Resin composition and adhesive

Abstract

To provide a thiol resin composition of a new composition and an adhesive.SOLUTION: A resin composition contains (A) a polythiol compound, (B) a cyclic carbodiimide compound, and (C) a curing catalyst. The ratio of a thiol group equivalent number of component (A) to a carbodiimide group equivalent number of component (B) (thiol group equivalent number of / carbodiimide group equivalent number) is 2.0-6.0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resinous composition, an adhesive containing the same, a cured product thereof, and a semiconductor device and an electronic part each containing the cured product. [Background technology]

[0002] 2. Description of the Related Art Currently, adhesives, sealants, etc. containing curable resin compositions are often used for the assembly and mounting of electronic components, such as semiconductor chips, used in semiconductor devices, for the purpose of maintaining reliability, etc.

[0003] As resin compositions used in adhesives and sealants for such electronic components, for example, epoxy-thiol resin compositions (Patent Documents 1 and 2) and ene-thiol resin compositions (Patent Document 3) using a thiol curing agent as a curing agent have been disclosed. The type of resin composition to be used can be selected according to the application location of the adhesive. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-211969 [Patent Document 2] Japanese Patent Application Publication No. 6-211970 [Patent Document 3] JP 2014-77024 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the current situation where adhesives are used in a wide variety of locations, there is a demand for thiol-based resin compositions with new compositions that can be used in a variety of applications.

[0006] Therefore, an object of the present invention is to provide a thiol-based resin composition and an adhesive having a new composition. [Means for solving the problem]

[0007] The present inventors considered that, since a carbodiimide group reacts with a hydroxyl group, a carbodiimide group also reacts with a thiol group. As a result of further investigation, they found that by appropriately selecting a cyclic carbodiimide compound from among the carbodiimide compounds, a curing reaction with a polythiol compound proceeds appropriately, the generation of voids during curing is suppressed, and a new resin composition that can be used as an adhesive and has high storage stability under refrigeration can be realized.

[0008] Specific means for solving the above problems are as follows. A first embodiment of the present invention is the following resin composition. (1)(A) a polythiol compound, (B) a cyclic carbodiimide compound, and (C) Curing catalyst Including, A resin composition, wherein the ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (number of thiol group equivalents / number of carbodiimide group equivalents) is 2.0 to 6.0. (2) The resin composition according to the above (1), wherein the ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (number of thiol group equivalents / number of carbodiimide group equivalents) is 2.0 to 4.0. (3) The resin composition according to (1) or (2) above, further comprising (D) a thermosetting resin monomer or prepolymer compound that reacts with the component (A). (4) The resin composition according to (3) above, wherein the component (D) comprises at least one of (D1) a (meth)acrylate compound and (D2) an epoxy compound.

[0009] A second embodiment of the present invention is (5) an adhesive containing the resin composition according to any one of (1) to (4) above. A third embodiment of the present invention is (6) a cured product obtained by curing the resin composition according to any one of (1) to (4) above, or the adhesive according to (5) above. A fourth embodiment of the present invention is (7) a semiconductor device including the cured product according to (6) above. A fifth embodiment of the present invention is (8) an electronic component including the semiconductor device according to (7) above. Effect of the Invention

[0010] According to the first embodiment of the present invention, a resin composition having excellent thermosetting properties, suppressing the generation of voids during curing, and having excellent storage stability under freezing can be obtained. According to the second embodiment of the present invention, an adhesive having excellent thermosetting properties, suppressing the generation of voids during curing, and having excellent storage stability under freezing can be obtained. Furthermore, according to the third embodiment of the present invention, a cured product in which voids are suppressed can be obtained. According to the fourth embodiment of the present invention, a semiconductor device including a cured product in which voids are suppressed can be obtained. According to the fifth embodiment of the present invention, an electronic component including a semiconductor device including a cured product in which voids are suppressed can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Resin composition] The resin composition according to the first embodiment of the present invention comprises: (A) a polythiol compound, (B) a cyclic carbodiimide compound, and (C) Curing catalyst Including, The ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (thiol group equivalents / carbodiimide group equivalents) is 2.0 to 6.0. According to this embodiment, it is possible to obtain a resin composition that has excellent thermosetting properties, suppresses the generation of voids during curing, and has excellent storage stability under refrigeration.

