KR102226486B1 - Method for preparing resin composition, adhesive for electronic component, and electronic component - Google Patents

Abstract

(Problem) A method for producing a resin composition capable of improving physical properties such as adhesiveness by increasing the dispersibility of the filler in the resin and enabling the filler to be used in a state closer to the primary particle diameter is provided.
(Solving means) A method for producing a resin composition containing a filler (a) having an average particle diameter A [µm], a filler (b) having an average particle diameter B [µm], and a curable compound (c), wherein A[µm] and B [Μm] satisfies the conditions represented by the following formulas (I) and (II), and before dispersing the fillers (a) and (b) in the curable compound (c), the fillers (a) and (b) ) A method for producing a resin composition having a step of stirring and mixing:
3 µm ≤ A ≤ 20 µm. (Ⅰ)
0.0005×A≤B≤0.020×A... (Ⅱ).

Description

Manufacturing method of resin composition, adhesive for electronic parts, and electronic parts {METHOD FOR PREPARING RESIN COMPOSITION, ADHESIVE FOR ELECTRONIC COMPONENT, AND ELECTRONIC COMPONENT}

The present invention relates to a method for producing a resin composition and an adhesive for electronic parts obtained by the method. More specifically, it relates to a method for producing a resin composition in which agglomeration of the filler is eliminated and the filler is highly dispersed. Since the resin composition obtained by this method does not have agglomerates of fillers, it has excellent precision coating workability such as jet dispensing, and can be bonded in parallel and with precise gap distances, and thus further adhesion strength. It has a high characteristic. Therefore, it is particularly suitable as an adhesive for electronic components such as semiconductors.

Conventionally, a thermosetting epoxy resin composition has been applied to resin compositions used in electronic components, such as resins for substrates, adhesives for semiconductor elements and substrates, adhesives for heat-resistant films and copper foils in flexible substrates, etc. Has become.

This epoxy resin composition is mainly composed of an epoxy resin, a curing agent, and a filler, and in particular, the filler is highly filled so as to occupy about 80% by mass (Patent Document 1). This is for the purpose of removing stress, suppressing deformation such as warpage due to heat, and improving adhesive strength.

However, in recent years, in response to the demand for miniaturization of electronic components including semiconductor packages, development of a three-dimensional mounting technology in which a plurality of electronic components are stacked to form a multilayer semiconductor chip stack has been developed. Further, research is being conducted to further downsize electronic components such as semiconductor chip laminates. Accordingly, for example, a semiconductor chip becomes a very thin thin film, and a fine wiring has been formed on the semiconductor chip. In such a three-dimensional mounting semiconductor chip stack, it is required to stack each semiconductor chip without damage and maintaining a horizontal level with a uniform distance between gaps.

When used for such a purpose, the dispersibility of the filler becomes a very important required characteristic. That is, if there are many aggregates in the highly charged filler, the distance between the gaps must be increased, making it difficult to laminate thin films, and also interfere with horizontal lamination.

In order to solve this problem, for example, a method of dispersing two types of fillers having different average particle diameters using a ball mill is disclosed (Patent Document 2). However, this method requires a special dispersing device such as a ball mill, and has a problem in that the viscosity of the resin composition to be produced is limited in the ball mill, and thus further improvement is required.

Japanese Laid-Open Patent Publication No. Hei 08-109242 Japanese Laid-Open Patent Publication No. Hei 5-86204

The present invention relates to a method for producing a resin composition and an adhesive for electronic parts obtained by the method. More specifically, it relates to a method for producing a resin composition in which agglomeration of the filler is eliminated and the filler is highly dispersed. Since the resin composition obtained by this method does not have agglomeration of fillers, it has excellent precision coating workability such as jet dispensing, and can be bonded in parallel and at an accurate gap-to-gap distance, resulting in higher adhesive strength. Have. Therefore, it is particularly suitable as an adhesive for electronic components such as semiconductors.

As a result of intensive examination, the present inventors used two types of fillers (fillers (a) and fillers (b)) having different average particle diameters, before dispersing in the curable compound (c), the fillers (a) and the fillers ( By stirring and mixing b), it was found that the dispersibility of the filler was improved and a very excellent resin composition could be provided, and the present invention was reached.

In addition, in this specification, "(meth)acryl" means "acrylic and/or methacryl", and "(meth)acryloyl group" means "acryloyl group and/or methacryloyl group".

