Curable resin composition, adhesive, and bonding method

Abstract

To provide a curable resin composition with excellent thread breakability, adhesion, and shape stability. [Solution] (A) A curable resin and (B) a BET specific surface area of ​​5m 2 A curable resin composition comprising (C) a curing agent and (g) or more calcium carbonate.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, an adhesive, and a bonding 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 may be used to bond multiple components together. Such curable resin compositions are typically applied by coating.

[0003] When applying a resin composition, stable and good application is required. In this regard, Patent Document 1 (Japanese Patent Application Publication No. 2002-177843) discloses a dispenser device having a specific configuration that can perform stable and good application even when applying a high-viscosity, high-thixotropic paste. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-177843 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In curable resin compositions used as adhesives and the like, it may be necessary to use high-viscosity curable resins or solid curable resins to impart properties such as toughness, high heat resistance, and high reliability.

[0006] However, when high-viscosity curable resins or solid curable resins are incorporated, the resin composition becomes viscous. As a result, the applicability may deteriorate. For example, when the resin composition is dispensed through a nozzle during application, stringing is more likely to occur. In other words, the string breakability deteriorates. As a result, the cycle time tends to increase. In addition, the resin composition is more likely to adhere to areas other than the target area. To improve thread breakability, the addition of inorganic fillers may be considered. However, in this case, adhesion to the bonding surface tends to decrease. In addition, thixotropy may decrease. That is, the shape stability (shape retention) of the resin composition after coating decreases, and the coated area tends to spread after application. Therefore, it was difficult to achieve a good balance of improving thread breakability, adhesion, and shape stability.

[0007] Therefore, the object of the present invention is to provide a curable resin composition in which thread breakability, adhesion, and shape stability are improved in a well-balanced manner. [Means for solving the problem]

[0008] As a result of their investigation, the inventors found that the above problem can be solved by the following means. [1] (A) Curable resin and (B) BET specific surface area 5m 2 Calcium carbonate of / g or more, (C) A curable resin composition comprising a curing agent. [2] The curable resin composition according to [1], wherein the curable resin (A) comprises at least one resin selected from a high-viscosity curable resin, which has a viscosity of 100 Pa·s or more as measured by an E-type viscometer at 25°C and 1 rpm, and a solid curable resin, which is a solid resin at 25°C. [3] The curable resin composition according to [2], wherein the high viscosity curable resin and the solid curable resin are in amounts of 5 to 100 parts by mass per 100 parts by mass of the curable resin (A). [4] A curable resin composition according to any one of [1] to [3], wherein the viscosity measured at 25°C and 1 rpm using an E-type viscometer is 10 to 500 Pa·s. [5]When the viscosity measured at 25 °C and 1 rpm with an E-type viscometer is V1 and the viscosity measured at 25 °C and 10 rpm with an E-type viscometer is V2, the ratio (V1 / V2) of the viscosity V1 to the viscosity V2 of the curable resin composition is 1.5 to 6.0, or when the viscosity measured at 25 °C and 2 rpm with an E-type viscometer is V3 and the viscosity measured at 25 °C and 20 rpm with an E-type viscometer is V4, the ratio (V3 / V4) of the viscosity V3 to the viscosity V4 of the curable resin composition is 1.5 to 6.0, the curable resin composition according to any one of [1] to [4]. [6]The curable resin composition according to any one of [1] to [5], wherein the (A) curable resin contains one or more selected from an epoxy resin and a compound 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 and 50 m 2 / g or less, the curable resin composition according to any one of [1] to [7]. [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 5 to 80 parts by mass with respect to 100 parts by mass of the 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 with respect to 100 parts by mass of the non-volatile components of the curable resin composition.

[12] The curable resin composition according to [1] to

[11] , wherein the (C) curing agent is 5 to 80 parts by mass with respect to 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 containing the curable resin composition according to any one of [1] to

[13] .

[15] The adhesive according to

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

[16] An adhesion method having a step of discharging the curable resin composition according to any one of [1] to

[13] from a nozzle.

Advantages of the Invention

[0009] According to the present invention, there is provided a curable resin composition in which thread breakability, adhesion, and shape stability are improved in a well-balanced manner.

Embodiments for Carrying Out the Invention

[0010] The curable resin composition according to the present embodiment contains (A) a curable resin, (B) calcium carbonate having a BET specific surface area of 5 m 2 / g or more, and (C) a curing agent. According to the present embodiment, since calcium carbonate having a BET specific surface area of 5 m 2 / g or more is blended, thread breakability, adhesion, and shape stability can be improved in a well-balanced manner.

