WO2018047849A1

WO2018047849A1 - Resin composition, adhesive, sealing material, dam agent, and semiconductor device

Info

Publication number: WO2018047849A1
Application number: PCT/JP2017/032054
Authority: WO
Inventors: 一希岩谷; 史紀新井
Original assignee: ナミックス株式会社
Priority date: 2016-09-12
Filing date: 2017-09-06
Publication date: 2018-03-15
Also published as: TWI771320B; TW202237673A; TW201811839A; JPWO2018047849A1; JP6873489B2; TWI808784B; JP2021119224A

Abstract

Provided is a light- and heat-curable resin composition that has high adhesive strength (especially high peel strength) after curing and that can also suppress reductions in adhesive strength after a post-curing moisture resistance test. The provided resin composition contains (A) an acrylic resin, (B) a thiol compound represented by C(CH₂OR¹)(CH₂OR²)(CH₂OR³)(CH₂OR⁴) (in the formula, R¹, R², R³, and R⁴ each independently are hydrogen or C₃H₆SH, and at least one of R¹, R², R³, and R⁴ is C₃H₆SH), and (C) a latent curing accelerator.

Description

Resin composition, adhesive, sealing material, dam agent, and semiconductor device

The present disclosure relates to a resin composition that is cured by light and heating, and an adhesive, a sealing material, a dam agent, and a semiconductor device using the same.

There are known light and thermosetting resin compositions that can be temporarily fixed by light irradiation and that can be further cured by heating. More specifically, an adhesive of a type that is temporarily fixed by ultraviolet (UV) irradiation and then cured by heat is used in many fields (for example, Patent Documents 1 and 2). This type of adhesive is often used particularly for image sensor module applications. When the temperature of the manufacturing process of the image sensor module is increased, the lenses used for the image sensor module are deteriorated. Therefore, low temperature curability is required for the adhesive and the sealing material used for manufacturing the image sensor module. However, it is very difficult to impart UV curability to the thiol-based adhesive. This is because the potting life is practically used because the curing reaction between UV-curing acrylic resin and thiol resin is easier to proceed than the curing reaction between resins other than acrylic resin (for example, epoxy resin) and thiol resin. This is because it will be shortened to a level where it cannot be done.

In view of the above problems, the present inventors have provided (A) an acrylic resin and (B) specific for the purpose of providing a light and thermosetting resin composition having a sufficiently long pot life. A resin composition containing (C) a latent curing accelerator, (D) a radical polymerization inhibitor, and (E) an anionic polymerization inhibitor was developed (Patent Document 3).

JP 2009-51954 A International Publication No. 2005/052021 Japanese Patent No. 4976575

However, the resin composition containing the above-mentioned (A) acrylic resin, (B) thiol compound, (C) latent curing agent, (D) radical polymerization inhibitor, and (E) anionic polymerization inhibitor. It has been found that the adhesive strength immediately after curing may be lowered after a moisture resistance test such as a reliability test including holding the test piece at 85 ° C. × 85% relative humidity. For this reason, development of the resin composition which can suppress the fall of adhesive strength which can be used also for the use for which high reliability is requested | required is desired.

The resin composition of the present disclosure was developed in view of the above problems. That is, the purpose of the present disclosure has high adhesive strength after curing (particularly high peel strength), and can suppress a decrease in adhesive strength (particularly peel strength) after the moisture resistance test after curing. An object is to provide a light and thermosetting resin composition, and an adhesive, a sealing material, a dam agent and a semiconductor device using the same.

The present inventors have intensively studied to solve the above problems. As a result, by using an acrylic resin, a thiol compound having a specific functional group, and a latent curing accelerator, it has high adhesive strength (particularly high peel strength), and adhesion after a moisture resistance test after curing. A light and thermosetting resin composition capable of suppressing a decrease in strength could be obtained.