That is, the present invention,

One)

A method for producing a resin composition containing a filler (a) having an average particle diameter A [µm], a filler (b) having an average particle diameter B [µm], and a curable compound (c), wherein A [µm] and B [µm] are , Before dispersing the filler (a) and filler (b) in the curable compound (c) and satisfying the conditions represented by the following formulas (I) and (II), stirring and mixing the filler (a) and the filler (b) Method for producing a resin composition having the following steps:

3 µm ≤ A ≤ 20 µm. (Ⅰ)

0.0005×A≤B≤0.020×A... (Ⅱ),

2)

The method for producing the resin composition according to 1), wherein (a) is an organic filler,

3)

The method for producing the resin composition according to 1) or 2), wherein (b) is silica and/or alumina,

4)

The method for producing a resin composition according to any one of 1) to 3), wherein (a) is a hydrophobic filler, and (b) is a hydrophilic filler,

5)

The method for producing a resin composition according to any one of the above 1) to 4), wherein (a) is one or two or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber, and silicone rubber,

6)

The method for producing a resin composition according to any one of the above 1) to 5), wherein the content of (a) when the total amount of the resin composition is 100 parts by mass is 5 parts by mass or more and less than 50 parts by mass,

7)

The method for producing a resin composition according to any one of the above 1) to 6), wherein the content of (b) when the total amount of the resin composition is 100 parts by mass is 1 part by mass or more and less than 20 parts by mass,

8)

The curable compound (c) is one or two or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin, and further containing a thermosetting agent (d) 1) to The method for producing the resin composition according to any one of 7),

9)

The method for producing the resin composition according to 8), wherein the curable compound (c) is a (meth)acrylic ester product of resorcin diglycidyl ether,

10)

The method for producing the resin composition according to 8) or 9), wherein the thermosetting agent (d) is an organic acid hydrazide compound,

11)

The method for producing the resin composition according to any one of the above 1) to 10) further containing a thermal radical polymerization initiator (e),

12)

The method for producing the resin composition according to any one of the above 1) to 11), which further contains a silane coupling agent (f),

13)

An adhesive for electronic parts obtained by the method for producing a resin composition according to any one of 1) to 12) above,

14)

An electronic component to which a cured product obtained by curing a resin composition obtained by the method for producing a resin composition according to any one of 1) to 12) above is adhered

It is about.

Since the resin composition obtained by the manufacturing method of the present invention does not have aggregates of fillers, it exhibits a very advantageous effect in an electronic component where precision is important and horizontally narrow gap property is required. In addition, the absence of aggregates of the filler contributes to high adhesive strength.

(Form for carrying out the invention)

The present invention is a step of stirring and mixing the above (a) and (b) before dispersing in the curable compound (c) using two types of fillers (filler (a) and filler (b)) having different average particle diameters. It is a method for producing a resin composition, characterized in that it has.

In the case of producing a resin composition containing two types of fillers, for example, in a curable compound such as an epoxy resin, two types of fillers are each added, stirred and mixed, and then the filler is mixed with a kneader such as a twin-screw roll. The method of dispersing is common. However, in this method, the two types of fillers are each independently dispersed in the curable compound and do not interact with each other.

In the present invention, a filler (a) having a large average particle diameter and a filler (b) having a small average particle diameter are stirred and mixed in advance to make the filler (b) adhere to the surface of the filler (a), which is a curable compound ( By dispersing in c), it is finally possible to produce a resin composition free of aggregates.

In addition, stirring and mixing of the filler (a) and the filler (b) can be performed using a planetary mixer, a jet mill pulverizer, or the like.

In addition, the average particle diameter of the filler (a) and the filler (b) used in the production method of the resin composition of the present invention satisfies the following formula. That is, when the average particle diameter of the filler (a) is set to A [µm] and the average particle size of the filler (b) is set to B [µm], A [µm] and B [µm] are represented by the following formula (I). , (II) satisfies the conditions.

3 µm ≤ A ≤ 20 µm. (Ⅰ)

0.0005×A≤B≤0.020×A... (Ⅱ)

[About Equation (Ⅰ)]

Formula (I) prescribes the average particle diameter of the filler (a) having a large average particle diameter. That is, the average particle diameter of the filler (a) is 3 µm or more and 20 µm or less. When the average filler particle diameter is small, the cohesive force tends to increase. Therefore, when it is less than 3 μm, the effects of the present invention are not sufficiently obtained. Moreover, if the average particle diameter of a filler is too large, even if it does not aggregate, it will not be suitable for manufacture of a liquid crystal display cell. A more preferable range of the average particle diameter is 3 µm or more and 15 µm or less, and particularly preferably 4 µm or more and 10 µm or less.

