mercaptobutyrate), trimethylolpropane bis(mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), trimethylolpropane bis(3-mercaptobutyrate), trimethylolpropane bis(4-mercaptobutyrate), pentaerythritol tris(mercaptoacetate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptobutyrate), and pentaerythritol Examples thereof include tris(4-mercaptobutyrate), dipentaerythritol tetrakis(mercaptoacetate), dipentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptobutyrate), and dipentaerythritol tetrakis(4-mercaptobutyrate).

[0033] Specific examples of complete esters of polyols and mercapto organic acids include ethylene glycol bis(mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptobutyrate), ethylene glycol bis(4-mercaptobutyrate), trimethylolethane tris(mercaptoacetate), trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolethane tris(4-mercaptobutyrate), trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(4-mercaptobutyrate), and pentaerythritol. Examples include tetrakis(mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(4-mercaptobutyrate), dipentaerythritol hexakis(mercaptoacetate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), and dipentaerythritol hexakis(4-mercaptobutyrate).

[0034] The content of the curing agent is, for example, 5 to 80 parts by mass, preferably 10 to 50 parts by mass, and more preferably 15 to 40 parts by mass, relative to 100 parts by mass of the nonvolatile components of the curable resin composition.

[0035] (D) Other ingredients In addition to the above-mentioned components, the curable resin composition may contain other components as needed, such as a storage stabilizer, a curing accelerator, a filler, a silane coupling agent, and a thermoplastic resin.

[0036] Storage stabilizers are used to improve the life of curable resin compositions. In particular, when a thiol compound is used as a curing agent, the life of the curable resin composition tends to be shortened. Therefore, it is preferable to add a storage stabilizer. Examples of the storage stabilizer include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids.

[0037] Examples of the borate compound include trimethyl borate, triethyl borate (TEB), tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl)borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0038] Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0039] Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

[0040] Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0041] 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, 2,6-dimethylphenyl isocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), isocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, bicycloheptane triisocyanate, and the like.

[0042] Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, and caprylic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; halogenated fatty acids such as monochloroacetic acid and dichloroacetic acid; monobasic oxyacids such as glycolic acid and lactic acid; aliphatic aldehyde acids and ketone acids such as glyoxalic acid and acetic acid; aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, halogenated benzoic acids, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polybasic acids such as phthalic acid and trimesic acid.

[0043] Examples of the acid anhydride include aliphatic or aliphatic polybasic acid anhydrides such as succinic anhydride, dodecynylsuccinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride; and aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolimellitic anhydride.

[0044] Examples of the mercapto organic acid include mercapto aliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid; mercapto aliphatic monocarboxylic acids obtained by an esterification reaction between a hydroxy organic acid and a mercapto organic acid; and mercapto aromatic monocarboxylic acids such as mercaptobenzoic acid.

[0045] Of these, as the storage stabilizer, borate compounds are preferred from the viewpoints of versatility, safety, and improving storage stability, and triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate are more preferred, and triethyl borate is even more preferred. The content of the storage stability improver is, for example, 0.001 to 50 parts by mass, preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total content of the (A) curable resin.

[0046] The curing accelerator is not particularly limited, and for example, a latent curing accelerator can be used. Examples of latent curing accelerators include solid-dispersed latent curing accelerators. A solid-dispersed latent curing accelerator is a compound that is insoluble in a curable resin composition at room temperature (25°C) and becomes soluble upon heating, functioning as a curing accelerator in the curable resin composition. Examples of solid-dispersed latent curing accelerators include, but are not limited to, imidazole compounds that are solid at room temperature and solid-dispersed amine adduct latent curing accelerators. Examples of solid-dispersed amine adduct latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adducts), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts). Among these, solid-dispersed amine adduct latent curing accelerators are preferred.

[0047] Examples of the imidazole compound that is solid at room temperature include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 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-isocyanuric acid adduct, Examples of the methylimidazole include, but are not limited to, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide.

[0048] Examples of epoxy compounds that can be used as one of the raw materials for producing the solid dispersion type amine adduct latent curing accelerator (amine-epoxy adduct) include polyglycidyl ethers obtained by reacting epichlorohydrin with polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol; glycidyl ether esters obtained by reacting epichlorohydrin with hydroxy acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; phthalic acid, terephthalic acid, and the like; Examples of epoxy compounds include, but are not limited to, polyglycidyl esters obtained by reacting polycarboxylic acids such as taric acid with epichlorohydrin; glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0049] The amine compound used as a raw material for producing the solid dispersion type amine adduct latent curing accelerator may have one or more active hydrogen atoms capable of addition reaction with epoxy groups in the molecule, and at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in the molecule. Examples of such amine compounds include, but are not limited to, aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0050] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing accelerators with excellent curing acceleration capabilities. Examples of such compounds include primary or secondary amines having a tertiary amino group in the molecule, such as amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, and imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 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-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine Examples include alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as lysine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide; and the like.

