JP2009114295A - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition affording a cured product having heat-resistant stress properties and low water absorbency. <P>SOLUTION: The adhesive composition includes (A) at least one resin and (D) a catalytic amount of an epoxy resin curing catalyst. (A) At least one resin is selected from the group consisting of a polyimide resin, an acrylic or a methacrylic resin and a phenoxy resin having 10,000-1,500,000 weight-average molecular weight (in terms of polystyrene) and a functional group reactive with following component (B) or component (C): (B) an epoxy resin and (C) an organopolysiloxane. Furthermore, (C) the organopolysiloxane is represented by formula (1) [wherein, R<SP>1</SP>s are each mutually independently a monovalent group selected from among a 1-8C substituted or un-substituted aliphatic group and an aromatic group; A's are each a group represented by formula (2) (wherein, R<SP>2</SP>is a 2-9C divalent aliphatic group; and R<SP>3</SP>is a hydrogen atom or a 1-8C substituted or un-substituted monovalent aliphatic group); k is an integer of 0-3; j is an integer of 0-3; m is an integer of 1-50; and n is an integer of 0-50, with the proviso that k+j+n is ≥2] and has at least two groups represented by formula (2) based on one molecule. The mass ratio of [component (B)+component (C)]/component (A) is 0.1-2.0. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive composition suitable for adhering a semiconductor chip to a substrate, and in particular, an adhesive layer having a low elastic modulus and a low water absorption by containing an organopolysiloxane having a phenolic hydroxyl group. It is related with the adhesive composition which gives.

  The semiconductor device (i) divides a large-diameter silicon wafer on which an IC circuit is formed into semiconductor chips in a dicing process, and (ii) leads the chip with a curable liquid adhesive (die bond material) or the like. It is manufactured by thermocompression-bonding (mounting) to a frame, (iii) after wire bonding between electrodes, and (iv) sealing to improve handling and protection from the external environment. As this sealing form, there are a hermetic sealing type such as metal sealing and ceramic sealing, and a non-hermetic sealing type using resin. At present, the latter method, particularly the transfer molding method using a resin, is most commonly used because it is excellent in mass productivity and inexpensive.

  Since the above liquid adhesive is likely to cause problems such as protrusion of the chip from the end of the chip and wire bonding due to the tilt of the chip due to uneven thickness, a die bond film having an adhesive layer provided on the film has recently been developed. in use.

  The adhesive transferred to the lead frame is cured after the mounting process and exposed to heat in processes such as wire bonding and resin sealing, but the semiconductor package has a packaging structure (CSP) of the same size as the chip. As packaging structures (stacked CSP, SiP) in which chips are stacked are becoming more and more compact year by year, their heat stress resistance and water absorption resistance are becoming severe.

As an adhesive excellent in these characteristics, a heat-resistant adhesive film made of polyimide silicone and an epoxy resin (Patent Document 1 and Patent Document 2) is known.
JP 7-224259 A JP-A-8-27427

  The present inventors have disclosed an adhesive containing a phenoxy resin and an epoxy resin (Japanese Patent Application No. 2007-91934), and an adhesive obtained by combining a phenoxy resin and an epoxy resin with a specific phenolic curing agent (Japanese Patent Application No. 2007-229217). Was invented. These give a cured product excellent in heat stress resistance. The present invention aims to further improve these adhesives in terms of water absorption resistance.

［式（１）中、Ｒ^１は、互いに独立に、炭素数１〜８の置換または非置換の脂肪族基及び芳香族基から選ばれる１価の基であり、Ａは下記式（２）で表される基であり、ｋは０〜３の整数、ｊは０〜３の整数、ｍは１〜５０の整数、ｎは０〜５０の整数であり、但し、ｋ＋ｊ＋ｎは２以上である

（式（２）中、Ｒ^２は炭素数２〜９の二価の脂肪族基、Ｒ^３は水素原子または炭素数１〜８の置換または非置換の一価脂肪族基である）］
を、（成分（Ｂ）＋成分（Ｃ））／成分（Ａ）の質量比０．１〜２．０で、並びに、
（Ｄ）エポキシ樹脂硬化触媒を触媒量で、
含む接着剤組成物。 The present inventors have found that a cured product having excellent heat stress resistance and water absorption resistance can be obtained by using an organopolysiloxane having a predetermined phenolic hydroxyl group.
That is, the present invention is as follows.
(A) A polyimide resin having a functional group reactive with the following (B) component or (C) component having a weight average molecular weight (polystyrene conversion) of 10,000 to 1,500,000, a (meth) acrylic resin, and At least one resin selected from the group consisting of phenoxy resins;
(B) an epoxy resin, and (C) an organopolysiloxane represented by the following formula (1) and having at least two groups per molecule represented by the following formula (2)

[In Formula (1), R ¹ is a monovalent group independently selected from a substituted or unsubstituted aliphatic group and aromatic group having 1 to 8 carbon atoms, and A is the following formula (2): K is an integer of 0 to 3, j is an integer of 0 to 3, m is an integer of 1 to 50, and n is an integer of 0 to 50, provided that k + j + n is 2 or more.

(In Formula (2), R ² is a divalent aliphatic group having 2 to 9 carbon atoms, and R ³ is a hydrogen atom or a substituted or unsubstituted monovalent aliphatic group having 1 to 8 carbon atoms)]
At a mass ratio of (component (B) + component (C)) / component (A) of 0.1 to 2.0, and
(D) a catalyst amount of an epoxy resin curing catalyst,
An adhesive composition comprising.

  The above-mentioned adhesive composition of the present invention gives a cured product excellent in water absorption resistance in addition to excellent heat stress resistance.