[0012] (A) Polythiol compound The resin composition of the present embodiment contains (A) a polythiol compound (hereinafter also referred to as "(A) component"). The (A) component is not particularly limited as long as it has two or more thiol groups. The (A) component preferably has three or more thiol groups. The (A) component preferably has a thiol equivalent of 90 to 150 g / eq, more preferably 90 to 140 g / eq, and even more preferably 90 to 130 g / eq.

[0013] In the present embodiment, from the viewpoint of moisture resistance, it is preferable to use a polythiol compound (A) that does not have an ester bond in the molecule. Examples of such a polythiol compound (A) include glycoluril compounds represented by the following general formula (1).

[0014] [ka]

[0015] In general formula (1), R 1 , and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. n is an integer of 0 to 10.

[0016] Furthermore, the component (A) may be a compound represented by the following chemical formula (2) or (3).

[0017] [ka]

[0018] [ka]

[0019] The compounds represented by chemical formula (2) or (3) are more preferred as component (A).

[0020] Furthermore, the (A) polythiol compound having no ester bond or the like in the molecule includes a polythiol compound represented by the general formula (4).

[0021] [ka]

[0022] In general formula (4), R 3 , R 4 , R 5 and R 6 are each independently hydrogen or C n H 2n SH (n is 2 to 6). Furthermore, R 3 , R 4、 R 5 and R 6 At least one of the following is C n H 2n SH (n is 2 to 6). In terms of curability, n of the polythiol compound of the component (A) represented by the general formula (4) is preferably 2 to 4. In terms of the balance between the physical properties of the cured product and the curing speed, this polythiol compound is more preferably a mercaptopropyl group in which n is 3. The component (A) represented by the general formula (4) itself has a sufficiently flexible skeleton, so it is effective when it is desired to lower the elastic modulus of the cured product. By adding the component (A) represented by the general formula (4), the elastic modulus of the cured product can be controlled, so that the adhesive strength (particularly the peel strength) after curing can be increased.

[0023] Commercially available products of component (A) that do not have an ester bond in the molecule include thiol glycoluril derivative manufactured by Shikoku Chemical Industry Co., Ltd. (product name: TS-G (corresponding to chemical formula (2)), thiol equivalent: 100 g / eq), C3 TS-G (corresponding to chemical formula (3)), thiol equivalent: 114 g / eq)), and thiol compound manufactured by SC Organic Chemical Co., Ltd. (product name: PEPT (corresponding to general formula (4)), thiol equivalent: 124 g / eq)).

[0024] Examples of polythiol compounds having an ester bond in the molecule include pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate, and the like. anurate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), and trimethylolethane tris(3-mercaptobutyrate).

[0025] Commercially available products of component (A) having an ester bond in the molecule include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: Examples of such amines include dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: KarenzMT (registered trademark) PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K.: KarenzMT (registered trademark) NR1).

[0026] As the component (A), any one of them may be used alone, or two or more of them may be used in combination. A component (A) having an ester bond in the molecule and a component (A) having no ester bond in the molecule may be used in combination.

[0027] (B) Cyclic carbodiimide compound The resin composition of the present embodiment contains (B) a cyclic carbodiimide compound (hereinafter also referred to as "component (B)"). The cyclic carbodiimide compound has a cyclic structure. The cyclic structure has one carbodiimide group (-N=C=N-), and the first nitrogen and the second nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and further preferably 10 to 20. The cyclic carbodiimide compound may have a plurality of cyclic structures.

[0028] The cyclic carbodiimide compound used in the present embodiment is preferably a cyclic carbodiimide compound represented by the following general formula (5).