[About Equation (Ⅱ)]

Equation (II) shows the relationship between the average particle diameter of the filler (a) and the filler (b). That is, the average particle diameter of the filler (b) is 1/2000 or more and 20/1000 or less of the average particle diameter of the filler (a). When the average particle diameter of the filler (b) is within this range, it is efficiently drawn in between the particles of the filler (a) and the particles of the filler (a), thereby exhibiting an effect of increasing the dispersibility of the filler (a). In addition, when the filler (a) is an organic filler, the shape may be deformed due to external stress, but if the filler (b) is within the above range, it is possible to follow the deformation and peeled from the filler (a). There is no case. The average particle diameter of the filler (b) is more preferably 2/1000 or more and 15/1000 or less, and particularly preferably 5/1000 or more and 10/1000 or less.

In this specification, the average particle diameter can be measured with a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishin Corporation; LMS-30). In addition, if it is a commercial item, it is also specified in each company's catalog.

The filler (a) means an organic filler and/or an inorganic filler.

Examples of the organic filler include polyamide fine particles such as nylon 6, nylon 12, and nylon 66, fluorine fine particles such as tetrafluoroethylene and vinylidene fluoride, olefin fine particles such as polyethylene and polypropylene, polyethylene terephthalate, polyethylene, etc. And polyester fine particles such as phthalate, rubber fine particles such as natural rubber, isoprene rubber, and acrylic rubber. Among these, preferred are rubber fine particles, such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), nitrile rubber (NBR), and ethylene. Propylene rubber (EPM, EP), chloroprene rubber (CR), acrylic rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM), urethane rubber (PUR), silicone rubber (SI, SR), fluorine rubber (FKM) , FPM), polysulfide rubber (thiochol), and the like. These solid components (I) may be used in combination of two or more. Among these, preferably, they are silicone rubber, styrene rubber, styrene olefin rubber, and acrylic rubber.

As the silicone rubber, KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Industries), Trefil ^RTM E-5500, 9701, EP-2001 (manufactured by Tore Dow Corning) are preferable. JB-800T, HB-800BK (Negami Industries Co., Ltd.), as styrene rubber ^{, Ravalon RTM} T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical) is preferred, and styrene olefin rubber As ^{examples, Septon RTM} SEPS2004 and SEPS2063 are preferable. In addition, in this specification, "RTM" which is a superscript means a registered trademark.

In addition, when the above acrylic rubber is used, it is preferable that it is an acrylic rubber having a core-shell structure composed of two types of acrylic rubber, and particularly preferably, the core layer is n-butyl acrylate, and the shell layer is methyl methacrylate. desirable. This is a Zefiac ^RTM F-351 sold from Aika Industries, Inc.

Examples of the inorganic filler include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., and preferably fused silica, crystalline silica, silicon nitride, boron nitride , Calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, more preferably fused silica, crystalline silica, alumina, and talc. You may mix and use 2 or more types of these inorganic fillers.

What is preferable as the filler (a) is an organic filler.

Among the organic fillers, preferred are one or two or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber, and silicone rubber, and more preferred are acrylic rubber and/or silicone rubber.

Especially preferred as organic fillers are KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Industries), AFX-8, AFX-15 (manufactured by Sekisui Kasei Industries Co., Ltd.), JB-800T, HB-800BK (Nega U.S. industrial manufacturing).

The filler (b) means an organic filler and/or an inorganic filler.

Examples of the organic filler include Zepiac ^RTM F-325, F-340, F-351 (manufactured by Aika Industries Co., Ltd.), and Paraloid EXL-2655 (manufactured by Kureha Chemical Industries, Ltd.).

As an example of the said inorganic filler, the thing similar to the thing mentioned in the said filler (a) is mentioned. However, the average particle diameter is limited to those satisfying the above formula (II) or those satisfying the above formula (II) through a disintegration step. In addition, although the inorganic filler may have been surface-treated by various methods, it is preferable that it is untreated.

As this filler (b), silica or alumina is preferable, and fumed silica and fumed alumina are particularly preferable.

Regarding the surface polarity of the filler (a) and the filler (b), when the filler (a) is hydrophobic and the filler (b) is hydrophilic, it is one of the preferred embodiments of the present invention. Since the curable compound (c) has a relatively high polarity, by protecting the surface of the hydrophobic filler (a) with the hydrophilic filler (b), higher dispersibility is obtained.