Hereinafter, each component will be described.
Ingredient (C)
The composition of the present invention contains (C) an organopolysiloxane represented by the above formula (1). As a result, a cured product having a low elastic modulus and excellent water absorption resistance can be obtained. The organopolysiloxane is actually a mixture of polysiloxanes having different numbers of siloxane units, and the formula (1) represents an average structure. Also, the bond between repeating units may be random. In the formula (1), R ¹ is a monovalent group selected from the group consisting of a substituted or unsubstituted aliphatic group and aromatic group having 1 to 8 carbon atoms. Examples of the aliphatic group include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, hexyl groups, cyclohexyl groups, 2-ethylhexyl groups, octyl groups and other alkyl groups, vinyl Alkenyl groups such as a group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, and a hexenyl group. Aromatic groups include aryl groups such as phenyl, tolyl and xylyl groups, aralkyl groups such as benzyl and phenylethyl groups, and some or all of the hydrogen atoms bonded to carbon atoms of these groups are fluorine, bromine And a group substituted with a halogen atom such as chlorine, for example, a halogen-substituted alkyl group such as a chloromethyl group, a bromoethyl group, and a 3,3,3-trifluoropropyl group. Of these, a methyl group and a phenyl group are preferred.

In the above formula (2), R ² is a divalent aliphatic group of 3-9 carbon atoms, such as ethylene group, propylene group, and an alkylene group such as a butylene group, preferably a propylene group. R ³ is a hydrogen atom or a substituted or unsubstituted monovalent aliphatic group having 1 to 8 carbon atoms, and those exemplified above for R ¹ can be mentioned, and preferably a hydrogen atom.

  In the formula (1), m is an integer of 1-50, preferably 1-20, more preferably 1-10. n is an integer of 0-50, preferably 0-20, more preferably 0-10. M + n is 100 or less, preferably 30 or less. When m + n exceeds 100, it may be separated without being compatible with the components (A) and (B).

k and j are each independently an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1. However, the total number of molecules A per molecule, that is, n + k + j is 2 or more, preferably 3 or more.

これらの式において、ｍ及びｎについては、既に述べたとおりである。 The following can be illustrated as a compound shown by Formula (1).

In these formulas, m and n are as already described.

Ingredient (A)
Component (A) is (A) a polyimide resin having a functional group reactive with (B) component or the above (C) component, having a weight average molecular weight (polystyrene conversion) of 10,000 to 1,500,000, ) At least one resin selected from the group consisting of acrylic resins and phenoxy resins. Preferably, the weight average molecular weight is 30,000 to 1,000,000. When the weight average molecular weight is outside the above range, it may be difficult to form a coating film.

  (B) As an epoxy group and functional group of a component, an epoxy group, a phenolic hydroxyl group, an amino group, an acid anhydride group, etc. are mentioned. Moreover, as a functional group with (C) component, an epoxy group, an acid anhydride group, an isocyanate group, etc. are mentioned. Among these, an epoxy group and a phenolic hydroxyl group are preferable.

（式中、Ｘは芳香族環又は脂肪族環を含む４価の有機基、Ｙは２価の有機基、ｑは１〜３００の整数である） The polyimide resin is preferably a polyimide resin having a phenolic hydroxyl group having a repeating unit of the following formula (3) from the viewpoint of adhesiveness, and more preferably a polyimide silicone resin having a phenolic hydroxyl group.

(Wherein X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, Y is a divalent organic group, and q is an integer of 1 to 300)

（式中、Ｘ、Ｙ、ｑは上で定義したとおりである。） In place of the polyimide silicone resin, a polyamic acid resin having a repeating unit of the following formula (4) may be used, but water may be generated as a by-product due to imidization, and peeling of the adhesive surface may occur in advance. It is preferable to use a polyimide resin obtained by imidizing polyamic acid.

(Wherein X, Y and q are as defined above.)

  Preferably q is an integer of 10 to 500, more preferably 20 to 300. If q is less than the lower limit value, the adhesive strength to the substrate may be insufficient. On the other hand, if q exceeds the upper limit value, the thermocompression bonding property to the substrate will be insufficient.

  The polyamic acid resin represented by the formula (4) has the following structural formula (5)

（但し、Ｘは上記と同様の意味を示す。）
で表されるテトラカルボン酸二無水物と、下記構造式（６）
Ｈ₂Ｎ−Ｙ−ＮＨ₂ （６）
（但し、Ｙは上記と同様の意味を示す。）
で表されるジアミンを、常法に従って、ほぼ等モルで、有機溶剤中で反応させることによって得ることができる。

(However, X has the same meaning as described above.)
A tetracarboxylic dianhydride represented by the following structural formula (6)
H ₂ N—Y—NH ₂ (6)
(However, Y has the same meaning as described above.)
Can be obtained by reacting in a substantially equimolar amount in an organic solvent according to a conventional method.

  Here, examples of the tetracarboxylic dianhydride represented by the formula (5) include, but are not limited to, the following.

  These tetracarboxylic dianhydrides represented by the above formula (5) may be used singly or in combination of two or more as desired.

  Examples of the diamine represented by the formula (6) include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 2,2′-bis (4-amino). Phenyl) propane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, 4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) benzene, 1,4-bis (m-aminophenyl) Thioether) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) Phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-Aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) pheny ] Aromatic ring-containing diamines such as methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane, and the like are preferable. p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane and the like.

  Among the diamines, preferably 1 to 80 mol%, more preferably 1 to 50 mol% is a diaminosiloxane compound represented by the following formula (7), solubility in an organic solvent, relative to the substrate. It is desirable from the viewpoint of adhesiveness and flexibility of the cured product.