[0029] [ka]

[0030] In general formula (5), Ar 1 ~Ar 4 are each independently an aromatic group. The aromatic group may be substituted with an alkyl group or an aryl group having 1 to 6 carbon atoms. Examples of the aromatic group include aromatic groups such as a phenylene group and a naphthalenediyl group.

[0031] Ar 1 ~Ar 4 is preferably a phenyl group, since this improves film-forming properties.

[0032] X is a divalent or tetravalent group. When X is divalent, q is 0, and when X is tetravalent, q is 1. X is preferably any one of the following formulae (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), and (5-vii).

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] In formula (5-i), n is an integer of 1 to 6. Examples of the group (5-i) include a methylene group, an ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentane group, and a 1,6-hexane group.

[0038] In the formulas (5-ii) to (5-v), m and n each independently represent an integer of 0 to 4. A methylene group where m=0 represents a single bond.

[0039] In addition, in formula (5-vi), R 1 and R 2 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, a sec-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, an iso-butyl group, an n-pentyl group, a sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, and the like.

[0040] Among the cyclic carbodiimide compounds represented by formula (5), a compound represented by the following general formula (5-0) is preferred.

[0041] [ka]

[0042] In the general formula (5-0), X is preferably any one of the above-mentioned (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), and (5-vii). Y and Z are each independently a substituent other than an alkyl group having 1 to 6 carbon atoms or a phenyl group. As the substituent other than an alkyl group having 1 to 6 carbon atoms or a phenyl group, a conventionally known substituent can be applied, and examples thereof include an alkyl group having 7 or more carbon atoms, an aryl group other than a phenyl group, an alkoxy group, a hydroxy group, an aldehyde group, an acyl group, a carboxyl group, an ester group, a nitro group, an amino group, a sulfo group, a sulfonyloxy group, a halogeno group, a silyl group, a vinyl group, a fluoroalkyl group, a cyano group, an isonitrile group, an amide group, an imide group, and a thiol group.

[0043] Among them, a compound represented by the following chemical formula (5-1) or the following chemical formula (5-2) is preferable.

[0044] [ka]

[0045] [ka]

[0046] In this embodiment, the ratio of the thiol group equivalent number of component (A) to the carbodiimide group equivalent number of component (B) (thiol group equivalent number / carbodiimide group equivalent number) is 2.0 to 6.0, preferably 2.0 to 4.0. In this specification, the functional group equivalent number such as carbodiimide equivalent number and thiol equivalent number represents the molecular weight of a compound per functional group, and the functional group equivalent number such as carbodiimide group equivalent number and thiol group equivalent number represents the number of functional groups (equivalent number) per compound mass (charge amount). Theoretically, the thiol equivalent number of component (A) is the number obtained by dividing the molecular weight of component (A) by the number of thiol groups in one molecule. The actual thiol equivalent number can be determined by, for example, measuring the thiol value by potential difference. The carbodiimide equivalent number of (B) cyclic carbodiimide compound is theoretically equal to the number obtained by dividing the molecular weight of the cyclic carbodiimide compound by the number of carbodiimide groups in one molecule. The actual carbodiimide equivalent can be measured, for example, by NMR. The thiol group equivalent number of the (A) component is the number of thiol groups (equivalent number) per mass (charge amount) of the (A) component, and is the quotient obtained by dividing the mass (g) of the (A) polythiol compound by the thiol equivalent of the polythiol compound (if multiple thiol compounds are included, the sum of such quotients for each thiol compound). The carbodiimide group equivalent number of the (B) component is the number of carbodiimide groups (equivalent number) per mass (charge amount) of the (B) component, and is the quotient obtained by dividing the mass (g) of the (B) cyclic carbodiimide compound by the carbodiimide equivalent of the cyclic carbodiimide compound (if multiple cyclic carbodiimide compounds are included, the sum of such quotients for each cyclic carbodiimide compound). By setting the ratio of [thiol group equivalents of component (A)] / [carbodiimide group equivalents of component (B)] in the range of 2.0 to 6.0, a certain amount or more of carbodiimide groups and thiol groups react with each other, and molecular crosslinks are sufficiently formed, making it easier to develop high adhesive strength.