The present disclosure relates to a resin composition, an adhesive, a sealing material, a dam agent, and a semiconductor device that have solved the above problems with the following configurations.
[1] As the component (A), an acrylic resin,
As the component (B), the general formula (1):

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or C ₃ H ₆ SH, and at least one of R ¹ , R ² , R ³ and R ⁴ A resin composition containing a latent curing accelerator as a component (C) and a thiol compound represented by C ₃ H ₆ SH.
[2] The resin composition according to [1], further including a thiol compound other than the component (B).
[3] The resin composition according to [1] or [2], further comprising a radical polymerization inhibitor as component (D).
[4] The component (D) is at least one compound selected from the group consisting of N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Resin composition.
[5] The resin composition according to any one of [1] to [4], further comprising an anionic polymerization inhibitor as component (E).
[6] The resin composition according to [5], wherein the component (E) is at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids.
[7] The resin composition according to any one of [1] to [6], wherein [thiol equivalent of the component (B)] / [acryl equivalent of the component (A)] is 0.5 to 2.0. object.
[8] An adhesive comprising the resin composition according to any one of [1] to [7].
[9] A sealing material comprising the resin composition according to any one of [1] to [7].
[10] A dam agent comprising the resin composition of any one of [1] to [7].
[11] A cured product of the resin composition of any one of [1] to [7], a cured product of the adhesive of [8], a cured product of the sealing material of [9], or the above [10] A semiconductor device including a cured product of a dam agent.

According to the embodiment [1], it has high adhesive strength after curing (particularly high peel strength), and can suppress a decrease in adhesive strength after the moisture resistance test after curing, and light and thermosetting. The resin composition can be provided.

According to the embodiment [8], it has high adhesive strength after curing (particularly high peel strength), and can suppress a decrease in adhesive strength after the moisture resistance test after curing, and light and thermosetting. The adhesive can be obtained. According to the embodiment [9], it has high adhesive strength after curing (particularly high peel strength), and can suppress a decrease in adhesive strength after the moisture resistance test after curing, and light and thermosetting. The sealing material can be obtained. According to the embodiment [10], it has high adhesive strength after curing (in particular, high peel strength), and can suppress a decrease in adhesive strength after the moisture resistance test after curing, and light and thermosetting. The dam agent can be obtained. According to the embodiment [11], it has high adhesive strength after curing (particularly high peel strength), and can suppress a decrease in adhesive strength after the moisture resistance test after curing, and light and thermosetting. A highly reliable semiconductor element, such as an image sensor module, can be obtained from the cured resin composition, adhesive, sealant, or dam agent.

The resin composition of the present embodiment (hereinafter referred to as a resin composition)
As the component (A), an acrylic resin,
As the component (B), the general formula (1):

Wherein R ¹ , R ² , R ³ , and R ⁴ are each independently hydrogen or C ₃ H ₆ SH. At least one of R ¹ , R ² , R ³ , and R ⁴ Is a C ₃ H ₆ SH), and a latent curing accelerator as the component (C).

The acrylic resin as component (A) can impart transparency and appropriate hardness to the cured resin composition. This component (A) is an acrylic ester monomer, a methacrylic ester monomer, or an oligomer thereof. Examples of acrylic ester monomers, methacrylic ester monomers, and oligomers that can be used in this embodiment include tris (2-hydroxyethyl) isocyanurate diacrylate and dimethacrylate, tris (2-hydroxyethyl) isocyanate. Nurate triacrylate and trimethacrylate, trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triacrylate and trimethacrylate, and oligomers thereof. Other examples include dipentaerythritol polyacrylate and polymethacrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, alkyl modification Examples include dipentaerythritol polyacrylates and polymethacrylates, and caprolactone-modified dipentaerythritol polyacrylates and polymethacrylates. Examples of the commercially available component (A) include polyester acrylate (product name: M7100) manufactured by Toa Gosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: light acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and A polyester acrylate (product name: EBECRYL810) manufactured by Daicel Ornex Co., Ltd. may be mentioned. As the component (A), a single substance may be used, or two or more kinds of substances may be used in combination.