（式中、Ｒ^４は夫々独立に炭素原子数３〜９の二価の有機基であり、Ｒ^５は夫々独立に、置換もしくは非置換の炭素原子数１〜８の一価炭化水素基であり、ｍは１〜２００の整数である。）

(Wherein R ⁴ is each independently a divalent organic group having 3 to 9 carbon atoms, and R ⁵ is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. And m is an integer from 1 to 200.)

In the siloxane diamine (or α, ω-diaminopolysiloxane) represented by the formula (7), as R ⁴ , for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH ₂ CH ( An alkylene group such as CH ₃ ) —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —;

のいずれかで表されるアリーレン基；これらを組み合わせたアルキレン・アリーレン基；−（ＣＨ₂）₃−Ｏ−，−（ＣＨ₂）₄−Ｏ−等のオキシアルキレン基；下記式

Any represented by an arylene group; these combinations alkylene-arylene group _{;-( CH 2) 3 -O -,} - (CH 2) 4 oxyalkylene group -O- and the like; formula

のいずれかで表されるオキシアリーレン基；下記式

An oxyarylene group represented by any of the following:

で表されるオキシアルキレン・アリーレン基等の、エーテル結合を含んでもよい二価炭化水素基が挙げられる。

And a divalent hydrocarbon group which may contain an ether bond, such as an oxyalkylene / arylene group represented by the formula:

Examples of R ⁵ include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, and an octyl group, and an allyl group. , Alkenyl groups such as propenyl group, isopropenyl group, butenyl group, isobutenyl group and hexenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, aralkyl groups such as benzyl group and phenylethyl group, and hydrocarbon groups thereof A group in which some or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom such as fluorine, bromine or chlorine, such as a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, etc. And a methyl group and a phenyl group are preferable.

  In the formula (7), m is an integer of 1 to 200, preferably 1 to 100, more preferably 1 to 80. The diaminosiloxane compound can also be used in a combination of two or more.

Examples of the diaminosiloxane compound include the following.

（上式中、Ｒ^６は、互いに独立に、水素原子又はフッ素、臭素、よう素などのハロゲン原子、あるいはアルキル基、アルケニル基、アルキニル基、トリフルオロメチル基、フェニル基などの非置換又は置換の炭素原子数１〜８の一価炭化水素基であり、各芳香環に付いている置換基は異なっていてもよく、ｎは０〜５の整数である。Ａ、Ｂはおのおの１種単独でも、２種以上の組み合わせでもよい。Ｒは水素原子、ハロゲン原子又は非置換もしくは置換の一価炭化水素基である。） The phenolic hydroxyl group can be obtained by using a diamine compound having a phenolic hydroxyl group. Examples of such a diamine include those having the following structure.

(In the above formula, R ⁶ is independently a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an unsubstituted or substituted alkyl group, alkenyl group, alkynyl group, trifluoromethyl group, phenyl group or the like. 1 to 8 monovalent hydrocarbon groups, the substituents attached to each aromatic ring may be different, and n is an integer of 0 to 5. A and B are each a single type. Or a combination of two or more, R is a hydrogen atom, a halogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms of R ⁶ include those similar to those exemplified for R ⁵ , and ethynyl, propynyl, butynyl, and hexynyl groups. And alkynyl groups. In addition, when R is an unsubstituted or substituted monovalent hydrocarbon group, the same as those exemplified for R ⁵ can be used.

（上式中、Ｒ^７は水素原子、フッ素、臭素、よう素などのハロゲン原子、又は炭素数１〜８の、アルキル基、アルケニル基、アルキニル基、トリフルオロメチル基、フェニル基などの非置換又はハロゲン置換の１価炭化水素基であり、各芳香族環に付いている置換基は異なっていてもよく、Ｘは単結合、メチレン基、又はプロピレン基であり、ｎは０〜１０の整数である。） Moreover, the following are mentioned as diamine which has another phenolic hydroxyl group.

(In the above formula, R ⁷ is a hydrogen atom, a halogen atom such as fluorine, bromine or iodine, or an unsubstituted alkyl group, alkenyl group, alkynyl group, trifluoromethyl group, phenyl group or the like having 1 to 8 carbon atoms. Or a halogen-substituted monovalent hydrocarbon group, the substituents attached to each aromatic ring may be different, X is a single bond, a methylene group, or a propylene group, and n is an integer of 0 to 10 .)

Among the diamine compounds having a phenolic hydroxyl group, diamine compounds represented by the following formula (8), particularly those in which R ⁷ is a methyl group are preferable.

（式（８）中、Ｒ^７は上で定義したとおりである。）

(In formula (8), R ⁷ is as defined above.)

  As a compounding quantity of the said diamine compound which has a phenolic hydroxyl group, it is preferable that it is 5-60 mol% with respect to the whole diamine compound, and especially 10-40 mol%. When a polyimide silicone resin having a blending amount in this range is used, a composition having a high adhesive force and forming a flexible adhesive layer can be obtained.

  In addition, the monoamine which has a phenolic hydroxyl group can also be used for introduction | transduction of a phenolic hydroxyl group, The monoamine which has the following structure is mentioned as the example.

（式中、Ｒ^６は上記Ｒ^７と同じであり、各芳香環に付いている置換基は異なっていても構わない。Ｄは１種単独で用いても２種以上を併用してもよい。また、ｐは１〜３の整数である。）

(In the formula, R ⁶ is the same as R ⁷ described above, and the substituents attached to each aromatic ring may be different. D may be used alone or in combination of two or more. In addition, p is an integer of 1 to 3.)