Here, hydrophilicity means that the surface is composed of a functional group having a hydrogen bonding hydroxyl group such as a hydroxyl group or an amino group, or is a hydrogen bond-accepting component such as a metal oxide. In addition, hydrophobicity means that the hydrophilic surface is chemically bonded with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil, or a coupling agent having a non-polar functional group at the terminal.

As the content in the resin composition of the filler (a), when the total amount of the resin composition is 100 parts by mass, it is preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass, and 10 to 30 parts by mass. Is more preferred.

In addition, as the content in the resin composition of the filler (b), when the total amount of the resin composition is 100 parts by mass, it is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and 3 to 10 parts by mass. The denial is more preferable.

The resin composition obtained by the production method of the present invention contains a curable compound (c).

Examples of the curable compound (c) include epoxy resins, (meth)acrylated epoxy resins, monomers of (meth)acrylic acid esters, oligomers of (meth)acrylic acid esters, and partially (meth)acrylated epoxy resins. In the case of adhesive use, among the above, it is particularly preferable that it is a curable resin consisting of one or two or more selected from an epoxy resin, a (meth)acrylated epoxy resin, and a partial (meth)acrylated epoxy resin. For example, an epoxy resin, a mixture of an epoxy resin and a (meth)acrylated epoxy resin, a (meth)acrylated epoxy resin, and a partial (meth)acrylated epoxy resin may be mentioned. In particular, in the case of using as an adhesive for liquid crystal display cells, and in the case of using in a portion in direct contact with the liquid crystal, it is preferable to have low contamination and solubility to the liquid crystal. Examples of suitable epoxy resins include bisphenol A type epoxy resin and bisphenol F type epoxy. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycy Dyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having a triphenolmethane skeleton, and other digly of bifunctional phenols Although cidyl ether product, diglycidyl ether product of difunctional alcohols, and their halides, hydrogenated products, etc. are mentioned, it is not limited to these. The (meth)acryloylated epoxy resin and the partial (meth)acryloylated epoxy resin can be obtained by a known reaction between an epoxy resin and (meth)acrylic acid. For example, a predetermined equivalent ratio of (meth)acrylic acid and a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstyrene, etc.) in an epoxy resin, and a polymerization inhibitor It is obtained by adding (for example, metoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) and performing an esterification reaction at, for example, 80 to 110°C. Although it does not specifically limit as an epoxy resin used as a raw material, A bifunctional or more epoxy resin is preferable, For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolak type epoxy resin, Cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, Dantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolak type epoxy resin having a triphenolmethane skeleton, other diglycidyl ether products of bifunctional phenols, diglycidyl ether of difunctional alcohols Cargoes, and their halides and hydrogenated substances, etc. are mentioned. Among these, from the viewpoint of liquid crystal contamination, more preferable ones are bisphenol-type epoxy resins and novolac-type epoxy resins. In addition, the ratio of the epoxy group and the (meth)acryloyl group is not limited, and is appropriately selected from the viewpoint of process suitability and liquid crystal contamination.

In the resin composition obtained by the production method of the present invention, if necessary, a monomer and/or oligomer of a (meth)acrylic acid ester may be used. Examples of such monomers and oligomers include a reaction product of dipentaerythritol and (meth)acrylic acid, and a reaction product of dipentaerythritol/caprolactone and (meth)acrylic acid, but are not particularly limited.

The resin composition obtained by the production method of the present invention may contain a thermosetting agent (d).

This thermosetting agent is not particularly limited, and polyvalent amines, polyhydric phenols, hydrazide compounds, and the like are exemplified, but solid organic acid hydrazide is particularly suitably used. For example, salicylic acid hydrazide, benzoic acid hydrazide, 1-naphthoic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, for example, aromatic hydrazides. , 2,6-pyridine dihydrazide, 1,2,4-benzene trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like. . In addition, if it is an aliphatic hydrazide compound, for example, formhydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid Dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, Iminodiacetic acid dihydrazide, N,N'-hexamethylenebis semicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis A dihydrazide compound having a hydantoin skeleton such as (hydrazinocarbonoethyl)-5-isopropylhydantoin, preferably a valinehydrantoin skeleton (a skeleton in which the carbon atom of the hydantoin ring is substituted with an isopropyl group), tris (1-hydrazinocarbonylmethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, tris(3) -Hydrazinocarbonylpropyl)isocyanurate, bis(2-hydrazinocarbonylethyl)isocyanurate, etc. are mentioned. These thermosetting agents may be used alone or in combination of two or more. From the balance of curing reactivity and potential, preferably, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, tris(1-hydrazinocarbonyl Methyl) isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, tris(3-hydrazinocarbonylpropyl)isocyanurate, particularly preferably malonic acid dihydrazide , Sebacic acid dihydrazide. The content in the case of using such a thermosetting agent is about 1 to 30 parts by mass when the total amount of the resin composition is 100 parts by mass.