[0047] The present inventors considered that carbodiimide groups react with hydroxyl groups, and therefore carbodiimide groups also react with thiol groups. As a result of further investigation, it was found that by appropriately selecting a cyclic carbodiimide compound from among the carbodiimide compounds, a curing reaction with a polythiol compound proceeds appropriately, the generation of voids during curing is suppressed, and a new resin composition with high storage stability under refrigeration can be realized that can be used as an adhesive. Since the cyclic carbodiimide compound has a cyclic structure having a carbodiimide group, it is believed that this reduces steric hindrance around the carbodiimide group, and the thermosetting reaction at a relatively low temperature proceeds efficiently, and the generation of voids during curing is also suppressed. On the other hand, a non-cyclic polycarbodiimide compound in which the carbodiimide group is not included in the cyclic structure has multiple carbodiimide groups in the molecule that can react with thiol groups, but because it is a chain, the degree of freedom of the molecular chain is large, and the carbodiimide group is subjected to steric hindrance of the molecular chain, so it is believed that the reactivity with the thiol group of the polythiol compound is reduced. Moreover, unlike cyclic carbodiimide compounds, such non-cyclic polycarbodiimide compounds generated voids during curing. This is thought to be because such non-cyclic polycarbodiimide compounds have inferior heat resistance to cyclic carbodiimide compounds, and molecular chains are cut during curing, generating voids. Furthermore, non-cyclic monocarbodiimide compounds having only one carbodiimide group in the molecule could not form three-dimensional crosslinks and did not cure by heat.

[0048] [Method of producing cyclic carbodiimide compound] In this embodiment, the method for producing the cyclic carbodiimide compound is not particularly limited, and the compound can be produced by a conventionally known method (for example, the method described in International Publication No. 2010 / 071211 and JP-A-2011-256139). For example, the compound can be produced from an amine via an isocyanate, from an amine via an isothiocyanate, from an amine via a triphenylphosphine, from an amine via a urea, from an amine via a thiourea, from a carboxylic acid via an isocyanate, or by inducing a lactam.

[0049] As the cyclic carbodiimide compound, a commercially available product may be used.

[0050] (C) Curing catalyst The resin composition of this embodiment contains a curing catalyst (C) (hereinafter, also referred to as "component (C)"). The curing catalyst (C) used in this embodiment is not particularly limited as long as it is a curing catalyst for a (meth)acrylate compound, and a known catalyst can be used, but it is preferably a latent curing catalyst. The latent curing catalyst of the component (C) is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst, and examples of the latent curing catalyst include imidazole compounds that are solid at room temperature; solid dispersion type amine adduct latent curing catalysts such as 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).

[0051] Examples of 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, 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, N,N'-(2-methylimidazolyl-(1)-ethyl)-adiboyldiamide, and the like, but are not limited thereto.

[0052] Examples of epoxy compounds that can be used as one of the raw materials for manufacturing a solid dispersion type amine adduct latent curing catalyst (amine-epoxy adduct system) 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 hydroxycarboxylic 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 a polycarboxylic acid such as glycidyl acid with epichlorohydrin; glycidyl amine compounds obtained by reacting 4,4'-diaminodiphenylmethane, m-aminophenol, or the like with epichlorohydrin; and further, 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.

[0053] The amine compound used as another raw material for manufacturing the solid dispersion type amine adduct latent curing catalyst may have at least one active hydrogen in the molecule capable of addition reaction with an epoxy group, and at least one functional group selected from a primary amino group, a secondary amino group, and a tertiary amino group in the molecule. Examples of such amine compounds are shown below, but are not limited to these. For example, 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; heterocyclic compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine; and the like, but are not limited to these.