  When a monoamine having a phenolic hydroxyl group is used, the blending amount is 1 to 10 mol% with respect to the entire diamine compound.

  The polyamic acid resin can be synthesized by dissolving the above starting materials in a solvent in an inert atmosphere and reacting them usually at 80 ° C. or lower, preferably 0 to 40 ° C. The obtained polyamic acid resin is usually heated to 100 to 200 ° C., preferably 150 to 200 ° C., thereby dehydrating and ring-closing the acid amide portion of the polyamic acid resin to synthesize the target polyimide resin. it can.

  The organic solvent used for the reaction may not be one that can completely dissolve the starting material as long as it is inert to the resulting polyamic acid. Examples include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide, preferably aprotic Polar solvents, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents can be used singly or in combination of two or more.

  In order to facilitate the dehydration ring closure, it is desirable to use an azeotropic dehydrating agent such as toluene or xylene. Further, dehydration ring closure can be performed at a low temperature using an acetic anhydride / pyridine mixed solution.

  In order to adjust the molecular weight of polyamic acid and polyimide resin, maleic anhydride, dicarboxylic acid anhydride such as phthalic anhydride and / or aniline, n-butylamine, monoamine having phenolic hydroxyl group mentioned above are added. You can also However, the addition amount of dicarboxylic anhydride is usually 0 to 2 parts by mass per 100 parts by mass of tetracarboxylic dianhydride, and the addition amount of monoamine is usually 0 to 2 parts by mass per 100 parts by mass of diamine. Part.

  Examples of the phenoxy resin include resins derived from epichlorohydrin and bisphenol A or F, for example, trade names PKHC, PKHH, PKHJ (all manufactured by Sakai Chemical Co., Ltd.), bisphenol A and bisphenol F mixed type trade names Epicoat 4250, Epicoat 4275, Epicoat 1255HX30, Epicoat 5580BPX40 (all manufactured by Nippon Kayaku Co., Ltd.) using brominated epoxy, bisphenol A type trade names YP-50, YP-50S, YP-55, YP-70 (all Toto Kasei Co., Ltd.) Product), JER E1256, E4250, E4275, YX6954BH30, YL7290BH30 (all manufactured by Japan Epoxy Resin Co., Ltd.) and the like. JER E1256 is preferably used in that it has the above-described weight average molecular weight. The phenoxy resin has an epoxy group at the terminal, which reacts with the component (B) and the component (C).

  The (meth) acrylic resin includes polymers and copolymers of (meth) acrylic acid and / or various derivatives thereof. (Meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Aromatic groups such as (meth) acrylic acid alkyl esters such as lauryl acid, hydroxyl ethyl (meth) acrylate, (meth) acrylic acid hydroxyl alkyl esters such as hydroxylpropyl (meth) acrylate, and benzyl (meth) acrylate (Meth) acrylic acid ester containing, (meth) acrylic acid amide such as dimethyl (meth) acrylic acid amide, (meth) acrylic acid ester containing imide group such as imide acrylate TO-1492 (manufactured by Toagosei Co., Ltd.), Contains epoxy groups such as glycidyl (meth) acrylate (Meth) acrylic acid ester. The copolymer also includes a copolymer of (meth) acrylic acid and / or various derivatives thereof and acrylonitrile, styrene, butadiene, or an allyl derivative.

  From the viewpoint of adhesiveness, the (meth) acrylic resin is preferably a glycidyl (meth) acrylic resin having an epoxy group. The introduction of the epoxy group can be performed by using a (meth) acrylic compound containing an epoxy group. A mixture of the glycidyl (meth) acrylic resin and a resin having no epoxy group may be used.

The (meth) acrylic resin preferably has a glass transition temperature of 80 ° C. or lower. When the glass transition temperature exceeds 80 ° C., the thermocompression bonding property of the adhesive may be inferior.

(B) Component (B) The epoxy resin preferably has at least two epoxy groups in one molecule, and examples of such an epoxy resin include bis (4-hydroxyphenyl) methane, 2,2 ′. -Diglycidyl ether of bis (4-hydroxyphenyl) propane or its halide and condensation polymers thereof (so-called bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc.), butadiene diepoxide, vinylcyclohexene dioxide, resorcinol Diglycidyl ether, 1,4-bis (2,3-epoxypropoxy) benzene, 4,4′-bis (2,3-epoxypropoxy) diphenyl ether, 1,4-bis (2,3-epoxypropoxy) cyclohexene, Bis (3,4-epoxy-6-methylcyclohexane (Silmethyl) adipate, 1,2-dioxybenzene or resorcinol, novolac type phenol resins such as epoxy glycidyl ether or polyglycidyl ester, phenol novolac, cresol novolac obtained by condensing polyphenol or polyhydric alcohol and epichlorohydrin ( Alternatively, an epoxy novolac obtained by condensing a halogenated novolac type phenolic resin and epichlorohydrin (ie, novolak type epoxy resin), an epoxidized polyolefin epoxidized by a peroxidation method, an epoxidized polybutadiene, a naphthalene ring-containing epoxy resin, biphenyl Type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, cyclopentadiene type epoxy resin, etc. Or a mixture of two or more. An epoxy resin having a softening temperature of 100 ° C. or lower is preferable in that the adhesive composition can be pressure-bonded at a lower temperature and a lower pressure, and may be a liquid resin. The softening temperature can be measured by, for example, the ring and ball method (JIS-K7234).

  In addition to the epoxy resin having at least two epoxy groups in one molecule, a monoepoxy compound may be used in combination, for example, styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl. Ether, allyl glycidyl ether, octylene oxide, dodecene oxide and the like may be used in combination.