The resin composition obtained by the production method of the present invention may further contain a thermal radical polymerization initiator (e). This thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates a radical by heating and initiates a chain polymerization reaction, but an organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, benzopinacol And the like, and benzopinacol is suitably used. For example, as an organic peroxide, Kayamek ^RTM A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Kadox B-40ES, Percadox 14, Trigonox ^RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Percadox 16, Kayacarbon ^RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akujo Co., Ltd.), Permek ^RTM N, H, S, F, D, G, Perhexa ^RTM H, HC, TMH, C, V, 22, MC, Percure ^RTM AH, AL, HB, Perbutyl ^RTM H, C, ND, L, Percumyl ^RTM H, D, Peroyl ^RTM IB, IPP, Perocta ^RTM ND (above, manufactured by Nichiyu Corporation), etc. are available as commercial items. . In addition, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001 (above, manufactured by Wako Pure Chemical Industries, Ltd.), etc. can be obtained as a commercial item. In addition, in this specification, RTM of a superscript means a registered trademark.

As the thermal radical polymerization initiator (e), preferred is a thermal radical polymerization initiator that does not have an oxygen-oxygen bond (-O-O-) or a nitrogen-nitrogen bond (-N=N-) in the molecule. Thermal radical polymerization initiators having oxygen-oxygen bonds (-OO-) or nitrogen-nitrogen bonds (-N=N-) in the molecule emit a large amount of oxygen or nitrogen when radicals are generated, thus leaving bubbles in the resin composition. It is cured in a state, and there is a concern that properties such as adhesive strength may be deteriorated. Benzopinacol-based thermal radical polymerization initiators (including those chemically modified benzopinacol) are particularly suitable. Specifically, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2- Diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1 ,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)- 1,1,2,2-tetraphenylethane, 1,2-bis(t-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1 ,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1 ,1,2,2-tetraphenylethane, etc. are mentioned, Preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tri Ethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethylsiloxane Si)-1,1,2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyl Siloxy)-1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane.

The benzopinacol is commercially available from Tokyo Kasei Kogyo Co., Ltd., Wako Junyaku Kogyo Co., Ltd. and the like. Further, etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. Further, silyl etherification of the hydroxy group of benzopinacol can be obtained by synthesizing the corresponding benzopinacol and various silylating agents by heating under a basic catalyst such as pyridine. As the silylating agent, trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), or triethylsilylating agent, which are commonly known trimethylsilylating agents. Examples include triethylchlorosilane (TECS), and t-butylmethylsilane (TBMS) as a t-butyldimethylsilylating agent. These reagents can be easily obtained from the market such as silicone derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 times mol with respect to 1 mol of the hydroxyl group of the target compound. More preferably, it is 1.5 to 3.0 times mole. When it is less than 1.0 times mole, the reaction efficiency is poor, and the reaction time becomes longer, thereby promoting thermal decomposition. If it is more than 5.0 times the mole, separation will be poor at the time of recovery, or purification will become difficult.

It is preferable that the thermal radical polymerization initiator (e) has a fine particle size and is uniformly dispersed. If the average particle diameter is too large, it becomes a factor of defects such as poor gap formation during manufacture of narrow-gap electronic components, and is therefore preferably 5 µm or less, and more preferably 3 µm or less. Further, even if it is made infinitely fine, there is no problem, but the lower limit is usually about 0.1 µm. The particle diameter can be measured with a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishin Corporation; LMS-30).

As the content of the thermal radical polymerization initiator (e), when the total amount of the resin composition produced in the present invention is 100 parts by mass, it is preferably 0.0001 to 10 parts by mass, more preferably 0.0005 to 5 parts by mass, and 0.001 to 3 Particularly preferred is a mass part.

The resin composition obtained by the production method of the present invention can improve adhesion strength and moisture resistance reliability by using a silane coupling agent (f). As the silane coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxysilane Hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, etc. are mentioned. These silane coupling agents, as KBM series, KBE series, etc., are sold by Shin-Etsu Chemical Co., Ltd. and the like, and are therefore readily available from the market. The content of the silane coupling agent in the resin composition is preferably 0.05 to 3 parts by mass when the entire resin composition used in the present invention is 100 parts by mass.