(B) Component thiol compound is represented by the general formula (1):

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or C ₃ H ₆ SH. At least one of R ¹ , R ² , R ³ and R ⁴ is , C ₃ H ₆ SH). This thiol compound preferably has 2 to 4 mercaptopropyl groups from the viewpoint of curability, and most preferably has 3 mercaptopropyl groups from the viewpoint of the balance between the physical properties of the cured product and the curing speed. . The component (B) may be a mixture containing a plurality of thiol compounds having different numbers of mercaptopropyl groups. This component (B) itself has a sufficiently flexible skeleton. Therefore, the elastic modulus of the cured product can be effectively reduced. By adding the component (B), the elastic modulus of the cured product can be controlled. Therefore, it is possible to increase the adhesive strength (particularly peel strength) after curing, and to suppress a decrease in the adhesive strength after the moisture resistance test of the cured resin composition. The component (B) does not contain an ester bond. Therefore, the cured product has excellent moisture resistance in the long term. Here, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3) used as the thiol compound disclosed in Patent Document 3 above. Both 3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) have an ester bond. The ester bond is easily hydrolyzed. Therefore, it is thought that the resin composition containing these thiol compounds may not have sufficient moisture resistance depending on the use. On the other hand, the component (B) does not contain an ester bond. Examples of the commercially available component (B) include thiol compounds (product name: PEPT) manufactured by SC Organic Chemical.

As the thiol compound that can be used in combination with the component (B), as the component (B1), a thiol compound having no ester bond (excluding the thiol compound of the component (B)), and having an ester bond as the component (B2) A thiol compound is mentioned.

(B1) As an example of component, for example, the following general formula (2)

(Wherein R ⁵ and R ⁶ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and n is an integer of 0 to 10). Compounds. Preferred examples include chemical formula (3) or chemical formula (4):

A polyfunctional group having a functional group (—CH ₂ —CH ₂ —SH or —CH ₂ —CH ₂ —CH ₂ —SH) bonded to each of the four nitrogen atoms of the nitrogen-containing heterocyclic ring represented by Examples thereof include nitrogen-containing heterocyclic compounds.

As a commercial product of the component (B1), a thiol glycol uril derivative (trade name: TS-G) manufactured by Shikoku Kasei Kogyo Co., Ltd. may be mentioned. As the component (B1), a single substance may be used, or two or more kinds of substances may be used in combination. When (B1) is used in combination, the relationship by weight is preferably (B1) :( B) = 15: 85 to 95: 5, more preferably 20:80 to 90:10. By using the component (B) and the component (B1) in combination, the elastic modulus after curing can be adjusted while maintaining moisture resistance. As a result, the adhesive strength (peel strength) can be further improved.

Examples of the component (B2) include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol. Tetrakis (3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, 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-mercapto Butyrate), and trimethylo Ruetantorisu (3-mercapto butyrate) may be mentioned. The ester bond of these components is easily hydrolyzed. Therefore, the cured product may not have sufficient moisture resistance. Therefore, when (B2) is used in combination, the weight of (B2) is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, when the component (B) is 100 parts by mass. From the viewpoint of peel strength, the weight of (B2) is preferably 25 parts by mass or more when the component (B) is 100 parts by mass.

The latent curing accelerator of component (C) is a compound that is in an inactive state at room temperature and that is activated by heating and functions as a curing accelerator. Examples of component (C) include solid-dispersed amine adduct-based latent curing accelerators such as imidazole compounds that are solid at room temperature, reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), and amine compounds. And a reaction product (urea type adduct system) of an isocyanate compound or a urea compound.

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, 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- Anoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) -urea, and N, N ′-(2-methylimidazolyl- (1) -ethyl) -adipoyldiamide It is done. However, the imidazole compound is not limited to these compounds.

Examples of epoxy compounds used as one of raw materials for producing solid dispersion type amine adduct type latent curing accelerator (amine-epoxy adduct type) include polyhydric phenols such as bisphenol A, bisphenol F, catechol, or resorcinol. And polyglycidyl ether obtained by reacting epichlorohydrin, and polyglycidyl ether obtained by reacting a polyhydric alcohol such as glycerin or polyethylene glycol with epichlorohydrin. . Other examples include glycidyl ether esters obtained by reacting a hydroxycarboxylic acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid with epichlorohydrin, such as phthalic acid or terephthalic acid. Reacts polyglycidyl ester obtained by reacting polycarboxylic acid with epichlorohydrin, and amine compounds such as 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin The glycidylamine compound obtained by making it contain is mentioned. In addition, other examples include polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolac resins, or epoxidized polyolefins, and monofunctional such as butyl glycidyl ether, phenyl glycidyl ether, or glycidyl methacrylate. An epoxy compound. However, the said epoxy compound is not limited to these compounds.