The components (A) to (C) have a mass ratio of (component (B) + component (C)) / component (A) of 0.1 to 2.0, preferably 0.2 to 1.5. Mix in such an amount. Moreover, when the functional group of component (A) is an epoxy group, the total of the epoxy group of component (B) is in a molar ratio of 0.8 to 1.2 with the phenolic hydroxyl group of component (C). In addition, when the functional group of the component (A) is a phenolic hydroxyl group, the sum of the component (C) and the phenolic hydroxyl group is 0.8 to 1. A molar ratio of 2 is more preferable.

(D) Component (D) The epoxy resin curing catalyst is not particularly limited and may be a known one. Examples include phosphorus catalysts and amine catalysts. Examples of the phosphorus catalyst include triphenylphosphine, triphenylphosphonium triphenylborate, tetraphenylphosphonium tetraphenylborate, and compounds as shown below.

（式中、Ｒは、互いに独立に、水素原子又はフッ素、臭素、よう素などのハロゲン原子、あるいはアルキル基、アルケニル基、アルキニル基、又は炭素原子数１〜８のアルコキシ基、トリフルオロメチル基、フェニル基などの非置換もしくは置換の炭素原子数１〜８の一価炭化水素基であり、総てまたは一部の置換基が同一でも、おのおの異なっていても構わない。）

(In the formula, R is independently of each other a hydrogen atom or a halogen atom such as fluorine, bromine or iodine, or an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group having 1 to 8 carbon atoms, or a trifluoromethyl group. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a phenyl group, and all or some of the substituents may be the same or different.

Examples of the monovalent hydrocarbon group include those similar to those exemplified for R ⁴ above, and alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the amine catalyst include imidazole derivatives such as dicyandiamide, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. Is mentioned. Preferably, dicyandiamide is used.

  The epoxy resin curing catalyst in the present invention can be used singly or in combination of two or more. In addition, the compounding quantity of an epoxy resin curing catalyst (D) should just be an effective quantity as a catalyst, and is 0.005-10 mass% normally about the epoxy resin whole quantity, and especially 0.01-5 mass%.

Component (E) The inorganic filler (E) used in the present invention includes inorganic fillers such as fine particles of silica, conductive particles such as alumina, titanium oxide, carbon black and silver particles, and organic systems such as silicone fine particles. These fillers are mentioned. Among these, silica particles and silicone fine particles having a particle diameter of 10 μm or less are particularly preferable.

The silica particles preferably have an average particle size of 10 μm, more preferably 5 μm or less, and a maximum particle size of 20 μm or less. If the average particle size exceeds this range, the smoothness of the surface of the adhesive film of the present invention may be impaired. The silica particles are preferably surface-treated with an organosilicon compound from the viewpoint of fluidity of the composition.

Silica particles include reinforcing properties such as fumed silica and precipitated silica, and crystalline silica such as silica quartz. Specifically, Aerosil R972, R974, R976, manufactured by Nippon Aerosil Co., Ltd., SE-2050, SC-2050, SC-2050, SE-1050, SO-E1, SO-C1, SO- from Admatechs Co., Ltd. Examples include E2, SO-C2, SO-E3, SO-C3, SO-E5, SO-C5, Musil 120A and Musil 130A manufactured by Shin-Etsu Chemical Co., Ltd., and a mixture thereof.

The blending amount of the silica particles is preferably 5 to 80% by mass, particularly 10 to 60% by mass, based on the total mass of the composition. If it is less than these ranges, the effect of lowering the moisture absorption rate and the linear expansion coefficient is lost, and if it exceeds, the elastic modulus may increase.

  As the silicone fine particles, composite silicone rubber fine particles are preferable. The composite silicone fine particles are particles in which microorganisms of a polyorganosilsesquioxane resin produced by polymerization on the surface are present on at least a part of the surface of the silicone rubber particles. By blending the composite silicone fine particles, it is possible to achieve a decrease in the elastic modulus and water absorption rate of the cured product in combination with the silica particles.

The composite silicone fine particles preferably have an average particle size of 0.1 to 10 μm, more preferably 0.5 to 5 μm. If the average particle size exceeds this range, the smoothness of the surface state of the adhesive film of the present invention may be impaired. Moreover, it is preferable that a maximum particle size is 20 micrometers or less, More preferably, it is 10 micrometers or less.

The compounding quantity of a composite silicone particle is 5-30 mass% of a composition total mass, Preferably it is 10-20 mass%. Outside these ranges, effects on the elastic modulus and water absorption of the cured product cannot be obtained, and the linear expansion coefficient of the cured product may increase and the strength may decrease.

The composite silicone fine particles can be prepared according to a method described in, for example, JP-A-7-196815. That is, an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane are added to an aqueous dispersion of spherical silicone rubber fine particles having an average particle size of 0.1 to 10 μm, and the organotrialkoxysilane is added on the surface of the spherical silicone rubber fine particles. Hydrolyze and polymerize, then dry it. The amount of the polyorganosilsesquioxane resin is preferably 1 to 500 parts by mass, more preferably 2 to 100 parts by mass with respect to 100 parts by mass of the silicone rubber spherical fine particles. If the amount is less than the lower limit, the dispersibility of the composite silicone fine particles in the adhesive composition may be deteriorated and the film composition may be nonuniform. On the other hand, when it exceeds the said upper limit, there exists a tendency for the elasticity modulus of adhesive hardened | cured material to become high.

As the composite silicone fine particles, for example, KMP-600, KMP-605, X-52-7030 and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be used. A mixture of two or more of these can also be used.

