JP2009114307A - Thermosetting adhesive composition for ceramics substrate and adhesive film using the same composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting adhesive composition for ceramics substrates having excellent adhesiveness to the ceramics substrates while ensuring sufficient heat resistance, and to provide an adhesive film using the composition. <P>SOLUTION: The thermosetting adhesive composition for the ceramics substrates includes (A) a polyamide-imide resin obtained by reacting a diimidodicarboxylic acid mixture comprising a diimidodicarboxylic acid using a diamine represented by general formula (1) and having ≥3 aromatic rings, a diimidodicarboxylic acid using a polyoxypropylenediamine represented by general formula (2), and a diimidodicarboxylic acid using a siloxanediamine represented by general formula (3) with at least one or more of aromatic diisocyanates represented by general formula (4a), (4b), (4c), (4d) or (4e), and (B) a thermosetting resin. The adhesive film is obtained by using the composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting adhesive composition for a ceramic substrate and an adhesive film using the composition.

  Examples of the wiring board using a ceramic substrate include a hybrid integrated circuit and a semiconductor package in which semiconductor elements are integrated. Various wiring boards using these ceramic substrates are composed of a ceramic substrate, a wiring board layer formed on the ceramic substrate, and an adhesive layer for bonding the ceramic substrate and the wiring board layer.

  Examples of the adhesive used for the adhesive layer include epoxy-based, acrylic-based, polyester-based (for example, see Patent Document 1), fluorine-based, and silicon-based adhesives.

  With conventional adhesives, there is a tendency that sufficient heat resistance cannot be obtained if sufficient adhesion to a ceramic substrate is obtained.

JP 2004-281502 A

  It is an object of the present invention to provide a thermosetting adhesive composition for a ceramic substrate having excellent adhesion to a ceramic substrate while ensuring sufficient heat resistance, and an adhesive film using the composition. It is.

  The present invention is a diimide dicarboxylic acid mixture containing a diimide dicarboxylic acid represented by the following general formula (1), a diimide dicarboxylic acid represented by the following general formula (2) and a diimide dicarboxylic acid represented by the following general formula (3). And (A) a polyamide-imide resin obtained by reacting at least one aromatic diisocyanate represented by the following general formula (4a), (4b), (4c), (4d) or (4e) and ( B) It relates to a thermosetting adhesive composition for a ceramic substrate containing a thermosetting resin.

  By combining such a polyamideimide resin, a thermosetting adhesive composition for a ceramic substrate having excellent adhesion to the ceramic substrate can be obtained while ensuring sufficient heat resistance.

〔式（１）中、Ｒ^１は下記一般式（１ａ）、（１ｂ）、（１ｃ）、（１ｄ）、（１ｅ）、（１ｆ）、（１ｇ）又は（１ｈ）で表される基を示す。〕

[In the formula (1), R ¹ represents a group represented by the following general formula (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h). Show. ]

〔一般式（２）中、Ｒ^２は、下記一般式（２ａ）、（２ｂ）、（２ｃ），（２ｄ）、（２ｅ）、（２ｆ）又は（２ｇ）で表される基を示す。〕

[In General Formula (2), R ² represents a group represented by the following General Formula (2a), (2b), (2c), (2d), (2e), (2f), or (2g). ]

〔一般式（２ｃ）中、ｎ_１は１〜７０の整数を示し、一般式（２ｄ）中、Ｘは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基又は単結合を示し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に水素原子、水酸基、メトキシ基、メチル基又はハロゲン化メチル基を示し、一般式（２ｅ）中、Ｙは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、オキシ基又はカルボニル基を示し、一般式（２ｆ）中、Ｚは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、カルボニル基又は単結合を示す。〕

[In the general formula (2c), _{n 1} represents an integer of 1 to 70, in the general formula (2d), X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, halogenated aliphatic having 1-3 carbon atoms A hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or In general formula (2e), Y represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group. In general formula (2f), Z represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a carbonyl group, or a single bond. ]