The amine compound used as another raw material for producing the solid dispersion type amine adduct-based latent curing accelerator has at least one active hydrogen in the molecule capable of undergoing addition reaction with an epoxy group, and a primary amino group, Any compound having at least one functional group selected from a secondary amino group and a tertiary amino group in the molecule may be used. Examples of such amine compounds are shown below. However, the amine compound is not limited to these compounds. Examples include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane, 4,4'- Aromatic amine compounds such as diaminodiphenylmethane or 2-methylaniline, and 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, or piperazine, The heterocyclic compound containing a nitrogen atom is mentioned. However, the amine compound is not limited to these compounds.

Of these, a compound having a tertiary amino group in the molecule is a raw material that provides a latent curing accelerator having excellent curing acceleration ability. Examples of such compounds include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, or N-methylpiperazine, And primary or secondary having a tertiary amino group in the molecule, such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, or 2-phenylimidazole. Examples include amines. Other examples include 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-butoxy Propyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-Hydroxy-3-butoxypropyl) -2-methylimi Zoline, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N-β-hydroxyethylmorpholine, 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, isonicotinic acid hydrazide and the like, alcohols having a tertiary amino group in the molecule, phenols, thiols, carboxylic acids, hydrazides and the like Can be mentioned. However, the compound having a tertiary amino group in the molecule is not limited to these compounds.

Examples of the isocyanate compound used as another raw material of the solid dispersion type amine adduct-based latent curing accelerator include monofunctional isocyanates such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, or benzyl isocyanate. Compounds, and hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, Or the polyfunctional isocyanate compound like bicycloheptane triisocyanate is mentioned. Furthermore, the terminal isocyanate group containing compound etc. which are obtained by reaction of these polyfunctional isocyanate compounds and 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 a reaction between toluylene diisocyanate and trimethylolpropane, and a reaction between toluylene diisocyanate and pentaerythritol. The addition compound which has a terminal isocyanate group obtained by is mentioned. However, the terminal isocyanate group-containing compound is not limited to these compounds.

Also, examples of urea compounds include urea and thiourea. However, the urea compound is not limited to these compounds.

The solid dispersion type latent curing accelerator that can be used in the present embodiment can be easily prepared as follows, for example. Two components of the amine compound and the epoxy compound, three components of the two components and an active hydrogen compound, or two components or a combination of three components of the amine compound and an isocyanate compound and / or a urea compound are formed. Each collected component is mixed. These components react at temperatures from room temperature to 200 ° C. Thereafter, the cooled and solidified reactant is pulverized. Alternatively, the above components react in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran. And after a solvent removal, the solid content is grind | pulverized.

Among representative examples of commercial products of the above-mentioned solid dispersion type latent curing accelerator, as an example of amine-epoxy adduct system (amine adduct system), “Amicure PN-23” (Ajinomoto Fine Techno Co., Ltd.) Name), "Amicure PN-40" (Ajinomoto Fine Techno Co., Ltd. trade name), "Amicure PN-50" (Ajinomoto Fine Techno Co., Ltd. trade name), "Hardner X-3661S" (ARC (Trade name), “Hardner X-3670S” (trade name, ARC Corporation), “Novacure HX-3742” (trade name, Asahi Kasei E-Materials Co., Ltd.), “Novacure HX-3721” ( Asahi Kasei E-Materials Co., Ltd. trade name), “Novacure HXA9322HP” (Asahi Kasei E-materials Co., Ltd. trade name), “FXR1121 (T & KTOKA (stock) trade name) and the like. Examples of urea type adduct systems include “Fujicure FXE-1000” (trade name of T & KTOKA Corp.) and “Fujicure FXR-1030” (trade name of T & KTOKA Corp.). However, the said commercial item is not limited to these. As the component (C), a single substance may be used, or two or more kinds of substances may be used in combination. The latent curing accelerator (C) is preferably a solid dispersion type amine adduct latent curing accelerator from the viewpoint of pot life and curability.