[0054] Among these, compounds having a tertiary amino group in the molecule are particularly useful as raw materials for providing latent curing catalysts with excellent curing acceleration ability. Examples of such compounds include 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. These compounds include primary or secondary amines having a tertiary amino group in the molecule, such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxyethyl)-2-methylaminoethanol, and 1-hydroxyethyl-2-methylaminoethanol. 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-hydroxyethyl mol Examples of the tertiary amino acid include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group in the molecule, such as holin, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 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.

[0055] As another isocyanate compound used as a raw material for the solid dispersion type amine adduct latent curing catalyst, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and further, compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds can also be used. Examples of such a terminal isocyanate group-containing compound include an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an addition compound having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol, but are not limited to these.

[0056] Examples of the urea compound include, but are not limited to, urea and thiourea.

[0057] The solid dispersion type latent curing catalyst that can be used in this embodiment is, for example, the above-mentioned combination of two components, (a) an amine compound and an epoxy compound, (b) a combination of three components, the above-mentioned two components and an active hydrogen compound, or (c) a combination of two or three components, the above-mentioned amine compound and an isocyanate compound and / or a urea compound. These can be easily prepared by mixing the components, reacting them at a temperature between room temperature and 200°C, cooling and solidifying 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.

[0058] Representative examples of commercially available solid dispersion-type latent curing catalysts as mentioned above include amine-epoxy adducts (amine adducts), such as "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACS Corporation), "Hardener X-3670S" (product name of ACS Corporation), "Novacure HX-3742" (product name of Asahi Kasei E-materials Corporation), "Novacure HX-3721" (product name of Asahi Kasei E-materials Corporation), "Novacure HXA9322HP" (product name of Asahi Kasei E-materials Corporation), "FXR1121" (product name of T&K Examples of urea-type adducts include "Fujicure FXE-1000" (product name of T&K TOKA Corporation) and "Fujicure FXR-1030" (product name of T&K TOKA Corporation), but are not limited to these. The component (C) may be used alone or in combination of two or more types.

[0059] The content of the (C) curing catalyst is preferably from 0.1 to 40 mass %, and more preferably from 1 to 20 mass %, based on the total mass of the resin composition, from the viewpoints of the curing speed and pot life of the resin composition.

[0060] (D) A thermosetting resin monomer or prepolymer compound that reacts with component (A). In this embodiment, the resin composition may further include (D) a thermosetting resin monomer or prepolymer compound that reacts with the component (A). As the thermosetting resin monomer or prepolymer compound, a (meth)acrylate compound, an epoxy compound, a phenol compound, a melamine compound, a urea compound, an unsaturated polyester compound, an alkyd compound, a polyurethane compound, a thermosetting polyimide compound, or the like may be used. These resins may be used alone or in a mixture of two or more kinds. Preferably, the component (D) may be at least one of (D1) a (meth)acrylate compound and (D2) an epoxy compound.

[0061] (D1) (Meth)acrylate compound The (D1) (meth)acrylate compound (hereinafter also referred to as "(D1) component") can impart transparency and appropriate hardness to the cured resin composition. The (meth)acrylate compound of the (D1) component is not particularly limited as long as it has one or more (meth)acryloyl groups. In consideration of ensuring heat resistance, a compound having two or more (meth)acryloyl groups is preferred, a compound having 2 to 6 (meth)acryloyl groups is more preferred, and a compound having two (meth)acryloyl groups is even more preferred. In addition, in order to adjust the viscosity and cured product properties (adhesive strength, flexibility, etc.), a compound having one (meth)acryloyl group can also be used in addition to a compound having two (meth)acryloyl groups.

[0062] Examples of the (D1) (meth)acrylate compound include diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or an oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate, or an oligomer thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol; caprolactone-modified tris(methacryloxyethyl)isocyanurate; Examples of the polyacrylate and / or polymethacrylate of lactone-modified dipentaerythritol; ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate; dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, as well as polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, etc. From the viewpoint of reactivity, it is preferable that the (D1) component is substantially free of methacrylate compounds and is an acrylate compound. As the (D1) (meth)acrylate compound, any one of the above-mentioned (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.