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

[0012] (A) Curing resin The curable resin may be any resin having a function of curing by heat, ultraviolet rays, or the like, and is not particularly limited.

[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, more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the non-volatile 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, phenol resins, melamine resins, and unsaturated polyester resins. Preferably, the curable resin contains an epoxy resin or a compound having a (meth)acryloyl group, and particularly preferably contains an epoxy resin.

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

[0016] "(meth)acryloyl group" refers to either an acryloyl group or a methacryloyl group, or both. Compounds having a (meth)acryloyl group include, for example, 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 paracumylphenol (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, tricyclodecanedimethanol 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 hydroxypivalate di(meth)acrylate, polyurethane having (meth)acryloyl groups, polyester having (meth)acryloyl groups, 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 include (tri / tetra)(meth)acrylate, glycerin propoxytri(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol (penta / hexa)(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified diglycerin tetra(meth)acrylate, and epoxy acrylate. Note that epoxy acrylate can also be considered epoxy resin.

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

[0018] A "high-viscosity curable resin" is a resin whose viscosity, as measured by an E-type viscometer at 25°C and 1 rpm, is 100 Pa·s or higher. The viscosity of a high-viscosity curable resin (E-type viscometer, 25°C, 1 rpm) is preferably 100 to 2000 Pa·s, 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. Furthermore, epoxy equivalent refers to the mass of 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, for example, "EXA-4816" (manufactured by DIC Corporation), "MX-135" (manufactured by Kaneka Corporation), and "EA-1010N" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0019] A "solid curing resin" is a resin that hardens to a solid state at 25°C. In a preferred embodiment, the curable resin includes a solid curable resin which 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. Specific examples of such solid curing resins include "1004AF" (manufactured by Mitsubishi Chemical Corporation).

[0020] The inclusion of a high-viscosity curable resin or a solid-curable resin can improve properties such as toughness, high heat resistance, and high reliability. On the other hand, the inclusion of such resins increases the viscosity of the resin composition, which generally worsens its ability to break threads. However, according to this embodiment, the problem of thread breakage is resolved by the use of calcium carbonate. Therefore, it is possible to realize a curable resin with excellent thread breakage properties while still containing a high-viscosity curable resin or a solid-curable resin. The total amount of high-viscosity curable resin and solid curable resin is, for example, 5 to 100 parts by mass per 100 parts by mass of curable resin.

[0021] Furthermore, the curable resin may include a low-viscosity curable resin in addition to a high-viscosity curable resin and / or a solid-curable resin. A "low-viscosity curable resin" is a resin having a viscosity of less than 100 Pa·s (E-type viscometer, 25°C, 1 rpm). The viscosity of the "low-viscosity curable resin" (E-type viscometer, 25°C, 1 rpm) 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, preferably 50 to 85 parts by mass, per 100 parts by mass of the curable resin.

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

[0023] (B) Calcium carbonate As mentioned above, calcium carbonate has a BET specific surface area of ​​5 m². 2 A material with a value of / g or higher is used. The BET specific surface area can be measured in accordance with the 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, for example, the "Macsorb HM-1210" manufactured by Mountec Co., Ltd. BET specific surface area 5m 2 By using calcium carbonate in amounts greater than / g, it is possible to improve thread breakability, shape stability, and adhesion in a well-balanced manner. Note: BET specific surface area 5m 2 If the amount is less than / g, it becomes difficult to achieve the desired shape stability, and adhesion also decreases. Furthermore, if other inorganic fillers such as silica are used instead of calcium carbonate, it is not possible to improve thread breakability, dimensional stability, and adhesion in a balanced manner.

[0024] The BET specific surface area of calcium carbonate should be 5 m 2 / g or more, preferably 6 m 2 / g or more, more preferably 7 m 2 / g or more, still more preferably 8 m 2 / g or more, particularly preferably 8 m 2 / g or more. Also, the BET specific surface area is preferably 50 m 2 / g or less, more preferably 40 m 2 / g or less, still more preferably 35 m 2 / g or less, particularly preferably 30 m 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, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the non-volatile components of the curable resin composition.

[0026] (C) Hardener The curing agent is a substance having a function of curing the curable resin by heat and / or ultraviolet irradiation, etc. The curing agent may be any substance having a function of curing the curable resin and is not particularly limited.