〔一般式（３）中、Ｒ^９及びＲ^１０はそれぞれ独立に２価の有機基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４はそれぞれ独立に炭素数１〜２０のアルキル基又は炭素数６〜１８のアリール基を示し、ｍは１〜５０の整数を示す。〕

[In General Formula (3), R ⁹ and R ¹⁰ each independently represent a divalent organic group, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms or carbon The aryl group of number 6-18 is shown, m shows the integer of 1-50. ]

  In the present invention, the cured product obtained from the thermosetting adhesive composition has a storage elastic modulus at 25 to 250 ° C of 2000 MPa or less, a thermal expansion coefficient of 2000 ppm or less, and a glass transition temperature of 100 to 230 ° C. The present invention relates to the above thermosetting adhesive composition for ceramic substrates. Thus, utilization value as a thermosetting adhesive composition increases more because hardened | cured material has sufficient heat resistance.

  Moreover, this invention relates to said thermosetting adhesive composition for ceramic substrates formed by containing 5-100 mass parts of (B) thermosetting resins with respect to 100 mass parts of (A) polyamideimide resin. The thermosetting resin functions as a better curing agent by blending at such a ratio.

  In the present invention, the diimide dicarboxylic acid represented by the general formula (2) is a polyoxypropylene diamine having an amine equivalent of 200 to 2500 g / mol or an alicyclic diamine having an amine equivalent of 50 to 200 g / mol and trimellitic anhydride. A compound obtained by reacting an acid with a diimide dicarboxylic acid represented by the general formula (3) obtained by reacting siloxane diamine having an amine equivalent of 200 to 2500 g / mol with trimellitic anhydride. The present invention relates to the above thermosetting adhesive composition for ceramic substrates. By using such an amine equivalent amine, the adhesiveness of the thermosetting adhesive composition to the ceramic substrate is further improved.

  The present invention also relates to the above thermosetting adhesive composition for ceramic substrates, wherein (B) the thermosetting resin is an epoxy resin and further contains an epoxy resin curing accelerator or curing agent. By using an epoxy resin, the adhesiveness and handleability of the thermosetting adhesive composition to the ceramic substrate are further improved.

  Furthermore, this invention relates to the adhesive film which has an adhesive layer which consists of said thermosetting resin composition for ceramic substrates. By using the said thermosetting adhesive composition, it is a film which has the outstanding adhesiveness with respect to a ceramic substrate, ensuring sufficient heat resistance.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the thermosetting adhesive composition for ceramic substrates and adhesive film which have the outstanding adhesiveness with respect to a ceramic substrate, ensuring sufficient heat resistance.

The best mode for carrying out the invention will be described below. However, the present invention is not limited to the best mode for carrying out the following invention.
The thermosetting adhesive composition for a ceramic substrate according to the present invention (hereinafter referred to as a thermosetting adhesive composition) is used as an adhesive for bonding the ceramic substrate to another member. For example, the thermosetting adhesive composition is used for manufacturing various wiring boards (circuit boards) by bonding a ceramic substrate and a wiring board layer (metal foil layer).

  In order to bond the ceramic substrate and the wiring board layer, a layer (adhesive layer) made of a thermosetting adhesive composition is formed on the ceramic substrate, and the wiring board layer is laminated thereon. In order to form the adhesive layer on the ceramic substrate, the thermosetting adhesive composition may be applied to the ceramic substrate, or the adhesive film may be pressed or laminated on the ceramic substrate.

  When the thermosetting adhesive composition is applied to the ceramic substrate, for example, the solution of the thermosetting adhesive composition is applied to the ceramic substrate and then dried by heating to form the adhesive layer. The heating conditions at this time are such that the reaction rate of the thermosetting adhesive composition is 5 to 10%. Usually, the drying temperature is preferably 120 to 150 ° C.