[The thiol equivalent of the component (B)] / [acryl equivalent of the component (A)] of the resin composition is preferably 0.5 to 2.0. The thiol equivalent of the component (B) is a numerical value obtained by dividing the molecular weight of the component (B) by the number of thiol groups in one molecule. The actual thiol equivalent can be determined, for example, by determining the thiol number by potentiometric measurement. The equivalent of the acrylic resin is equal to a numerical value obtained by dividing the molecular weight of the acrylic resin by the number of acrylic groups (or methacrylic groups) in one molecule. The actual acrylic equivalent can be measured, for example, by NMR. By setting [[thiol equivalent of component (B)] / [acryl equivalent of component (A)] within the range of 0.5 to 2.0, the acrylic and thiol react more than a certain amount, thereby ensuring more certainty. High polymers can be formed. Therefore, it becomes possible to make high adhesive strength easy to express. When the equivalent is less than 0.5 or more than 2.0, sufficient molecular crosslinking is not formed. For this reason, there is a fear that bleeding is likely to occur on the surface of the cured product, or peel strength is likely to be reduced.

The component (A) is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of the adhesive strength of the resin composition.

The component (C) is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of the curing speed and pot life of the resin composition.

The resin composition preferably further contains a radical polymerization inhibitor as component (D). The radical polymerization inhibitor (D) is added to increase the stability of the resin composition during storage. That is, in order to suppress the progress of the unintended radical polymerization reaction, the radical polymerization inhibitor (D) is added. The acrylic resin of component (A) may generate radicals from itself with a low probability. Therefore, an unintended radical polymerization reaction may proceed with the radical as a base point. By adding the radical polymerization inhibitor, it is possible to suppress the progress of the radical polymerization reaction of the unintended component (A).

As the component (D), a known radical polymerization inhibitor can be used. Preferably, for example, at least one selected from the group consisting of N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone is used. Also, known radical polymerization inhibitors disclosed in JP 2010-117545 A and JP 2008-184514 A can be used. As the component (D), a single substance may be used, or two or more kinds of substances may be used in combination.

The resin composition preferably further contains an anionic polymerization inhibitor as the component (E). The anionic polymerization inhibitor as the component (E) imparts stability during storage to the resin composition. That is, the anionic polymerization inhibitor of the component (E) is added in order to suppress an unintended reaction between the amino group that can be contained in the component (C) and the component (B). The imidazole and tertiary amine that can be contained in the component (C) have an amino group. The amino group reacts with the component (B) to initiate polymerization. The latent curing accelerator is designed so that amino group reaction hardly occurs at room temperature. However, there is a slight possibility that the amino group will react with the component (B) at room temperature. The component (E) has a function of suppressing the reaction between the unintended amino group and the component (B) by reacting with the amino group before the amino group reacts with the component (B).

(E) A well-known anionic polymerization inhibitor can be used as a component. Preferably, for example, at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids is used. As the boric acid ester, for example, the boric acid esters disclosed in Japanese Patent Application Laid-Open No. 2011-026539 and Table No. 2005/070991 can be used. As the aluminum chelate, for example, the aluminum chelate disclosed in Table 2005/077091 can be used. As the organic acid, for example, the organic acid disclosed in JP-T-2002-509178 can be used. Examples of the commercially available component (E) include triisopropyl borate and barbituric acid. As the component (E), a single substance may be used, or two or more kinds of substances may be used in combination.

The content of the component (D) is preferably 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the resin composition. When the content of the component (D) is within this range, the stability of the resin composition during storage can be further increased, so that the pot life of the resin composition can be further extended.

The content of component (E) is preferably 0.0001 to 1.0 part by mass with respect to 1 part by mass of component (C). When content of (D) component exists in this range, stability at the time of the preservation | save of a resin composition can be improved more. As a result, the pot life of the resin composition can be further extended.

The resin composition of the present embodiment preferably further includes (F) a glycidyl group-containing compound other than the acrylic resin having a glycidyl group. The reactivity of the component (F) with the component (B) by heating is lower than the reactivity of the component (A) with the component (B). Therefore, like the anionic polymerization inhibitor which is the component (E), the component (F) contributes to increasing the stability of the resin composition during storage.