[0027] Preferably, a thiol compound having a mercapto group is used as the curing agent. More preferably, as the thiol compound, a polythiol compound having two or more mercapto groups in one molecule can be mentioned. That is, a polyfunctional thiol compound is preferably used. When a polyfunctional thiol compound is used, the curable resin composition can be rapidly cured at a low temperature. Also, since the polyfunctional thiol compound has a low viscosity, even when a high-viscosity resin is used, it is easy to lower the viscosity of the entire resin composition.

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

[0029] Examples of polythiol compounds include partial esters of polyols and mercaptoorganic acids, and complete esters of polyols and mercaptoorganic acids. Here, a partial ester is an ester of a polyol and a carboxylic acid in which some of the hydroxyl groups of the polyol form ester bonds. A complete ester is one in which all of the hydroxyl 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 mercapto and carboxyl groups obtained by the esterification reaction 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 mercapto organic acids, mercaptoaliphatic 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 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 curing agent content 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, per 100 parts by mass of the nonvolatile components of the curable resin composition.

[0035] (D) Other ingredients In addition to the components described above, the curable resin composition may contain other components as needed. Examples of other components include preservatives, stabilizers, curing accelerators, fillers, silane coupling agents, and thermoplastic resins.

[0036] Preservatives are used to improve the lifespan of curable resin compositions. In particular, when thiol compounds are used as curing agents, the lifespan of the curable resin composition tends to be shortened. Therefore, it is preferable to add preservatives. Examples of preservatives and stabilizers include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto-organic acids.

[0037] Examples of the borate compounds mentioned above 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-tetraoxowndecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxowndecyl)borane, trimenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

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

[0039] Examples of the above-mentioned aluminate compounds include triethylaluminate, tripropylaluminate, triisopropylaluminate, tributylaluminate, and trioctylaluminate.

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

[0041] Examples of the above isocyanate compounds 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, and tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene). Examples include isocyanates, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylenediisocyanate, and bicycloheptane triisocyanate.

[0042] Examples of the above-mentioned carboxylic acids 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 such as glyoxalic acid and violet acid; aliphatic polybasic acids such as ketonic acid, oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; and aromatic polybasic acids such as phthalic acid and trimesic acid.

[0043] Examples of the above-mentioned acid anhydrides include aliphatic or aliphatic polybasic acid anhydrides such as succinic anhydride, dodecinyl succinic anhydride, maleic anhydride, adducts of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride, as well as aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyrrolimellitic anhydride.

[0044] Examples of the above-mentioned mercapto-organic acids include mercaptoaliphatic monocarboxylic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, and dimercaptosuccinic acid; mercaptoaliphatic monocarboxylic acids obtained by the esterification reaction of a hydroxy organic acid with a mercapto-organic acid; and mercaptoaromatic monocarboxylic acids such as mercaptobenzoic acid.

[0045] Of these, borate compounds are preferred as preservatives due to their versatility, safety, and ability to improve preservation stability. 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, when the total content of (A) the curable resin is 100 parts by mass.

[0046] The curing accelerator is not particularly limited, but for example, a latent curing accelerator can be used. An example of a latent curing accelerator is a solid-dispersed latent curing accelerator. A solid-dispersed latent curing accelerator is a compound that is insoluble in the curable resin composition at room temperature (25°C), becomes solubilized by heating, and functions 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-type latent curing accelerators. Examples of solid-dispersed amine adduct-type latent curing accelerators include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems), etc. Of these, solid-dispersed amine adduct-type latent curing accelerators are preferred.

[0047] Examples of the imidazole compounds that are 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, and 2,4-diamino-6-(2′-methylimidazolyl-(1)′)-ethyl-S-triazine isocyanuric acid adduct. Examples 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)-azivoyldiamide.

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

[0049] The amine compound used as a raw material for the production of the solid-dispersible amine adduct-type latent curing accelerator described above may have at least one active hydrogen atom capable of addition reaction with an epoxy group, and at least one functional group selected from primary, secondary, and tertiary amino groups. 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 heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0050] Furthermore, 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 amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine, as well as primary or secondary amines having a tertiary amino group in the molecule, such as 2-methylimidazole, 2-ethylimidal, 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-Phenylimidazolin, 1-(2-Hydroxy-3-Butoxypropyl)-2-Methylimidazolin, 2-(Dimethylaminomethyl)phenol, 2,4,6-Tris(Dimethylaminomethyl)phenol, N-β-Hydroxyethylmorpholine, 2-Dimethylaminoethanethiol, 2-Mercaptophi Examples include alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in their 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.