  The said adhesive film is equipped with the support base material by which the mold release process was carried out, and the layer (adhesion layer) which consists of a thermosetting adhesive composition formed in this support base material. When forming an adhesive layer using an adhesive film, the supporting base material is removed before laminating the adhesive film on the ceramic substrate.

  Examples of the supporting substrate include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, and polyfluorinated ethylene films. The thickness of the supporting substrate is preferably 25 to 100 μm. The thickness of the adhesive layer laminated on the support substrate is preferably 5 to 50 μm, and more preferably 10 to 40 μm.

  Various wiring boards can be formed by forming a wiring board layer on the adhesive layer. The wiring board layer may be formed with a circuit pattern or may cover the entire surface. Alternatively, an adhesive layer may be formed on both surfaces of the ceramic substrate, and a wiring board layer may be formed on both outer surfaces thereof. Gold, silver, copper, nickel, aluminum etc. are mentioned as a metal which comprises a wiring board layer. Copper is preferred when electrically connected.

  The ceramic used for the ceramic substrate is not particularly limited. For example, oxide ceramics such as an aluminum oxide sintered body and a mullite sintered body, an aluminum nitride sintered body, and a silicon carbide sintered body. Non-oxide ceramics such as

An oxide film is usually formed on the surface of the non-oxide ceramic substrate.
Among these, the thermosetting adhesive composition according to the present invention is particularly useful when an oxide ceramic such as an aluminum oxide sintered body and a mullite sintered body is used as an adherend.

  When the ceramic is an aluminum oxide sintered body, a suitable organic solvent or solvent is added to the raw material powder such as alumina, silica, calcia, magnesia and mixed to form a slurry, and then the ceramic green is obtained by a doctor blade method or a calender roll method. A sheet (ceramic green sheet) is formed. This ceramic green sheet is punched out and formed into a predetermined shape by processing such as press molding, and then fired at a high temperature of about 1600 ° C. to obtain a ceramic.

  The thermosetting adhesive composition according to the present invention includes a diimide dicarboxylic acid represented by the general formula (1), a diimide dicarboxylic acid represented by the general formula (2), and a diimide dicarboxylic acid represented by the general formula (3). It contains a polyamidoimide resin obtained by reacting a diimide dicarboxylic acid mixture containing an acid with the aromatic diisocyanate represented by the general formula (4), and a thermosetting resin.

The diimide dicarboxylic acid represented by the general formula (1) is obtained by reacting a diamine having three or more aromatic rings with trimellitic anhydride. Examples of the diamine having three or more aromatic rings include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone. 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene and the like. BAPP is preferable as the diamine having three or more aromatic rings because the property balance of the polyamide-imide resin is good and the cost is low. That is, R ¹ in the general formula (1) is preferably a group represented by the general formula (1a). These may be used alone or in combination of two or more.

  The diimide dicarboxylic acid represented by the general formula (2) is a compound obtained by reacting polyoxypropylene diamine or alicyclic diamine with trimellitic anhydride, and in particular, polyoxypropylene diamine and trimellitic anhydride. A compound obtained by reacting with an acid is preferable.

That is, R ² in the general formula (2) is preferably a group represented by the general formula (2c). Polyoxypropylene diamine is represented by the following general formula (20). In general formula (20), n shows the integer of 1-70.

  Commercially available polyoxypropylene diamines include Jeffamine D-230 (amine equivalent 115), Jeffamine D-400 (amine equivalent 200), Jeffamine D-2000 (amine equivalent 1,000), Jeffamine D-4000 (amine equivalent 2,000) (above, trade name, manufactured by Sun Techno Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

Here, in order to make the adhesion effect of the polyamide-imide resin even more remarkable, it is preferable that the amine equivalent of polyoxypropylene diamine is 200 to 2500 g / mol.
Moreover, it is preferable that the amine equivalent of alicyclic diamine shall be 50-200 g / mol.

The diimide dicarboxylic acid represented by the general formula (3) is obtained by reacting siloxane diamine and trimellitic anhydride. Siloxane diamine is represented by the following general formula (30).
In general formula (30), R ⁹ and R ¹⁰ each independently represent a divalent organic group, and R ^{11 to} R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms. N represents an integer of 1 to 50.