[0063] From the viewpoint of preparation and dispensability of the resin composition, it is preferable that the (D1) component has a viscosity of 0.01 to 80 Pa s at 25° C. In this specification, the viscosity refers to a value measured at a measurement temperature of 25° C. using a viscometer appropriate for the viscosity range.

[0064] Commercially available products of the component (D1) include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toa Gosei Co., Ltd., and dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd. As the component (A), any one of these may be used alone, or two or more of them may be used in combination.

[0065] (D2) Epoxy compounds The epoxy compound (D2) (hereinafter also referred to as "component (D2)") is not particularly limited as long as it is a compound containing at least one epoxy group. In consideration of ensuring heat resistance, a compound having two or more epoxy groups is preferable, a compound having 2 to 6 epoxy groups is more preferable, and a compound having two epoxy groups is even more preferable. Epoxy compounds are broadly classified into aliphatic epoxy compounds and aromatic epoxy compounds.

[0066] Examples of aliphatic epoxy compounds include: -(Poly)ethylene glycol diglycidyl ether, (Poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether diepoxy compounds such as cyclohexane-type diglycidyl ether and dicyclopentadiene-type diglycidyl ether; - Triepoxy compounds such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; -alicyclic epoxy compounds such as vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; - glycidylamine type epoxy compounds such as tetraglycidylbis(aminomethyl)cyclohexane; - Hydantoin type epoxy compounds such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and Epoxy compounds having a silicone skeleton, such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane These include, but are not limited to, the following:

[0067] Among the above examples, "cyclohexane-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are bonded to a divalent saturated hydrocarbon group having one cyclohexane ring as a parent structure via an ether bond. "Dicyclopentadiene-type diglycidyl ether" refers to a compound having a structure in which two glycidyl groups are bonded to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure via an ether bond. The aliphatic epoxy compound is preferably one having an epoxy equivalent of 90 to 450 g / eq. In addition, as the cyclohexane-type diglycidyl ether, cyclohexane dimethanol diglycidyl ether is particularly preferable.

[0068] Aromatic epoxy compounds are epoxy compounds that have a structure containing an aromatic ring such as a benzene ring. Many of the epoxy compounds that have been frequently used in the past, such as bisphenol A type epoxy compounds, are of this type. Examples of aromatic epoxy compounds include: -Bisphenol A type epoxy compounds; - Branched polyfunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; -Bisphenol F type epoxy compounds; -Novolac type epoxy compounds; -Tetrabromobisphenol A type epoxy compounds; -fluorene type epoxy compounds; -biphenyl aralkyl epoxy compounds; -Diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; -biphenyl-type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; - glycidylamine type epoxy compounds such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and -Naphthalene ring-containing epoxy compounds Examples of the aromatic epoxy compound include, but are not limited to, bisphenol F type epoxy compounds, bisphenol A type epoxy compounds, and glycidylamine type epoxy compounds, and among these, those having an epoxy equivalent of 90 to 200 g / eq are particularly preferred, and those having an epoxy equivalent of 110 to 190 g / eq are most preferred.

[0069] From the viewpoint of the adhesive strength of the resin composition, the content of the component (D) is preferably from 10 to 60 mass %, and more preferably from 20 to 50 mass %, based on the total mass of the resin composition.

[0070] The resin composition may further contain, as necessary, a solvent, an inorganic filler, a stabilizer, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, a viscosity modifier, a flame retardant, and / or other additives, within a range that does not impair the object of this embodiment.

[0071] The resin composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing the components (A) to (C), optionally the component (D), and optionally other additives, simultaneously or separately, while optionally applying a heat treatment. The device for mixing, stirring, dispersing, etc. is not particularly limited. As this device, a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, etc. equipped with a stirring and heating device can be used. Moreover, these devices may be used in appropriate combination.

[0072] The resin composition thus obtained has thermosetting properties. The thermosetting temperature of the resin composition is preferably 70 to 160°C, and when low-temperature curing is required, it is preferably 70 to 130°C.