[0051] When producing a latent curing accelerator by addition reaction of the epoxy compound and amine compound mentioned above, an active hydrogen compound having two or more active hydrogen atoms in its molecule can also be added. Examples of such active hydrogen compounds include, but are not limited to, polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resins, polyhydric alcohols such as trimethylolpropane, polyhydric carboxylic 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.

[0052] Examples of isocyanate compounds used as raw materials for the production of the above-mentioned solid-dispersible 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 also terminal isocyanate group-containing compounds obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, addition compounds having terminal isocyanate groups obtained by the reaction of tolylene diisocyanate and trimethylolpropane, and addition compounds having terminal isocyanate groups obtained by the reaction of tolylene diisocyanate and pentaerythritol.

[0053] Furthermore, examples of urea compounds used as raw materials for the production of the above-mentioned solid-dispersed amine adduct-based latent curing accelerator include, but are not limited to, urea and thiourea.

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

[0055] Representative examples of commercially available solid-disperse latent curing accelerators include, for example, amine-epoxy adduct systems (amine adduct systems) such as "PN-F," "Amicure PN-23," and "Amicure PN-H" from Ajinomoto Fine Techno Co., Ltd., "Hardener X-3661S" and "Hardener X-3670S" from ACR Co., Ltd., and "NovaCure HX-3742" and "NovaCure HX-3721" from Asahi Kasei Corporation. Examples of urea-type adduct systems include "FXE-1000" and "FXR-1030" from T&K TOKA Co., Ltd., but are not limited to these.

[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, when the total content of (A) the curable resin is 100 parts by mass.

[0057] Examples of fillers include finely powdered silica. Using finely powdered silica in combination with calcium carbonate can sometimes help balance thixotropy and adhesion. Furthermore, when a solid dispersion type substance is used as a curing accelerator, finely powdered silica also functions as a precipitate inhibitor. A specific example of such finely powdered silica is "RY-300" manufactured by Nippon Aerosil Co., Ltd.

[0058] Silane coupling agents can be used, for example, to improve adhesion and suppress the shedding of inorganic fillers.

[0059] Thermoplastic resins may be added for viscosity adjustment purposes, etc., to the extent that they do 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 of 10 to 500 Pa·s (E-type viscometer, 25°C, 1 rpm). More preferably, the viscosity of the curable resin composition (E-type viscometer, 25°C, 1 rpm) is 30 to 450 Pa·s, and more preferably 30 to 400 Pa·s.

[0061] Furthermore, when the viscosity of the curable resin composition is measured at 25°C and 1 rpm using an E-type viscometer, V1 is the viscosity measured at 25°C and 1 rpm, and V2 is the viscosity measured at 25°C and 10 rpm using an E-type viscometer, the ratio of V1 to V2 (V1 / V2) is preferably 1.5 to 6.0. The ratio (V1 / V2) is 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 is measured at 25°C and 2 rpm using an E-type viscometer, V3 is the viscosity measured at 25°C and 2 rpm, and V4 is the viscosity measured at 25°C and 20 rpm using an E-type viscometer, the ratio of viscosity V3 to V4 (V3 / V4) is preferably 1.5 to 6.0. The ratio (V3 / V4) is 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 thread breakability of 15 mm or less, preferably 10 mm or less. "Thread breakability" is measured by the method described in the examples below.

[0064] The curable resin composition has good adhesion. Specifically, the curable resin composition has, for example, 1.5 N / mm² 2 Preferably 2.0 N / mm2 Preferably, the above range is 2.0 to 10.0 N / mm². 2 It has strong adhesion. "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 components that make up an electronic component together. Examples of electronic components include camera modules. Furthermore, the curable resin composition is preferably an adhesive used by being applied to LCP (liquid crystal polymer).

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

[0067] The curable resin composition is preferably dispensed from a nozzle during application. For example, in a dispenser, it is filled into a syringe and dispensed to the required portion via a nozzle. When using the curable resin composition in this manner, it is important that it has good thread-breakability and dimensional stability. The curable resin composition according to this embodiment can achieve good thread-breakability without degrading adhesion and dimensional stability. Therefore, it is particularly suitable for applications where it is dispensed from a nozzle.