The resin composition obtained by the production method of the present invention may contain, for example, a photopolymerization initiator, a radical polymerization inhibitor, a curing accelerator, a pigment, a leveling agent, an antifoaming agent, a solvent, etc. in addition to the above components and the components contained if necessary.

The photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical or an acid by irradiation with ultraviolet rays or visible light to initiate a chain polymerization reaction. For example, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, Diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl sulfide, and the like. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 396, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF), SEIKUOL ) ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Chemical Co., Ltd.), etc. are mentioned.

In addition, from the viewpoint of liquid crystal contamination, it is preferable to use one having a (meth)acrylic group in the molecule, and, for example, 2-methacryloyloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)- The reaction product with phenyl]-2-hydroxy-2-methyl-1-propan-1-one is suitably used. This compound can be prepared and obtained by the method described in International Publication No. 2006/027982.

When a photoinitiator is used, the content rate in the total amount of the resin composition is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass.

The radical polymerization inhibitor is not particularly limited as long as it reacts with a radical generated from a photoinitiator or a thermal radical polymerization initiator to prevent polymerization, and a quinone-based, piperidine-based, hindered phenol-based, nitroso-based, etc. may be used. I can. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2 ,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl, 2,2,6,6-tetramethyl-4-methoxypiperidin-1-oxyl, 2,2,6, 6-tetramethyl-4-phenoxypiperidin-1-oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t -Butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearylβ-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene Bis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-) t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl], 2,4, 8,10-tetraoxaspiro[5,5]undecane, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate)methane, 1, 3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-sec-triazine-2,4,6-(1H,3H,5H)trione, paramethoxy Aluminum salt of phenol, 4-methoxy-1-naphthol, thiodiphenylamine, and N-nitrosophenylhydroxyamine, brand name ADKSTAB LA-81, brand name Adecastab LA-82 (Adeca Co., Ltd.) Manufacturing) etc. are mentioned, but it is not limited to these. Among these, naphthoquinone-based, hydroquinone-based, nitroso-based, and piperazine-based radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p -Cresol, Polystop 7300P (manufactured by Hakuto Corporation) is more preferable, and Polystop 7300P (manufactured by Hakuto Corporation) is most preferable.

The radical polymerization inhibitor is added when synthesizing the component (c) or dissolved in the component (c) during the production of the resin composition. However, in order to obtain a more effective effect, the component is added during the production of the resin composition. It is preferable to dissolve in (c).

The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and particularly preferably 0.01 to 0.2% by mass, based on the total amount of the resin composition.

Examples of the curing accelerator include organic acids and imidazole.

Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, but organic carboxylic acids are preferred. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid and furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexane Dicarboxylic acid, tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanurate, tris(2-carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate And the like.

Moreover, as an imidazole compound, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6-(2'-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6-(2 '-Undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4-methylimidazole (1')) ethyl-s-tri 2 of azine, 2,4-diamino-6-(2'-methylimidazole (1')) ethyl-s-triazine/isocyanuric acid adduct, 2-methylimidazole isocyanuric acid :3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole And 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.

In the case of using a curing accelerator, when the total amount of the resin composition is 100 parts by mass, it is usually 0.1 to 10% by mass, preferably 1 to 5% by mass.

The resin composition obtained by the production method of the present invention is suitably used for electronic parts, particularly for electronic parts requiring a narrow gap. As an electronic component requiring a narrow gap, a liquid crystal display cell is mentioned, for example.

In a liquid crystal display cell, a pair of substrates in which predetermined electrodes are formed on a substrate are opposed to each other at predetermined intervals, the periphery is sealed with the resin composition of the present invention, and a liquid crystal is enclosed in the gap. The kind of liquid crystal to be encapsulated is not particularly limited. Here, the substrate is composed of a combination of a substrate made of glass, quartz, plastic, silicon, or the like in which at least one of the substrates is light-transmitting. As the manufacturing method, a spacer (gap control material) such as glass fiber was added to the resin composition obtained in the present invention, and then the resin composition was applied to one of the pair of substrates using a dispenser or a screen printing device. Thereafter, if necessary, temporary curing is performed at 80 to 120°C. Thereafter, liquid crystal is dripped inside the weir of the resin composition, and the other glass substrates are stacked on top of each other in a vacuum to make a gap. After the gap is formed, a liquid crystal display cell can be obtained by irradiating ultraviolet rays of 1000 mJ/cm 2 to 6000 mJ/cm 2 as necessary and then curing at 90 to 130°C for 1 to 2 hours. The liquid crystal display cell thus obtained has no display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance. Examples of the spacer include glass fibers, silica beads, and polymer beads. The diameter varies depending on the purpose, but is usually 2 to 8 µm, preferably 4 to 7 µm. The amount used is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, and more preferably about 0.9 to 1.5% by mass based on 100% by mass of the resin composition of the present invention.