[0051] When producing a latent curing accelerator by addition reaction of the above-mentioned epoxy compound and amine compound, an active hydrogen compound having two or more active hydrogen atoms 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 novolac resin, polyhydric alcohols such as trimethylolpropane, polycarboxylic acids such as adipic acid and phthalic acid, 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid, but are not limited thereto.

[0052] Examples of isocyanate compounds used as raw materials for producing the solid dispersion-type amine adduct-based latent curing accelerator include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such a terminal isocyanate group-containing compound include, but are not limited to, an addition compound having a terminal isocyanate group obtained by reacting tolylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting tolylene diisocyanate with pentaerythritol.

[0053] Furthermore, examples of urea compounds used as raw materials for producing the solid dispersion-type amine adduct latent curing accelerator include, but are not limited to, urea and thiourea.

[0054] The solid dispersion-type latent curing accelerator can be easily obtained, for example, by appropriately mixing the above-mentioned production raw materials, reacting them at a temperature of from room temperature to 200°C, cooling them to solidify them, and then pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content.

[0055] Representative examples of commercially available solid dispersion-type latent curing accelerators include, for example, amine-epoxy adducts (amine adducts), such as "PN-F," "Amicure PN-23," and "Amicure PN-H" manufactured by Ajinomoto Fine-Techno Co., Ltd., "Hardener X-3661S" and "Hardener X-3670S" manufactured by ACC Corporation, and "Novacure HX-3742" and "Novacure HX-3721" manufactured by Asahi Kasei Corporation, and urea-type adducts, such as "FXE-1000" and "FXR-1030" manufactured by T&K TOKA Corporation, but are not limited thereto.

[0056] The content of the curing accelerator is, for example, 0.1 to 100 parts by mass, preferably 1 to 60 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total content of the (A) curable resin.

[0057] Examples of fillers include finely powdered silica. The combined use of finely powdered silica with calcium carbonate can sometimes facilitate a balance between thixotropy and adhesion. Furthermore, when a solid dispersion-type substance is used as a curing accelerator, the finely powdered silica also functions as a precipitation inhibitor. Specific examples of such finely powdered silica include "RY-300" manufactured by Nippon Aerosil Co., Ltd.

[0058] The silane coupling agent can be used, for example, to improve adhesion and prevent the inorganic filler from falling off.

[0059] A thermoplastic resin may be added for the purpose of adjusting viscosity, etc., within a range that does not affect the effects of the present invention.

[0060] (E) Curable resin composition The curable resin composition according to this embodiment preferably has a viscosity (E-type viscometer, 25°C, 1 rpm) of 10 to 500 Pa·s. The viscosity (E-type viscometer, 25°C, 1 rpm) of the curable resin composition is more preferably 30 to 450 Pa·s, and even more preferably 30 to 400 Pa·s.

[0061] Furthermore, when the viscosity of the curable resin composition measured with an E-type viscometer at 25°C and 1 rpm is V1 and the viscosity measured with the E-type viscometer at 25°C and 10 rpm is V2, the ratio of V1 to V2 (V1 / V2) is preferably 1.5 to 6.0, more preferably 1.5 to 4.0, and even more preferably 1.5 to 3.5.

[0062] Alternatively, when the viscosity of the curable resin composition measured with an E-type viscometer at 25°C and 2 rpm is V3 and the viscosity measured with the E-type viscometer at 25°C and 20 rpm is V4, the ratio of the viscosity V3 to the viscosity V4 (V3 / V4) is preferably 1.5 to 6.0, more preferably 1.5 to 4.0, and even more preferably 1.5 to 3.5.

[0063] The curable resin composition has good thread breakability, specifically, the curable resin composition has a thread breakability of 15 mm or less, preferably 10 mm or less. The "fiber breakage resistance" is measured by the method described in the examples below.

[0064] The curable resin composition has good adhesion. Specifically, the curable resin composition has a strength of, for example, 1.5 N / mm 2 More than 2.0N / mm2 or more, preferably 2.0 to 10.0 N / mm 2 It has an adhesive strength of . The "adhesion" is measured by the method described in the examples below.

[0065] The curable resin composition is preferably used as an adhesive. More preferably, the curable resin composition is used as an adhesive for bonding members constituting an electronic component, such as a camera module. The curable resin composition is preferably an adhesive that is applied to an LCP (liquid crystal polymer).