In the general formula (30), examples of the divalent organic group represented by R ⁹ and R ¹⁰ include alkylene groups such as methylene group, ethylene group and propylene group, and arylene groups such as phenylene group, tolylene group and xylylene group. It is done.

In the general formula (30), examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and structural isomers thereof.

In the general formula (30), examples of the aryl group having 6 to 18 carbon atoms represented by R ^{11 to} R ¹⁴ include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like. May be substituted with a group, a nitro group, a cyano group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like.

  Examples of such siloxane diamines include those represented by the following general formula (30a), (30b), or (30c). In formula, n shows the integer of 1-50.

  Commercially available siloxane diamines include amino-modified silicone oils X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), and X-22-161B (which are siloxane-based amines at both ends). Amine equivalent 1500) (above, Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) (above, Toray Dow Corning Silicone Co., trade name), etc. Is mentioned. These may be used alone or in combination of two or more.

  Here, in order to make the adhesion effect of the polyamideimide resin even more remarkable, it is preferable that the amine equivalent of siloxane diamine is 200 to 2500 g / mol. Examples of such siloxane diamines include X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1540) (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

  Examples of the aromatic diisocyanate represented by the general formula (4) include 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) represented by the general formula (4a) and 2,4 represented by the general formula (4b). -Tolylene diisocyanate (hereinafter referred to as TDI), 2,6-tolylene diisocyanate represented by general formula (4c), 2,4-tolylene dimer represented by general formula (4d), general formula (4e) And naphthalene-1,5-diisocyanate represented by the formula:

  As the above-mentioned aromatic diisocyanate, MDI and TDI are particularly preferable because they are excellent in imparting flexibility and preventing crystallinity. These may be used alone or in combination of two or more.

  Moreover, in order to improve heat resistance, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate are used in a proportion of about 5 to 10 mol% with respect to the aromatic diisocyanate. can do.

  The weight average molecular weight of the polyamideimide resin is preferably 30,000 to 300,000, more preferably 40,000 to 200,000, and particularly preferably 50,000 to 100,000. If the weight average molecular weight is less than 30,000, the strength and flexibility in the film state will decrease, the tackiness will increase, and the micro-layer separation structure will tend to disappear. If it exceeds 300,000, There is a tendency that the flexibility and adhesiveness of the resin deteriorate.

  In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography method, and is converted with the analytical curve produced using standard polystyrene.

  Hereinafter, a method for producing the polyamideimide resin used in the present invention will be described. First, a diamine mixture of diamine (1 ′), polyoxypropylene diamine (2 ′) and siloxane diamine (3 ′) having three or more aromatic rings and trimellitic anhydride (hereinafter referred to as TMA) are aprotic polar The reaction is carried out at 50 to 90 ° C. for 0.2 to 1.5 hours in the presence of a solvent.

  Next, an aromatic hydrocarbon capable of azeotroping with water is added at a 0.1 to 0.5 weight ratio of an aprotic polar solvent and reacted at 120 to 180 ° C. This reaction includes the aromatic diimide dicarboxylic acid represented by the general formula (1), the polyoxypropylene diimide dicarboxylic acid represented by the general formula (2), and the siloxane diimide dicarboxylic acid represented by the general formula (3). A diimide dicarboxylic acid mixture is obtained.

  The polyamideimide resin used in the present invention is prepared by reacting the obtained diimidedicarboxylic mixture with (4 ′) aromatic diisocyanate represented by the general formula (4) at about 150 to 250 ° C. for about 0.5 to 3 hours. Can be manufactured.

  The mixing ratio of the mixture of diamine (1 ′), polyoxypropylene diamine (2 ′) and siloxane diamine (3 ′) having three or more aromatic rings is (1 ′) / (2 ′) / (3 ′). = 0.01 to 70.0 / 10.0 to 70.0 / 10.0 to 50.0 (The unit of each numerical value is mol%, and the sum of (1 ′), (2 ′) and (3 ′)) The amount is preferably 100 mol%.).