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

[0069] The curing of the curable resin composition is not particularly difficult and can be carried out according to conventionally known methods. For example, the curable resin composition can be cured by heating the applied material at a temperature above 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, more preferably 15 to 45 minutes. [Examples]

[0070] The present invention will be described in more detail below with reference to examples. However, the present invention should not be interpreted as being limited to the following examples.

[0071] [Preparation of curable resin composition] The curable resin compositions for Examples 1-9 and Comparative Examples 1-8 were prepared by mixing each component according to the formulations shown in Tables 1-1 to 1-4. In the tables, the amount of each component represents parts by mass. Specifically, the curable resin and curing agent in the amounts shown in the table were measured out into a dedicated plastic container. Then, using a rotating / revolving mixer, Awatori Rentaro (Sinky Co., Ltd.: 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, a preservative stabilizer, and a curing accelerator were added to this liquid mixture and mixed using a rotating / revolving mixer at 2000 rpm at room temperature (25°C) for approximately 30 seconds to 1 minute. Finally, the mixture was degassed under vacuum (pressure set to 0) at 900 rpm for 2 minutes using a Kyoritsu Seiki Co., Ltd. automatic revolving stirring and degassing machine HM-200W 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: Manufactured by Mitsubishi Chemical Corporation, bisphenol A (BPA) type liquid epoxy resin, epoxy equivalent weight 190 g / eq, molecular weight 380, viscosity 10-20 Pa·s (E-type viscometer, 25°C, 1 rpm)

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

[0075] (3) High viscosity curable resin EXA-4816: DIC Corporation, modified epoxy resin, epoxy equivalent 400g / eq, 800, viscosity 1400 Pa·s (E-type viscometer, 25℃, 1 rpm) MX-135: Manufactured by Kaneka Corporation, core-shell dispersed epoxy resin, epoxy equivalent weight 223 g / eq, molecular weight 446, viscosity 190 Pa·s (E-type viscometer, 25°C, 1 rpm) EA-1010N: Manufactured by Shin-Nakamura Chemical Industry 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℃, 1 rpm)

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

[0077] (5) Calcium carbonate Shiratsuka CC: Manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 50 nm, BET specific surface area 26.0 m² 2 / g Shiraishi Kogyo Co., Ltd. manufactured, calcium carbonate (CaCO3), average particle size 80nm, BET specific surface area 18.0m². 2 / g Vigot-10: Manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 100 nm, BET specific surface area 13.5.0 m² 2 / g Vigot-15: Manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 150 nm, BET specific surface area 10.0 m². 2 / g WB: Manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate (CaCO3), average particle size 3.6 μm, BET specific surface area 0.6 m² 2 / g

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

[0079] (7) Preservatives and stabilizers TEB: Triethyl borate, manufactured by Tokyo Chemical Industry Co., Ltd.

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

[0081] [Evaluation of shape stability] The curable resin compositions obtained in the examples and comparative examples were kept at a temperature of 25°C (±2°C), and their viscosity (Pa·s) was measured using an E-type viscometer (RE-85U, manufactured by Toki Sangyo Co., Ltd., 3°×R9.7 rotor) with a sample size of 0.22 ml and rotation speeds of 1 rpm and 10 rpm. Subsequently, 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 some cases exceeded the measurement limit, measurements were also taken under conditions of 2 rpm and 20 rpm rotation speeds, and the TI value (2 / 20 rpm) was also calculated based on 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 Co., Ltd., and filled by centrifugal degassing using a Musashi Engineering Co., Ltd. syringe centrifugal degasser AWATRON (AW-50-3). A needle (PN-21G-A) manufactured by Musashi Engineering Co., Ltd. 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, using a Musashi Engineering Co., Ltd. dispenser robot (350PC SmartSM-ΩX), the movement height after adhesive discharge was varied from 1 mm to 25 mm, and dots were applied to a glass plate. The height at which the adhesive broke directly above the discharge point was defined as the thread breakage (mm), and observations were made.