[0073] The resin composition is preferably stored at a temperature of -80°C to 0°C. By storing it frozen at -80°C to 0°C, the reaction of the resin composition is inhibited, and the resin composition can be stored in a stable state. The resin composition is more preferably stored at -80°C to -10°C, and further preferably stored at -80°C to -20°C.

[0074] The resin composition of the present embodiment can be used, for example, as an adhesive for bonding parts together, or as a raw material thereof.

[0075] [glue] The adhesive according to the second embodiment of the present invention includes the resin composition according to the first embodiment. This adhesive enables good bonding to engineering plastics, ceramics, and metals, and can be used, for example, to fix, bond, and protect components constituting a semiconductor device or electronic component.

[0076] [Cured product of resin composition or adhesive] The cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive of the second embodiment described above.

[0077] [Semiconductor equipment, electronic components] The semiconductor device according to the fourth embodiment of the present invention has high moisture resistance because it includes the cured product according to the third embodiment described above. The electronic component according to the fifth embodiment of the present invention has high moisture resistance because it includes the semiconductor device according to the fourth embodiment. EXAMPLES

[0078] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % indicate parts by mass and % by mass, unless otherwise specified.

[0079] [Examples 1 to 8, Comparative Examples 1 to 5] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulation shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass (unit: g). The components used in the examples and comparative examples are as follows.

[0080] (A) Polythiol compound (component (A)) (A1): Pentaerythritol tetrakis(3-mercaptopropionate) represented by the following formula (Product name: PEMP, manufactured by SC Organic Chemicals, thiol equivalent: 122 g / eq) [ka] (A2): Glycoluril derivative represented by formula (3) (product name: C3 TS-G, manufactured by Shikoku Chemical Industry Co., Ltd., thiol equivalent: 114 g / eq) [ka] (A3): Polythiol compound represented by the following formula (Product name: PEPT, manufactured by SC Organic Chemicals, thiol equivalent: 124g / eq) [ka] (A4): Trimethylolpropane tris(3-mercaptopropionate) represented by the following formula (product name: TMMP, manufactured by SC Organic Chemicals, thiol equivalent: 133 g / eq) [ka] (B) Cyclic carbodiimide compound (component (B)) (B1) Cyclic carbodiimide compound of formula (5-1) (carbodiimide equivalent: 256 g / eq) [ka] (B') Acyclic carbodiimide compound (B'1): Acyclic polycarbodiimide compound (product name: Carbodilite V-02B, manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 600 g / eq) (B'2): Acyclic polycarbodiimide compound (product name: Carbodilite V-04PF, manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 336 g / eq) (B'3): Acyclic polycarbodiimide compound (product name: Carbodilite V-05, manufactured by Nisshinbo Chemical Inc., carbodiimide equivalent: 262 g / eq) (B'4): Bis(2,6-diisopropylphenyl)carbodiimide of the following formula (manufactured by Tokyo Chemical Industry Co., Ltd., carbodiimide equivalent: 363 g / eq) (monocarbodiimide compound) [ka] ·(C) Curing catalyst (component (C)) (C1) Amine-epoxy adduct-based latent curing catalyst (product name: Fujicure FXR1121, manufactured by T&K TOKA Corporation) (D) Thermosetting resin monomer or prepolymer compound (component (D)) (D1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., acryloyl equivalent: 188 g / eq) (D2): Bisphenol F epoxy resin / bisphenol A epoxy resin mixture (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165g / eq)

[0081] In the examples and comparative examples, the properties of the cured products obtained by curing the resin compositions were measured as follows.

[0082] [Curing evaluation] The curability of the prepared resin composition was evaluated by dropping a drop of the resin composition to make a hemispherical sample, and then heating the sample at temperatures of 150°C and 120°C for 1 hour and observing the state of the sample. If the hemispherical sample was solid and not stringy, it was judged to be sufficiently cured and rated as "cured". If the hemispherical sample did not become solid or became solid but was stringy, it was judged to be uncured and rated as "uncured". The measurement results are shown in Table 1 below.