  Resins obtained using a diamine mixture with a mixing ratio outside this range tend to warp or have a reduced molecular weight. This mixing ratio is more preferably (0.01 to 65.0) / (20.0 to 60.0) / (10.0 to 40.0) (mol%).

  The mixture is reacted with trimellitic anhydride (TMA), and the diimide dicarboxylic acid represented by the general formula (1), the diimide dicarboxylic acid represented by the general formula (2), and the general formula (3) are represented. The amount of raw materials used to obtain a diimide dicarboxylic acid mixture containing diimide dicarboxylic acid is the sum of diamine (1 ′), polyoxypropylene diamine (2 ′), and siloxane diamine (3 ′) having three or more aromatic rings. The molar ratio of the number of moles to the number of moles of TMA ((1 ′) + (2 ′) + (3 ′) / TMA = 1 / 2.20 to 1 / 2.05) is preferable, and 1 / 2.15 If the molar ratio is less than 1 / 2.20, TMA remains, and the molecular weight of the resin finally obtained tends to decrease. If exceeded, diamine remains The molecular weight of the finally obtained resin tends to decrease.

  Diimide dicarboxylic acid mixture ((1) + () containing diimide dicarboxylic acid represented by general formula (1), diimide dicarboxylic acid represented by general formula (2) and diimide dicarboxylic acid represented by general formula (3) 2) + (3)) and (4 ′) aromatic diisocyanate represented by the general formula (4) are reacted to obtain a polyamideimide resin at a molar ratio of ((1) + (2) + ( 3)) / (4) = 1 / 1.50 to 1 / 1.05, more preferably 1 / 1.3 to 1 / 1.1. If this molar ratio is less than 1 / 1.50 or exceeds 1 / 1.05, the molecular weight of the resulting resin tends to decrease.

  The aprotic polar solvent is preferably a diamine having 3 or more aromatic rings, polyoxypropylene diamine, alicyclic diamine, siloxane diamine, or an organic solvent that does not react with TMA, such as dimethylacetamide, dimethylformamide Dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone and the like. Since the imidization reaction requires high temperature, N-methyl-2-pyrrolidone having a high boiling point is more preferable. These may be used alone or in combination of two or more.

  The amount of water contained in the aprotic polar solvent is preferably 0.1 to 0.2% by mass. If the water content exceeds 0.2% by mass, the trimellitic acid produced by hydration of TMA does not allow the reaction to proceed sufficiently, and the molecular weight of the polymer tends to decrease.

  Moreover, the usage-amount of an aprotic polar solvent becomes the range of 10-80 mass% with respect to the total amount of the diamine which has three or more aromatic rings, polyoxypropylene diamine, alicyclic diamine, siloxane diamine, and TMA. It is preferable that it is in the range of 50 to 80% by mass. If the amount used is less than 10%, the solubility of TMA tends to decrease, and the progress of the reaction tends to be insufficient.

  The cured product obtained from the thermosetting adhesive composition according to the present invention has a storage elastic modulus at 25 to 250 ° C. of 2000 MPa or less, a thermal expansion coefficient of 2000 ppm or less, and a glass transition temperature of 100 to 230 ° C. preferable. Such hardened | cured material can be implemented by those skilled in the art by combining suitably said diimide dicarboxylic acid, aromatic diisocyanate, and a thermosetting resin.

  The thermosetting resin used in the present invention is not limited as long as it reacts with the amide group in the modified polyamideimide resin skeleton in a liquid state by heat or the like, but an epoxy resin, a phenol resin, a bismaleimide triazine resin or the like is preferable. An epoxy resin is preferable as the thermosetting resin because of its good adhesiveness and handleability. These may be used alone or in combination of two or more.