[0083] [Adhesion] Two LCP test specimens (CM-529B, manufactured by ENEOS LCD Co., Ltd.) measuring 100mm x 25mm x 2mm thick were prepared, and their surfaces were lightly wiped with a cloth dampened with ethanol. The resin composition was uniformly applied to the surface of the LCP test specimens to a thickness of approximately 1mm. The two test specimens were joined together with two clips so that the coated surfaces overlapped by approximately 12mm, and then compressed. Any resin composition that seeped out was immediately wiped away with a cloth. The test specimens were evenly arranged in an oven and heated and cured at 80°C for 30 minutes to bond them together. Two test specimens were prepared for each type of resin. The tensile shear bond strength of the obtained test specimens was measured using a Tensilon universal testing machine (UTM-5T, manufactured by TOYO BALDWIN Co., Ltd.) in accordance with JIS-K-6850 (measurement environment: temperature 25°C / humidity 60%, tensile speed: 5mm / min). Based on the maximum load (N) at which the test specimen broke, the bonding area (mm²) 2 The tensile shear bond strength was calculated using the following formula 3, and the obtained tensile shear bond strength was defined as the "adhesion force". (Equation 3) [Tensile shear bond strength (N / mm²)] 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 ​​for )) are shown in Tables 2-1 to 2-1. Furthermore, regarding the TI value, those with a value of 2.0 or higher were evaluated as ○, those with a value between 1.5 and 2.0 as △, and those with a value of 1.5 or lower as ×. Regarding thread breakage, we evaluated it as follows: ○ for breakage of 10mm or less, △ for breakage between 10mm and 15mm, and × for breakage of 15mm or more. Regarding adhesion strength, 2.0 N / mm 2 The above items are marked with a circle (〇), and the values ​​are 1.5~2.0 N / mm². 2 The one with the triangle symbol, 1.5 N / mm 2 The following were marked with an "X".

[0085] [Discussion of evaluation results] The results of each of the above evaluations are shown in Tables 2-1 to 2-4. Comparative Examples 7 and 8, which lacked calcium carbonate, exhibited inferiority in thread breakability and dimensional stability. In contrast, the BET specific surface area is 5m² 2 The resin compositions according to Examples 1 to 9, which contained calcium carbonate of 1 / g or more, showed excellent balance in at least two of the following properties: dimensional stability, string breakability, and adhesion. On the other hand, the average particle size of calcium carbonate is 5m 2 In Comparative Example 1, where the value was less than / g, the desired shape stability was not achieved. Furthermore, when silica was used instead of calcium carbonate (Comparative Examples 2-6), although some properties were improved compared to Comparative Examples 7 and 8, it was not possible to achieve the same level of balanced improvement in shape stability, thread breakability, and adhesion as in Examples 1-9.

[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) Curable resin and (B) BET specific surface area 5m 2 Calcium carbonate of / g or more, (C) Hardener and A curable resin composition containing [the specified ingredient].

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 by an E-type viscometer at 25°C and 1 rpm, and a solid curable resin that is a 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 in amounts of 5 to 100 parts by mass with respect to 100 parts by mass of the curable resin (A).

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

5. When V1 is the viscosity measured at 25°C and 1 rpm using an E-type viscometer, and V2 is the viscosity measured at 25°C and 10 rpm using an E-type viscometer, the ratio of viscosity V1 to viscosity V2 of the curable resin composition (V1 / V2) is 1.5 to 6.0, or When V3 is the viscosity measured at 25°C and 2 rpm using an E-type viscometer, and V4 is the viscosity measured at 25°C and 20 rpm using an E-type viscometer, the ratio of viscosity V3 to viscosity V4 (V3 / V4) of the curable resin composition is 1.5 to 6.

0. A 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 curable resin (A) comprises one or more selected from epoxy resins and compounds having a (meth)acryloyl group.

7. (A) A curable resin composition according to any one of claims 1 to 6, wherein component (A) comprises an epoxy resin.

8. The BET specific surface area of ​​the aforementioned (B) calcium carbonate is 5 m². 2 / g or more 50m 2 A curable resin composition according to any one of claims 1 to 7, wherein the amount is less than or equal to / g.

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

10. The curable resin composition according to any one of claims 1 to 9, wherein the curable resin (A) is 5 to 80 parts by mass with respect to 100 parts by mass of the nonvolatile component of the curable resin composition.

11. The curable resin composition according to any one of claims 1 to 10, wherein the amount of (B) calcium carbonate is 3 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.

12. The curable resin composition according to claims 1 to 11, wherein the amount of the curing agent (C) is 5 to 80 parts by mass per 100 parts by mass of the nonvolatile component of the curable resin composition.

13. A curable resin composition according to any one of claims 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 claims 1 to 13.

15. The adhesive according to claim 14, for bonding components of a camera module.

16. A bonding method comprising the step of discharging a curable resin composition according to any one of claims 1 to 13 from a nozzle.

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