As the component (F), an epoxy resin, a vinyl compound having at least one glycidyl group, and a polybutadiene having at least one glycidyl group are preferable from the viewpoint of reactivity with the component (B). Examples of commercially available epoxy resins include DIC epoxy resins (product name: EXA835LV) and Nippon Steel & Sumikin epoxy resins (product name: YDF8170). Commercially available products of polybutadiene having at least one glycidyl group include ADEKA epoxidized 1,2-polybutadiene. As the component (F), a single substance may be used, or two or more kinds of substances may be used in combination.

The content of the component (F) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin composition, from the viewpoint of pot life of the resin composition and UV curability. When an epoxy resin is used, the value of (thiol equivalent) / [(acryl equivalent) + (epoxy equivalent)] is preferably 0.5 to 2.0.

The resin composition preferably further contains a radical polymerization initiator. By including a radical polymerization initiator in the resin composition, the resin composition can be cured by a short heating time and UV irradiation. The radical polymerization initiator that can be used is not particularly limited. Known materials can be used. Specific examples of the radical polymerization initiator include dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis (2-t-butylperoxyisopropyl) benzene, or 2,5-dimethyl-2,5-bis ( dialkyl peroxides such as t-butylperoxy) hexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (t-amylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, or ethyl 3,3- (t-butylperoxy) Peroxyketals such as butyrate and t-butylperoxy 2-ethylhexanoer Alkyl peroxyesters such as 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, or t-butylperoxybenzoate It is done. Other examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyldimethyl ketal, benzophenone , Benzoy Benzoic acid, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxan Son, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, and camphorquinone. As the radical polymerization initiator, a single substance may be used, or two or more kinds of substances may be used in combination.

The resin composition includes carbon black, titanium black, silica filler, alumina filler, talc filler, calcium carbonate filler, and PTFE filler as long as the characteristics of the resin composition of the present embodiment are not impaired. , A silane coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a decoloring agent, or other additives may be added. Moreover, you may make a resin composition mix | blend a viscosity modifier, a flame retardant, or a solvent. Here, carbon black and titanium black can be used as a light shielding material. From the viewpoint of achieving both light shielding properties and UV curability (curing depth), titanium black is preferably used. Examples of Titanium Black include Titanium Black 12S (Mitsubishi Materials Electronics Chemical Co., Ltd.), Titanium Black 13M (Mitsubishi Materials Co., Ltd.), Titanium Black 13M-C (Mitsubishi Materials Corporation), TilacD (Ako Kasei Co., Ltd.) Company-made). Titanium black 13M is particularly preferred.

The resin composition can be obtained, for example, by stirring, melting, mixing, and dispersing the components (A) to (C) and other additives simultaneously or separately, optionally with heat treatment. . The apparatus for mixing, stirring, dispersing, etc. is not particularly limited. A lykai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like equipped with a stirring device and a heating device can be used. Moreover, you may use combining these apparatuses suitably.

The resin composition thus obtained is photocurable and thermosetting. The heat curing temperature of the resin composition is preferably 70 to 80 ° C. when used for an image sensor module.

The resin composition of the present embodiment can be used, for example, as an adhesive, a sealing material, a dam agent, and a raw material for joining parts together. Here, the dam agent is formed in advance on the outer periphery of the substrate in advance, for example, before sealing a plurality of semiconductor chips or the like on the substrate with a low viscosity fill agent or the like. By forming the dam with this dam agent, it is possible to suppress the outflow of the low-viscosity fill agent that seals a plurality of subsequent semiconductor chips. Moreover, the adhesive agent containing the resin composition of this embodiment enables favorable joining also to engineering plastics, ceramics, and metals.

Hereinafter, the resin composition of the present embodiment will be described with reference to examples. However, this embodiment is not limited by these examples. In the following examples, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

[Examples 1 to 24, Comparative Examples 1 and 2]
Resin compositions were prepared using a three-roll mill with the formulations shown in Tables 1 to 3. The component (B ′) in Tables 1 to 3 corresponds to the component (B2) described above. The component (B ″) corresponds to the component (B1) described above.