[0066] The curable resin composition is preferably a one-component type. A one-component type curable resin composition is a resin composition that is provided in a state in which a curing agent and a curable resin are mixed in advance. When used, the curable resin composition is applied to a required area. Then, the curable resin composition is cured by heat, ultraviolet light, or the like.

[0067] The curable resin composition is preferably discharged from a nozzle during application. For example, in a dispenser, the composition is filled into a syringe and discharged through a nozzle onto the required area. When using a curable resin composition in this manner, it is important that the composition has good thread breakability and shape stability. The curable resin composition according to this embodiment can achieve good thread breakability without deteriorating adhesion and shape stability. Therefore, it is particularly suitable for applications in which the composition is discharged from a nozzle.

[0068] The method for producing the curable resin composition is not particularly limited and can be carried out according to a known method. That is, the curable resin, calcium carbonate, and a curing agent may be mixed with other components as needed.

[0069] Curing of the curable resin composition is not particularly difficult and can be carried out in accordance with conventionally known methods. For example, the applied curable resin composition can be cured by heating it at a temperature equal to or higher than room temperature. The heating temperature is, for example, 70 to 150°C, preferably 75 to 120°C. The heating time is, for example, 1 to 60 minutes, preferably 10 to 50 minutes, and more preferably 15 to 45 minutes. [Example]

[0070] The present invention will be described in more detail below using examples, but the present invention should not be construed as being limited by the following examples.

[0071] [Preparation of Curable Resin Composition] The components were mixed according to the blending ratios shown in Tables 1-1 to 1-4 to prepare curable resin compositions according to Examples 1 to 9 and Comparative Examples 1 to 8. In the tables, the blending amount of each component means parts by mass. Specifically, the amounts of curable resin and curing agent shown in the table were weighed into dedicated plastic containers. Then, using a planetary centrifugal mixer (Thinky Corporation: ARE-310), the mixture was thoroughly mixed at 2000 rpm at room temperature (25°C) for approximately 30 seconds to 1 minute to obtain a liquid mixture. Calcium carbonate, silica, storage stabilizer, and curing accelerator were added to the liquid mixture, and the mixture was mixed at 2000 rpm at room temperature (25°C) for approximately 30 seconds to 1 minute using a planetary centrifugal mixer (Kyoritsu Seiki Co., Ltd.: HM-200W) for 2 minutes at 900 rpm under vacuum (set to zero pressure) to obtain the desired curable resin composition.

[0072] The details of the materials used are as follows:

[0073] (1)Low viscosity curable resin YL-980: Mitsubishi Chemical Corporation, bisphenol A (BPA) liquid epoxy resin, epoxy equivalent 190 g / eq, molecular weight 380, viscosity 10-20 Pa·s (E-type viscometer, 25°C, 1 rpm)

[0074] (2) Solid curable resin 1004AF: Mitsubishi Chemical Corporation, bisphenol A (BPA) solid epoxy resin, epoxy equivalent 925g / eq, molecular weight 1850, solid at room temperature

[0075] (3) High viscosity curable resin EXA-4816: DIC Corporation, modified epoxy resin, epoxy equivalent 400 g / eq, 800, viscosity 1400 Pa·s (E-type viscometer, 25°C, 1 rpm) MX-135: Kaneka Corporation, core-shell dispersed epoxy resin, epoxy equivalent 223 g / eq, molecular weight 446, viscosity 190 Pa·s (E-type viscometer, 25°C, 1 rpm) EA-1010N: Shin-Nakamura Chemical Co., Ltd., glycidyl ether-containing epoxy acrylate, functional group equivalent weight 267 g / eq, molecular weight 420, viscosity 550 Pa·s (E-type viscometer, 25°C, 1 rpm)

[0076] (4) Hardener TMTP: Yodo Chemical Co., Ltd., trimethylolpropane tris(3-mercaptopropionate), thiol functional group equivalent 140g / eq PE-1: Showa Denko Co., Ltd., pentaerythritol 3-mercaptobutanoate (pentaerythritol tetrakis(3-mercaptobutyrate)), thiol functional group equivalent: 136 g / eq

[0077] (5) Calcium carbonate Hakuenka CC: manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate CaCO3, average particle size 50 nm, BET specific surface area 26.0 m 2 / g Hakuenka CC-R: manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate CaCO3, average particle size 80 nm, BET specific surface area 18.0 m 2 / g Vigot-10: Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 100 nm, BET specific surface area 13.5 m 2 / g Vigot-15: Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 150 nm, BET specific surface area 10.0 m 2 / g WB: Shiraishi Kogyo Co., Ltd., calcium carbonate CaCO3, average particle size 3.6 μm, BET specific surface area 0.6 m 2 / g

[0078] (6) Silica SP-04MS: Tokuyama Corporation, silica, average particle size 400 nm YA050C: Admatechs, silica, average particle size 50 nm RY-300: Nippon Aerosil Co., Ltd., fumed silica, average particle size 7 nm

[0079] (7) Storage stabilizer TEB: Triethyl borate, manufactured by Tokyo Chemical Industry Co., Ltd.