The method for producing the resin composition of the present invention includes, for example, the following methods. First, if necessary, the component (f) is dissolved in the component (c) (in the case of a plurality of cases, heat mixing is performed and cooling). Subsequently, components (a) and (b) previously mixed, and if necessary, components (d) and (e), antifoaming agents, leveling agents, solvents, etc. are added, and a known mixing device, such as a twin-screw roll, is added. , Uniformly mixed with a triaxial roll or the like, and filtered through a metal mesh.

Since the resin composition obtained by the production method of the present invention does not have aggregates of fillers, it is excellent in coating workability such as dispensing and screen printing, and does not cause cell gap defects in liquid crystal display cells. In addition, the resistance of the liquid crystal penetration path is also good, and also in the bonding process of the substrate and the heating process in the liquid crystal dropping method, the phenomenon that the liquid crystal penetrates or the seal does not collapse occurs. Therefore, it is possible to create a stable liquid crystal display cell. Further, the elution of the constituent components into the liquid crystal is also very small, and it is possible to reduce display defects of the liquid crystal display cell. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. In addition, the cured product has excellent properties of various cured products such as adhesive strength, heat resistance, and moisture resistance, and particularly has very low moisture permeability. Therefore, it is possible to create a liquid crystal display cell excellent in reliability by using the resin composition of the present invention. In addition, the liquid crystal display cell produced by using the resin composition of the present invention also satisfies the characteristics required as a liquid crystal display cell of high voltage retention and low ion density.

Since the resin composition obtained by the production method of the present invention has high resistance to the penetration path of liquid crystal, it can be applied to a liquid crystal dropping method only by heat, and is more preferable from the viewpoint of production tact and the like.

(Example)

Hereinafter, the present invention will be described in more detail by way of synthesis examples and examples, but the present invention is not limited to the examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on mass.

[Synthesis Example 1]

[Synthesis of all acrylates of resorcin diglycidyl ether]

181.2 g of resorcin diglycidyl ether (EX-201: manufactured by Nagase Chemtex Co., Ltd.) was dissolved in 266.8 g of toluene, 0.8 g of dibutylhydroxytoluene as a polymerization inhibitor was added thereto, and the temperature was raised to 60°C. Thereafter, 117.5 g of acrylic acid in the amount of 100% of the epoxy group was added, the temperature was further raised to 80°C, and 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, followed by stirring at 98°C for about 30 hours to obtain a reaction solution. The reaction solution was washed with water and toluene was distilled off to obtain 293 g of the target epoxy acrylate of resorcin diglycidyl ether. The reactive group equivalent of the obtained epoxy acrylate is 183 as a theoretical value.

[Synthesis Example 2]

[Synthesis of 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane]

100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Kasei) was dissolved in 350 parts of dimethylformaldehyde. To this, 32 parts (0.4 moles) of pyridine as a base catalyst and 150 parts (0.58 moles) of BSTFA (manufactured by Shin-Etsu Chemical Industries) were added as a silylating agent, and the mixture was heated to 70°C and stirred for 2 hours. The resulting reaction solution was cooled and stirred, 200 parts of water was added to precipitate the product, and at the same time, the unreacted silylating agent was deactivated. The precipitated product was separated by filtration and sufficiently washed with water. Subsequently, the obtained product was dissolved in acetone, and water was added to recrystallize and purified. 105.6 parts (yield 88.3%) of the target 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane were obtained.

As a result of analysis by HPLC (high-speed liquid chromatography), the purity was 99.0% (area percentage).

[Examples 1 to 7 and Comparative Examples 1 to 4]

A resin composition was produced using components (a), (b) and the like in amounts shown in Table 1 below. The manufacturing method is as shown below.

First, the component (f) was added to the component (c) that was heat-mixed and cooled, followed by stirring. After that, components (a), (b), (d) and (e) were sequentially added, and uniformly mixed with a triaxial roll.

Further, in Examples 1 to 7 and Comparative Examples 3 to 4, components (a) and (b) were premixed and added to the mixture of components (c) and (f), but in Comparative Examples 1 to 2, In the mixture of components (c) and (f), components (a) and (b) are added and mixed in this order.