Furthermore, in addition to the above components (A) to (E), the composition of the present invention may contain various additives in amounts that do not impair the object of the present invention. Examples of the additive include a wetting improver, an antioxidant, and a heat stabilizer.

Production Method of Composition The adhesive composition of the present invention can be prepared by mixing the above (A) to (D) and other components with a mixer or the like according to a conventional method.

Method of using composition and adhesive film The obtained adhesive composition is dissolved in an aprotic polar solvent such as toluene, cyclohexanone and NMP at an appropriate concentration, applied onto a substrate, dried and then bonded. The substrate and the adherend can be bonded by pressure-bonding the adherend to the agent composition and heating and curing the adhesive composition. In addition, an adhesive composition dissolved in an appropriate concentration in a solvent is applied onto a supporting substrate, dried, and an adhesive layer is formed to obtain a film (hereinafter referred to as an adhesive film). The substrate and the adherend can be bonded together by sandwiching an adhesive film between the substrate and the adherend, press-bonding, and heat-curing. As this film-forming support substrate, polyethylene, polypropylene, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polytetrafluoroethylene, paper, metal foil, etc., or those whose surfaces have been subjected to mold release treatment should be used. Can do.

  Drying when forming the adhesive layer is preferably performed at room temperature to 200 ° C., particularly 80 to 150 ° C. for 1 minute to 1 hour, particularly 3 to 10 minutes. There is no restriction | limiting in particular in the film thickness of an adhesive bond layer, It can select according to the objective, It is preferable that it is 10-100 micrometers, and it is especially preferable that it is 15-50 micrometers. The adhesive layer is cured by pressure bonding at a pressure of 0.01 to 10 MPa, particularly 0.1 to 2 MPa, and then at a temperature of 100 to 200 ° C., particularly 120 to 180 ° C. for 30 minutes to 5 hours, particularly 1 to 5 It can be performed by time curing.

  The adhesive composition of the present invention can be used not only in the production of electronic parts such as semiconductor devices but also in various productions including an adhesion process, for example, the production of LED parts, sensors, liquid crystal parts and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Preparation of Adhesive Composition As shown in Table 1 below, (A) Resin, (B) Epoxy Resin, (C) Organopolysiloxane, (D) Catalyst, and (E) Filler are blended in the amounts shown in the same table. -It mixed with the revolution type mixer (made by Shinki Co., Ltd.), and prepared the adhesive composition. As the component (A), 40 parts by mass of each resin was dissolved in 60 parts by mass of cyclohexanone and blended as a resin solution. In addition, all the compounding quantities in Table 1 are solid content, and a unit is the mass%.

オルガノポリシロキサンＢ（平均構造式）

（Ｄ）硬化触媒
２ＰＨＺ（２−フェニル−４，５−ジヒドロキシメチルイミダゾール）、四国化成社製
（Ｅ）充填剤
シリカ粒子：ＳＥ−２０５０、球状シリカ、平均粒径０．５μｍ、アドマテックス社製
複合シリコーンゴム微粒子：Ｘ−５２−７０３０、平均粒径０．７μｍ、信越化学工業社製

比較例で使用のフェノールノボラック樹脂
ＤＬ−９２、明和化成工業社製
Each substance in Table 1 is as follows.
(A) Resin Polyimide resin A: Synthesis example 1
Polyimide resin B: Synthesis example 2
Polyimide resin C: Synthesis example 3
Phenoxy resin: JER E1256, Mw about 60,000, Japan Epoxy Resin Acrylic resin A: Synthesis example 4
Acrylic resin B: SG-P3, epoxy functional group amount 0.021 mol / 100 g, Tg 12 ° C., Mw 850,000, manufactured by Nagase ChemteX Corporation (B) epoxy resin epoxy resin 1: RE-310S, liquid epoxy resin, Nippon Kayaku Epoxy resin 2: EOCN-1020, Nippon Kayaku Epoxy resin 3: jER-1002, (C) Organopolysiloxane Organopolysiloxane A (average structural formula) manufactured by Japan Epoxy Resin Co., Ltd.

Organopolysiloxane B (average structural formula)

(D) Curing catalyst 2PHZ (2-phenyl-4,5-dihydroxymethylimidazole), manufactured by Shikoku Kasei Co., Ltd. (E) filler silica particles: SE-2050, spherical silica, average particle size 0.5 μm, manufactured by Admatechs Composite silicone rubber fine particles: X-52-7030, average particle size 0.7 μm, manufactured by Shin-Etsu Chemical Co., Ltd.

Phenol novolac resin DL-92 used in the comparative example, manufactured by Meiwa Kasei Kogyo Co., Ltd.

で示されるジメチルジアミノポリシロキサン（以後、「ジアミノシロキサン−１」という）３８．４６質量部（上式においてｊは整数であり、その平均が、該ジメチルジアミノポリシロキサンのアミン当量が６４１となるような大きさである）を２−メチルピロリドン４０質量部に分散させた溶液を滴下し、室温にて１時間撹拌反応させた。次いでジアミノプロピルテトラメチルジシロキサン７．４６質量部を２−メチルピロリドン２０質量部に溶解した溶液を滴下し、室温にて１時間撹拌反応させることにより、酸無水物リッチのアミック酸オリゴマーを合成した。該アミック酸オリゴマー溶液に、下記式、