[Peel strength]
An area of 20 mm × 60 mm on the lower substrate (made of SUS-304, smooth plate: 40 mm × 60 mm × 0.3 mm) was coated with the resin composition. The resin composition on the coated area had a thickness of 50 μm. The upper substrate (SUS-304 ribbon (thickness 20 μm, width 5 mm, length 50 mm)) was placed on the resin composition, taking care not to bite the bubbles. In this way, five test pieces having an adhesive surface of 5 mm × 20 mm were produced. Next, the resin composition of the test piece was thermally cured by holding the produced test piece at 80 ° C. for 60 minutes with a blower dryer. Thereby, the test piece for peel strength measurement was obtained.

Thereafter, the upper base material of the obtained test piece was gripped by a peel tester (load measuring device LTS-500N-S100 manufactured by Minebea Co., Ltd., and 90 ° peeling jig) at room temperature. Thereafter, one end of the cured product was slightly peeled off, and then the upper substrate was peeled from the test piece at a 90 ° angle and a lifting speed of 50 mm / min to a lifting distance of 15 mm. At this time, the test piece moved horizontally by the same distance as the lifting distance so as to follow the peeling operation. The average value of the measured values when the lifting distance was 5 to 15 mm was defined as the initial peel strength.

Further, the peel strength after the moisture resistance test was also determined by the following method. The test piece for peel strength measurement was left in a constant temperature and humidity chamber for 100 hours under conditions of a temperature of 85 ° C. and a humidity of 85%. It was confirmed that the temperature of the test piece taken out from the thermostatic chamber was the same as the room temperature within 1 hour. Using this test piece, the peel strength determined by the same measurement method as described above was defined as the peel strength after the moisture resistance test. Further, the retention rate was calculated by the following formula.
Retention rate = [(peel strength after moisture resistance test) / (initial peel strength) × 100] (unit:%)
The peel strength is preferably 0.3 N / mm or more, more preferably 0.5 N / mm or more. Tables 1 to 3 show the measurement results (unit: N / mm).

[Elastic modulus]
A stainless steel plate (made of SUS-304, smooth plate: 40 mm × 60 mm × 0.3 mm) was applied with a resin composition so that the film thickness when cured was 500 ± 100 μm, whereby a coating film was formed. . The coating film was hardened by leaving it at 80 ° C. for 1 hour. From the coating film peeled off from the stainless steel plate, a coating film having a predetermined dimension (5 mm × 40 mm) was cut out with a cutter. The cut end was smoothly finished with sandpaper. The storage elastic modulus of the cut coating film was measured at a frequency of 10 Hz by a tensile method using dynamic thermomechanical measurement (DMA) manufactured by Seiko Instruments Inc. according to JISC6481. This storage elastic modulus at 25 ° C. was defined as the initial elastic modulus. Table 4 shows the measurement results. M means mega. The coating film was left in a constant temperature and humidity chamber for 100 hours under the conditions of a temperature of 85 ° C. and a humidity of 85%. Thereafter, the elastic modulus after the moisture resistance test of the coating film was also measured. Table 4 shows the measurement results.

As can be seen from Tables 1 to 3, in all of Examples 1 to 24, the initial peel strength and the peel strength after the moisture resistance test were 0.3 N / mm or more. Moreover, the retention was 30% or more. Thus, good results were obtained. In contrast, in Comparative Example 1 in which the component (B ′) was used instead of the component (B), the peel strength after the moisture resistance test was remarkably low at 0 N / mm. In Comparative Example 2 in which the component (C ′) was used instead of the component (C), curing occurred at the time of blending. Therefore, the peel strength could not be measured (described as “x” in Table 2). In Comparative Example 1 of Table 4, the shape of the cured product was not maintained after the moisture resistance test. Therefore, the elastic modulus could not be measured (indicated as “x” in Table 4).

[Adhesive strength test of different materials]
<Adhesive strength>
Various materials shown in Table 5 (SUS-304 smooth plate, alumina, LCP (liquid crystal polymer), PC (polycarbonate), PI (polyimide), PA (polyamide), FR-4 (glass epoxy), PE (polyethylene) And a lower substrate made of one material selected from PP (polypropylene)) was applied with the adhesive of Example 1 or the adhesive of Comparative Example 1. Then, the test piece was produced by mounting the upper side base material (SUS-304 ribbon (width 5mm, thickness 20micrometer, length 50mm)) by the same method as the above. Next, the prepared test piece was held at 80 ° C. for 60 minutes, whereby the adhesive of the test piece was thermally cured. Here, LCP, PC, PI, PA, and FR-4 are engineering plastics. Among these, LCP and PI are super engineering plastics.