In addition, the premixing of the components (a) and (b) was performed in three passes using a jet mill pulverizer, which was mixed in a ratio of (a):(b)=75:18.

About the resin composition prepared in Examples 1-7 and Comparative Examples 1-4, the following evaluation was performed. The results are summarized in Table 2.

[Filtration test]

As a method of evaluating the presence of aggregates, a filterability test was performed.

This is a method in which 4 g of the resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 4 is filtered through a 635 mesh metal mesh of 6 mmφ to measure the time and the filterable amount. Since the mesh is gradually clogged in the resin composition having many aggregates, the filtration speed is slowed, but the dispersed resin composition can be filtered at a constant speed.

Evaluation of filterability

○: The resin composition 4 g can be filtered at a constant rate.

(Triangle|delta): Although the speed|rate gradually slows down, 4 g of resin compositions can be filtered.

×: The resin composition 4g cannot be filtered and is clogged.

[Adhesion strength test]

If aggregates are present, the adhesion strength is reduced because the uniformity of the filler in the resin composition is lost, but the resin composition uniformly dispersed does not have the deflection of the filler, so that the adhesion strength is improved.

To 100 g of the resin composition, 1 g of glass fiber (PF-30S: manufactured by Nippon Denki Glass Co., Ltd.) having a diameter of 3 µm was added as a spacer to perform mixing and stirring. This resin composition was applied onto a 50 mm x 50 mm glass substrate, a 1.5 mm x 1.5 mm glass piece was bonded onto the resin composition, and then put in a 120°C oven for 1 hour to cure. The shear adhesive strength of the glass piece was measured using a bond tester (SS-30WD: manufactured by Seishin Corporation). The results are shown in Table 2.

From the results of Table 2, the resin composition obtained by the present invention had no aggregates, and the result was that the filtration rate did not drop. On the other hand, it can be seen that the filterability of the resin composition of the comparative example is gradually deteriorating from the presence of aggregates.

In addition, it was confirmed that the resin composition obtained by the present invention was excellent also in adhesive strength.

Since the resin composition obtained by the method of the present invention has no filler aggregates, it is excellent in coating workability such as dispensing and screen printing, and does not cause gap defects in electronic parts. In addition, since it is excellent in general properties as an adhesive such as adhesive strength, it is possible to easily manufacture an electronic component having excellent long-term reliability.

Claims (12)

A method for producing a resin composition containing a filler (a) having an average particle diameter A [µm], a filler (b) having an average particle diameter B [µm], and a curable compound (c), wherein A [µm] and B [µm] are , Before dispersing the filler (a) and filler (b) in the curable compound (c) and satisfying the conditions represented by the following formulas (I) and (II), stirring and mixing the filler (a) and the filler (b) Method for producing a resin composition having a dry process:
3 µm ≤ A ≤ 20 µm. (Ⅰ)
0.0005×A≤B≤0.020×A... (Ⅱ). The method of claim 1,
The method for producing a resin composition in which (a) is an organic filler. The method of claim 1,
The method for producing a resin composition wherein (b) is silica, alumina, or silica and alumina. The method of claim 1,
The method for producing a resin composition wherein (a) is a hydrophobic filler, and (b) is a hydrophilic filler. The method of claim 1,
The method for producing a resin composition wherein (a) is one or two or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber, and silicone rubber. The method of claim 1,
A method for producing a resin composition in which the content of (a) when the total amount of the resin composition is 100 parts by mass is 5 parts by mass or more and less than 50 parts by mass. The method of claim 1,
A method for producing a resin composition in which the content of (b) when the total amount of the resin composition is 100 parts by mass is 1 part by mass or more and less than 20 parts by mass. The method of claim 1,
The curable compound (c) is one or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin,
Further, a method for producing a resin composition containing at least one selected from the group consisting of the following components (d) to (f):
Thermosetting agent (d)
Thermal radical polymerization initiator (e)
Silane coupling agent (f). The method of claim 8,
The method for producing a resin composition wherein the curable compound (c) is a (meth)acrylic ester product of resorcin diglycidyl ether. The method of claim 8,
A method for producing a resin composition containing at least a thermosetting agent (d), and wherein the thermosetting agent (d) is an organic acid hydrazide compound. The adhesive for electronic parts obtained by the manufacturing method of the resin composition in any one of Claims 1-10. An electronic component to which a cured product obtained by curing a resin composition obtained by the method for producing a resin composition according to any one of claims 1 to 10 is adhered.