に示すフェノール性水酸基を有する芳香族ジアミン（以後、「フェノールジアミン−１」という）１９．７９質量部と２−メチルピロリドン１４０質量部を滴下した後、室温で１６時間撹拌してポリアミック酸溶液を合成した。その後、トルエン８０ｍｌを投入してから温度を上げ、約１８０℃で４時間還流させた。水分定量受器に所定量の水がたまっていること、水の流出が見られなくなっていることを確認し、水分定量受器にたまっている流出液を除去しながら、１８０℃でトルエンを除去した。反応終了後、得られた反応液を大過剰のメタノール中に滴下してポリマーを析出させ、減圧乾燥してポリイミド樹脂−Ａを得た。 Synthesis Example 1. Polyimide resin-A
To a 1 L separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer and a stirrer was added 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 32.2. Part by mass and 150 parts by mass of 2-methylpyrrolidone as a solvent were charged and stirred to disperse the acid anhydride. In the dispersion, the following formula

38.46 parts by mass of dimethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-1”) (in the above formula, j is an integer, and the average is such that the amine equivalent of the dimethyldiaminopolysiloxane is 641) A solution in which 2-methylpyrrolidone is dispersed in 40 parts by mass of 2-methylpyrrolidone was added dropwise, and the mixture was stirred at room temperature for 1 hour. Next, a solution in which 7.46 parts by mass of diaminopropyltetramethyldisiloxane was dissolved in 20 parts by mass of 2-methylpyrrolidone was added dropwise, and the mixture was reacted with stirring at room temperature for 1 hour to synthesize an acid anhydride-rich amic acid oligomer. . In the amic acid oligomer solution, the following formula:

19.79 parts by mass of an aromatic diamine having a phenolic hydroxyl group (hereinafter referred to as “phenol diamine-1”) and 140 parts by mass of 2-methylpyrrolidone were added dropwise, and the mixture was stirred at room temperature for 16 hours to give a polyamic acid solution. Synthesized. Thereafter, 80 ml of toluene was added, the temperature was raised, and the mixture was refluxed at about 180 ° C. for 4 hours. After confirming that a predetermined amount of water has accumulated in the moisture meter and that no water has flowed out, remove toluene at 180 ° C while removing the effluent accumulated in the meter. did. After completion of the reaction, the obtained reaction solution was dropped into a large excess of methanol to precipitate a polymer, and dried under reduced pressure to obtain polyimide resin-A.

The infrared absorption spectrum of the obtained resin was measured, absorption due to polyamic acid and indicating the presence of unreacted functional groups did not appear, based on the imide group in 1780 cm ^-1 and 1720 cm ^-1 absorption, 3500 cm ^-1 The absorption based on the phenolic hydroxyl group was confirmed. It was 54,000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent.

で示されるフェノール性水酸基を有する芳香族ジアミン（フェノールジアミン−２）８．６４質量部とＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）８．２１質量部を使用しかつ合計で２５６質量部の２−メチルピロリドンを用いた以外は、合成例１に準じて、ポリイミド樹脂−Ｂを得た。分子量は、６５，０００であった。 Synthesis Example 2. Polyimide resin-B
In Synthesis Example 1, instead of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 35.8 parts by weight of bis (3,4-dicarboxyphenyl) sulfone dianhydride was added to diaminosiloxane-1 Instead of diaminosiloxane-1, only 32.56 parts by weight of dimethyldiaminopolysiloxane (hereinafter referred to as “diaminosiloxane-2”), which differs from amine equivalent by amine equivalent (407), is replaced by the following formula:

8.64 parts by mass of an aromatic diamine having a phenolic hydroxyl group (phenoldiamine-2) and 8.21 parts by mass of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) And according to the synthesis example 1 except having used a total of 256 mass parts 2-methylpyrrolidone, polyimide resin-B was obtained. The molecular weight was 65,000.

Synthesis Example 3. Polyimide resin-C
In Synthesis Example 1, in place of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 35.8 parts by mass of bis (3,4-dicarboxyphenyl) sulfone dianhydride, diaminosiloxane- 44.77 parts by mass of diaminosiloxane-2 instead of 1, and 18.47 parts by mass of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) instead of phenoldiamine-1 And according to the synthesis example 1 except having used 297 mass parts 2-methylpyrrolidone in total, polyimide resin-C was obtained. The molecular weight was 62,000.

Synthesis Example 4 To a 1 L separable flask equipped with an acrylic resin reflux condenser, a thermometer, and a stirrer, 30 parts by mass of imide acrylate TO-1492 (manufactured by Toagosei Co., Ltd.), 50 parts by mass of butyl acrylate, and ethyl acrylate 16 Part by mass, 4 parts by mass of glycidyl methacrylate, and 60 parts by mass of methyl ethyl ketone were charged and stirred at 85 ° C. for 30 minutes while introducing nitrogen into the solution. To this was added a mixed solution of 0.5 parts by mass of azobis-based polymerization catalyst V-59 and 40 parts by mass of methyl ethyl ketone, and after stirring for 30 minutes, 1.0 part by mass of polymerization catalysts V-59 and 80 again. A mixed solution with parts by mass of methyl ethyl ketone was added, 60 parts by mass of imide acrylate TO-1492 (manufactured by Toagosei Co., Ltd.), 100 parts by mass of butyl acrylate, 32 parts by mass of ethyl acrylate, 8 parts by mass of glycidyl methacrylate and 120 parts by mass of methyl ethyl ketone. Part of the mixed solution was added dropwise over about 40 minutes. After completion of dropping, the mixture was heated and stirred at 85 to 95 ° C. for 5 hours under a nitrogen stream to obtain an acrylic resin solution. When the molecular weight of the obtained resin was measured by GPC, it was a weight average molecular weight of 120,000.

Preparation of Adhesive Film Each adhesive composition is applied onto a PET film having a thickness of 50 μm coated with a fluorosilicone release agent, and dried by heating at 120 ° C. for 10 minutes to form an adhesive layer having a thickness of 50 μm. Thus, adhesive films I to X were produced.