[0083] [Evaluation of storage stability] The resin compositions of the Examples and Comparative Examples were placed in a syringe with a tip diameter of 5 mm and frozen for 24 hours at -20° C. After the frozen resin compositions were allowed to stand at room temperature (25° C.) for 1 hour, the storage stability of the resin compositions was confirmed by checking whether the resin compositions could be manually pushed out from the tip of the syringe.

[0084] [Evaluation of voids in cured material] 0.2 g of the resin composition was applied onto a 25 mm x 25 mm glass with a release agent. The resin composition was sandwiched between the glass with the release agent using 100 μm spacers on both ends of the glass and fixed with clips. Then, the glass was held at 120 ° C and 150 ° C for 60 minutes to harden. After cooling, the glass was peeled off and visually observed for the occurrence of voids.

[0085] [Table 1]

[0086] As can be seen from Table 1, resin compositions containing the (B) cyclic carbodiimide compound in an amount such that the ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (thiol group equivalents / carbodiimide group equivalents) is 2.0 to 6.0 have excellent thermosetting properties, suppress the generation of voids during curing, and have excellent storage stability under refrigeration. Comparison of Examples 1, 4, 5, and 6 shows that the resin composition contains the cyclic carbodiimide compound (B), and therefore has excellent thermosetting properties, suppresses the generation of voids during curing, and has excellent storage stability under refrigeration, regardless of the type of polythiol compound (A). (B) Regarding Comparative Examples 1 to 3, which contain a polycarbodiimide compound instead of a cyclic carbodiimide compound, Comparative Examples 1 and 2 had poor curing properties at 120°C, and voids occurred during curing in all of Comparative Examples 1 to 3, and Comparative Example 3 hardened during freezing storage, resulting in poor storage stability. (B) Comparative Example 4, which contained a monocarbodiimide compound instead of a cyclic carbodiimide compound, was unable to cure at either 120°C or 150°C. Comparative Example 5, in which the ratio of the thiol group equivalents of component (A) to the carbodiimide group equivalents of component (B) (thiol group equivalents / carbodiimide group equivalents) was 8.0, was unable to cure at either 120°C or 150°C. From Examples 7 and 8, it can be seen that even when (D) a thermosetting resin monomer or prepolymer compound is used in combination, the composition hardens at both 120°C and 150°C, the generation of voids during hardening is suppressed, and storage stability under refrigeration is not impaired. [Industrial Applicability]

[0087] INDUSTRIAL APPLICABILITY The present invention relates to a resin composition which has excellent thermosetting properties, suppresses the generation of voids during curing, and has excellent storage stability under refrigeration, and is extremely useful as an adhesive.

Claims

1. (A) a polythiol compound, (B) a cyclic carbodiimide compound having a plurality of cyclic structures; (C) a curing catalyst, and (D1) (Meth)acrylate compound Including, the ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (thiol group equivalents / carbodiimide group equivalents) is 2.0 to 6.0; The content of the (D1) component is 10 to 60 mass% based on the total mass of the resin composition. Resin composition.

2. The resin composition according to claim 1, wherein the ratio of the number of thiol group equivalents of component (A) to the number of carbodiimide group equivalents of component (B) (thiol group equivalents / carbodiimide group equivalents) is 2.0 to 4.

0.

3. (B) A cyclic carbodiimide compound having a plurality of cyclic structures represented by the following general formula (5): 【Chemistry 5】 is a cyclic carbodiimide compound represented by the formula: In formula (5), Ar 1 to Ar 4 each independently represent an aromatic group; X is a tetravalent group; q is 1; The resin composition according to claim 1 or 2.

4. A resin composition described in any one of claims 1 to 3, comprising (D2) an epoxy compound.

5. An adhesive comprising the resin composition according to any one of claims 1 to 4.

6. A cured product obtained by curing the resin composition according to any one of claims 1 to 4 or the adhesive according to claim 5.

7. A semiconductor device comprising the cured product according to claim 6.

8. An electronic component comprising the semiconductor device according to claim 7.

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