The peel strength before and after the moisture resistance test was calculated by the same method as above. A peel strength of 0.3 N / mm or more was evaluated as “◯”. A peel strength of less than 0.3 N / mm was evaluated as “x”. Table 5 shows the results.

As can be seen from Table 5, in Example 1, the test piece having the base material of SUS, alumina, and engineering plastic had high peel strength after the moisture resistance test. On the other hand, in Comparative Example 1, all the test pieces having SUS, alumina, engineering plastic, PE, and PP exhibited low peel strength after the moisture resistance test. In Example 1, the test piece having the PE and PP base materials showed low initial peel strength.
The resin composition of the present embodiment may be the following first to seventh resin compositions.
The first resin document is (A) acrylic resin, (B) general formula (1):

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or C ₃ H ₆ SH, and at least one of R ¹ , R ² , R ³ and R ⁴ is A thiol compound represented by (C ₃ H ₆ SH), and (C) a latent curing accelerator.
The second resin composition is the first resin composition further including a thiol compound other than (B).
The third resin composition is the resin composition according to 1 or 2, further comprising (D) a radical polymerization inhibitor.
In the fourth resin composition, the component (D) is at least one selected from the group consisting of N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. It is a 3rd resin composition.
The fifth resin composition is the resin composition according to any one of claims 1 to 4, further comprising (E) an anionic polymerization inhibitor.
The sixth resin composition is the fifth resin composition, wherein the component (E) is at least one selected from the group consisting of boric acid esters, aluminum chelates, and organic acids.
7. The resin composition according to any one of 1 to 6 above, wherein the [thiol equivalent of the component (B)] / [acryl equivalent of the component (A)] is 0.5 to 2.0. It is a thing.
The adhesive of this embodiment may contain any one of the first to seventh resin compositions.
The sealing material of the present embodiment may contain any one of the first to seventh resin compositions.
The dam agent of this embodiment may contain any one of the first to seventh resin compositions.
The semiconductor device of the present embodiment may include a cured product of the first to seventh resin compositions, a cured product of the adhesive, a cured product of the sealing material, or a cured product of the dam agent. .

The resin composition of the present embodiment has high adhesive strength (particularly, high peel strength) after curing, and can suppress a decrease in adhesive strength after a moisture resistance test after curing, and light and thermosetting. It is a resin composition. Therefore, this resin composition is very useful particularly as an adhesive, a sealing material, and a dam agent.

Claims

As the component (A), an acrylic resin,
As the component (B), the general formula (1):

Wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen or C 3 H 6 SH, and at least one of R 1 , R 2 , R 3 and R 4 Is a thiol compound represented by C 3 H 6 SH), and a resin composition containing a latent curing accelerator as the component (C).
The resin composition according to claim 1, further comprising a thiol compound other than the component (B).
Furthermore, the resin composition of Claim 1 or 2 containing a radical polymerization inhibitor as (D) component.
The resin composition according to claim 3, wherein the component (D) is at least one compound selected from the group consisting of N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. object.
The resin composition according to any one of claims 1 to 4, further comprising an anionic polymerization inhibitor as component (E).
The resin composition according to claim 5, wherein the component (E) is at least one compound selected from the group consisting of boric acid esters, aluminum chelates, and organic acids.
The resin composition according to any one of claims 1 to 6, wherein [thiol equivalent of the component (B)] / [acryl equivalent of the component (A)] is 0.5 to 2.0.
An adhesive comprising the resin composition according to any one of claims 1 to 7.
A sealing material comprising the resin composition according to any one of claims 1 to 7.
A dam agent comprising the resin composition according to any one of claims 1 to 7.
A cured product of the resin composition according to any one of claims 1 to 7, a cured product of the adhesive according to claim 8, a cured product of the sealing material according to claim 9, or a cured product according to claim 10. A semiconductor device comprising a cured product of the dam agent.