The following tests were conducted using the adhesive film obtained above. The results are shown in Table 1.
(1) Young's modulus The adhesive layer (50 μm thickness) of the adhesive film was cured by heating at 175 ° C. for 4 hours. After cutting into a size of 40 mm × 10 mm, the PET film is peeled off to make a test piece, using a dynamic viscoelasticity measuring device, in a tension mode, a distance between chucks of 10 mm, a measurement temperature of 25 ° C., and a measurement frequency of 1 Hz. The Young's modulus was measured with

(2) Four adhesive layers (50 μm thickness) of the water-absorbing adhesive film are peeled off from the PET film and thermally laminated at 90 ° C. to create a sheet having a thickness of about 200 μm and heat-treated at 175 ° C. for 4 hours. , Dried and cured. A test piece having a shape of 50 mm × 50 mm × 200 μm was cut out, immersed in water for 168 hours, the surface adhering water was wiped off, and the weight (W) was measured. Next, the test piece was dried at 120 ° C. for 4 hours, and the weight at that time was measured (W ₀ ). The water absorption was calculated by the following formula.
Water absorption rate (%) = [(W−W ₀ ) / W] × 100

(3) Adhesion test (initial)
The adhesive film 170 mm × 170 mm obtained above was thermocompression bonded to a 450 μm 6-inch silicon wafer. Next, the silicon wafer was diced into 3 mm × 3 mm using a dicer DAD341 (manufactured by Disco Corporation). A silicon chip with an adhesive layer on the back surface was picked up, a 10 mm × 10 mm BT substrate on which resist AUS303 (manufactured by Unitechno Co., Ltd.) was applied and cured, and a silicon substrate at 150 ° C., 0. It was fixed by thermocompression bonding for 2 seconds under the condition of 1 MPa. The obtained test body was heated at 175 ° C. for 4 hours to cure the adhesive layer, thereby preparing an adhesive test piece. The shear adhesive strength at 260 ° C. was measured with a bond tester (manufactured by DAGE, 4000PXY).

(4) Adhesion test (after humidification)
The adhesion test piece obtained in the above (3) was held for 168 hours under the condition of 85 ° C./60% RH, then passed through a reflow furnace at 260 ° C. three times, and then at 240 ° C. in the same manner as described above. The adhesive force was measured.

比較例１−３は、各々、実施例１，２，５においてオルガノポリシロキサンエポキシ樹脂硬化剤の代わりに、フェノールノボラック樹脂をエポキシ樹脂硬化剤として用いたものである。これらの硬化物は、実施例１，２，５に夫々比べて、ヤング率が高く、吸水率も大きく、加湿による接着力の低下が顕著であった。

In Comparative Examples 1-3, phenol novolac resin was used as an epoxy resin curing agent in Examples 1, 2, and 5, instead of the organopolysiloxane epoxy resin curing agent. These cured products had a high Young's modulus and a large water absorption rate as compared with Examples 1, 2, and 5, respectively, and the decrease in adhesive force due to humidification was remarkable.

  The adhesive composition of the present invention gives a cured product that is soft and has low hygroscopicity, and is suitable as an adhesive for semiconductor elements and electronic parts.

Claims (9)

(A) A polyimide resin having a functional group reactive with the following (B) component or (C) component having a weight average molecular weight (polystyrene conversion) of 10,000 to 1,500,000, a (meth) acrylic resin, and At least one resin selected from the group consisting of phenoxy resins;
(B) an epoxy resin, and (C) an organopolysiloxane represented by the following formula (1) and having at least two groups per molecule represented by the following formula (2)

[In Formula (1), R ¹ is a monovalent group independently selected from a substituted or unsubstituted aliphatic group and aromatic group having 1 to 8 carbon atoms, and A is the following formula (2): K is an integer of 0 to 3, j is an integer of 0 to 3, m is an integer of 1 to 50, and n is an integer of 0 to 50, provided that k + j + n is 2 or more.

(In Formula (2), R ² is a divalent aliphatic group having 2 to 9 carbon atoms, and R ³ is a hydrogen atom or a substituted or unsubstituted monovalent aliphatic group having 1 to 8 carbon atoms)]
At a mass ratio of (component (B) + component (C)) / component (A) of 0.1 to 2.0, and
(D) a catalyst amount of an epoxy resin curing catalyst,
An adhesive composition comprising. The adhesive composition according to claim ¹ , wherein R ^{1 of} component (C) is a methyl group or a phenyl group. Component (C) ^{R 2} is a propylene group, ^{R 3} is a hydrogen atom, k and J is 0 or 1, and m is an integer of 1 to 20, n is an integer of 0 to 20, according to claim 1 or 2, wherein Adhesive composition. The adhesive composition according to any one of claims 1 to 3, wherein the (B) epoxy resin is a bisphenol A type epoxy resin or a cresol novolac type epoxy resin. The adhesive composition according to any one of claims 1 to 4, wherein the functional group of the component (A) is at least one selected from a phenolic hydroxyl group, an amino group, and an epoxy group. The adhesive composition according to any one of claims 1 to 5, wherein the component (A) is at least one selected from a polyimide resin having a phenolic hydroxyl group, a glycidyl (meth) acrylic resin, and a phenoxy resin. The adhesive composition according to any one of claims 1 to 6, further comprising (E) a filler of 5 to 80% by mass of the adhesive composition. The adhesive composition according to claim 7, wherein the component (E) is at least one selected from spherical silica and silicone rubber powder. The film provided with the contact bonding layer which consists of an adhesive composition which concerns on any one of Claims 1-8.