[0080] (8) Curing accelerator PN-F: Ajinomoto Fine-Techno Co., Ltd., amine epoxy adduct curing agent

[0081] [Evaluation of shape stability] The temperature of each curable resin composition obtained in the examples and comparative examples was kept at 25°C (±2°C), and the viscosity (Pa s) was measured using an E-type viscometer (Toki Sangyo Co., Ltd., "RE-85U", 3° x R9.7 rotor) with a 0.22 ml measurement sample at rotation speeds of 1 rpm and 10 rpm. Thereafter, the TI value (1 / 10 rpm) was calculated based on the following formula 1. (Equation 1) [TI value (1 / 10 rpm)] = [Viscosity measured at 1 rpm] / [Viscosity measured at 10 rpm] In addition, since there were some cases where the measurement limit was exceeded, measurements were also carried out at rotation speeds of 2 rpm and 20 rpm, and the TI value (2 / 20 rpm) was also calculated using the following formula 2. (Equation 2) [TI value (2 / 20 rpm)] = [Viscosity measured at 2 rpm] / [Viscosity measured at 20 rpm]

[0082] [Thread breakage] Each resin composition obtained in the examples and comparative examples was placed in a 10 ml syringe (PSY-10E) manufactured by Musashi Engineering, and filled by centrifugal degassing using a Musashi Engineering centrifugal degassing machine for syringes, AWATRON (AW-50-3). A Musashi Engineering needle (PN-21G-A) was attached to the filled syringe, and evaluation was performed under conditions of a discharge pressure of 300 kPa and a discharge time of 0.2 s. Specifically, a Musashi Engineering dispenser robot (350PC SmartSM-ΩX) was used to apply a spot of adhesive to a glass plate, varying the height of movement after dispensing from 1 mm to 25 mm. The height at which the adhesive broke directly above the discharge point was recorded as the thread breakage (mm) and observed.

[0083] [Adhesion] Two LCP test pieces (CM-529B, manufactured by ENEOS Liquid Crystal Co., Ltd.) measuring 100 mm x 25 mm x 2 mm thick were prepared, and their surfaces were lightly wiped with a cloth moistened with ethanol. The resin composition was uniformly applied to the surface of the LCP test piece to a thickness of approximately 1 mm. The two test pieces were attached and clamped with two clips so that the coated surfaces overlapped by approximately 12 mm. Any exuded resin composition was immediately wiped off with a cloth. The test pieces were evenly arranged in an oven and heated to 80°C for 30 minutes for curing and adhesion. Two test pieces were prepared for each resin. The tensile shear adhesive strength of the obtained test pieces was measured in accordance with JIS-K-6850 using a Tensilon universal testing machine (UTM-5T, manufactured by TOYO BALDWIN Co., Ltd.) (measurement environment: temperature 25°C / humidity 60%, tensile speed: 5 mm / min). Based on the maximum load (N) at which the test piece broke, the adhesive area (mm 2 The tensile shear adhesive strength was calculated using the following formula 3. The obtained tensile shear adhesive strength was used as the "adhesion strength." (Equation 3) [Tensile shear adhesive strength (N / mm 2 )]=[Maximum load (N)] / [Adhesive area (mm) 2 )]

[0084] Shape stability (TI value), thread breakage resistance (mm), adhesion strength (tensile shear adhesive strength (N / mm 2The measured values ​​of )) are shown in Tables 2-1 to 2-1. Furthermore, with regard to the TI value, those that were 2.0 or more were evaluated as ◯, those that were 1.5 to 2.0 were evaluated as △, and those that were 1.5 or less were evaluated as ×. Regarding thread breakage, threads with a breakage of 10 mm or less were evaluated as ◯, threads with a breakage of 10 mm to 15 mm as △, and threads with a breakage of 15 mm or more as ×. Adhesion strength: 2.0N / mm 2 Above: 〇, 1.5~2.0N / mm 2 △, 1.5N / mm 2 The following were evaluated as x:

[0085] [Discussion of evaluation results] The results of the above evaluations are shown in Tables 2-1 to 2-4. Comparative Examples 7 and 8, which lacked calcium carbonate, were inferior in resistance to thread breakage and shape stability. In contrast, the BET specific surface area is 5m 2 The resin compositions according to Examples 1 to 9 containing calcium carbonate of 1 / g or more were rated good in at least two of shape stability, resistance to thread breakage, and adhesion, and were excellent in balance of these properties. On the other hand, the average particle size of calcium carbonate is 5m 2 In Comparative Example 1, where the density was less than 1 / g, the desired shape stability was not obtained. Furthermore, when silica was used instead of calcium carbonate (Comparative Examples 2 to 6), some of the properties were improved compared to Comparative Examples 7 and 8, but the shape stability, thread breakage resistance, and adhesion could not be improved in a balanced manner to the same extent as in Examples 1 to 9.

[0086] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] Table 2-1 Table 2-2 Table 2-3 Table 2-4

Claims

1. (A) a curable resin; (B) BET specific surface area 5m 2 / g or more of calcium carbonate, (C) a curing agent; A curing accelerator; Including, the (A) curable resin contains an epoxy resin, The BET specific surface area of ​​the calcium carbonate (B) is 5 m 2 / g or more 30m 2 / g or less, the curing accelerator comprises at least one selected from the group consisting of an imidazole compound that is solid at room temperature, a reaction product of an amine compound with an epoxy compound, and a reaction product of an amine compound with an isocyanate compound or a urea compound, the (A) curable resin is 5 to 80 parts by mass per 100 parts by mass of the non-volatile components of the curable resin composition, the (B) calcium carbonate is 3 to 80 parts by mass per 100 parts by mass of the non-volatile components of the curable resin composition, A curable resin composition, wherein the (C) curing agent is 5 to 80 parts by mass per 100 parts by mass of the non-volatile components of the curable resin composition.

2. 2. The curable resin composition according to claim 1, wherein the curable resin (A) comprises at least one resin selected from a high-viscosity curable resin having a viscosity of 100 Pa s or more as measured at 25°C and 1 rpm with an E-type viscometer, and a solid curable resin that is a resin that is solid at 25°C.

3. The curable resin composition according to claim 2, wherein the high-viscosity curable resin and the solid curable resin are contained in an amount of 5 to 100 parts by mass relative to 100 parts by mass of the curable resin (A).

4. The curable resin composition according to any one of claims 1 to 3, having a viscosity of 10 to 500 Pa·s as measured at 25°C and 1 rpm using an E-type viscometer.

5. When V1 is a viscosity measured at 25°C and 1 rpm using an E-type viscometer and V2 is a viscosity measured at 25°C and 10 rpm using an E-type viscometer, the ratio of the viscosity V1 to the viscosity V2 of the curable resin composition (V1 / V2) is 1.5 to 6.0, or When a viscosity measured with an E-type viscometer at 25°C and 2 rpm is V3 and a viscosity measured with an E-type viscometer at 25°C and 20 rpm is V4, the ratio of the viscosity V3 to the viscosity V4 of the curable resin composition (V3 / V4) is 1.5 to 6.0; The curable resin composition according to any one of claims 1 to 4.

6. The curable resin composition according to any one of claims 1 to 5, wherein the (A) curable resin contains a compound having a (meth)acryloyl group.

7. The BET specific surface area of ​​the calcium carbonate (B) is 6 m 2 / g or more 30m 2 The curable resin composition according to any one of claims 1 to 6, wherein the viscosity is less than 1 / g.

8. The curable resin composition according to any one of claims 1 to 7, wherein the (C) curing agent comprises a polythiol compound having two or more mercapto groups in one molecule.

9. The curable resin composition according to any one of claims 1 to 8, wherein the (A) curable resin is 20 to 80 parts by mass per 100 parts by mass of non-volatile components of the curable resin composition.

10. The curable resin composition according to any one of claims 1 to 9, wherein the (B) calcium carbonate is 5 to 50 parts by mass per 100 parts by mass of non-volatile components of the curable resin composition.

11. The curable resin composition according to any one of claims 1 to 10, wherein the (C) curing agent is 10 to 50 parts by mass per 100 parts by mass of non-volatile components of the curable resin composition.

12. The curable resin composition according to any one of claims 1 to 11, which is applied by being discharged from a nozzle.

13. An adhesive comprising the curable resin composition according to any one of claims 1 to 12.

14. The adhesive of claim 13 for bonding between components of a camera module.

15. A bonding method comprising a step of discharging the curable resin composition according to any one of claims 1 to 12 from a nozzle.

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