  The epoxy resin is not particularly limited as long as it is a liquid bifunctional or higher functional epoxy resin, and liquid epoxy resins such as bisphenol A type and bisphenol F type can be used. As these liquid resins, Epicoat 827, Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.), Epomic R140P, Epomic R110 (manufactured by Mitsui Petrochemical Co., Ltd.), YD127, YD128, YDF170 (Toto Kasei Co., Ltd.) ) And the like. These may be used alone or in combination of two or more. The epoxy resin preferably has an epoxy equivalent of 150 to 250, and more preferably 160 to 200.

  It is preferable that the compounding quantity of a thermosetting resin is 5-100 mass parts with respect to 100 mass parts of polyamide-imide resins, It is more preferable that it is 30-80 mass parts, It is 20-50 mass parts. Particularly preferred. When the blending amount is less than 5 parts by mass, the function as a curing agent tends to be insufficient, and when it exceeds 100 parts by mass, the crosslinked structure of the cured resin becomes dense and tends to be brittle.

  The thermosetting adhesive composition according to the present invention preferably further contains a curing accelerator or a curing agent for the thermosetting resin. The curing accelerator or curing agent is not particularly limited as long as it reacts with an epoxy resin or accelerates the curing reaction. For example, amines and imidazoles are used. These may be used alone or in combination of two or more.

  Examples of amines include dicyandiamide, diaminodiphenylmethane, guanylurea and the like. These may be used alone or in combination of two or more. Examples of imidazoles include alkyl group-substituted imidazoles such as 2-ethyl-4-methylimidazole and benzimidazoles. These may be used alone or in combination of two or more.

  In the case of amines, the compounding amount of the curing accelerator or curing agent is preferably such that the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are approximately equal. In the case of imidazole, the amount is preferably 0.1 to 2.0 parts by weight with respect to 100 parts by weight of the epoxy resin. If this blending amount is small, uncured epoxy resin remains, and the glass transition temperature of the crosslinked resin is lowered. If too large, unreacted curing accelerator or curing agent remains, pot life, insulation properties, etc. Tends to be insufficient.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these.
(Synthesis of polyamide-imide resin)
A 1-liter separable flask equipped with a 25 ml water quantitative receiver with a cock connected to a reflux condenser, a thermometer, and a stirrer was prepared.

  There, BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane), which is a diamine having three or more aromatic rings, and Jeffamine D-2000 (Sun Techno Chemical Co., Ltd.), which is a polyoxypropylene diamine. Company product name, amine equivalent 1000), reactive silicone oil X-22-161-B (trade name, amine equivalent 1540), siloxane diamine, TMA (trimellitic anhydride), aprotic NMP (N-methyl-2-pyrrolidone) and γ-BL (γ-butyrolactone) were added as polar polar solvents in the mixing ratios shown in Table 1, respectively, to prepare a reaction solution.

  The reaction solution was reacted at 80 ° C. with stirring for 30 minutes. Next, 100 ml of toluene which is an aromatic hydrocarbon azeotropic with water was added, and then the reaction solution was heated and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated about 3.6 ml or more in the moisture determination receiver and that no water has flowed out. The solution was warmed to remove toluene.

  After returning the reaction solution to room temperature, MDI (4,4'-diphenylmethane diisocyanate) and TDI (2,4-tolylene diisocyanate), which are aromatic diisocyanates, were added at a blending ratio shown in Table 1. The temperature of the reaction solution was raised again and reacted at 190 ° C. for 2 hours. The reaction product was dissolved in NMP to obtain polyamideimide resins A-1 to A-3.

＊１：２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン
＊２：ジェファーミンＤ−２０００（サンテクノケミカル（株）製、商品名、アミン等量 １０００）
＊３：反応性シリコーンオイル（信越化学工業（株）製、商品名）アミン等量 １５４０
＊４：無水トリメット酸
＊５：Ｎ−メチル−２−ピロリドン
＊６：γ−ブチロラクトン
＊７：４，４’−ジフェニルメタンジイソシアネート
＊８：２，４’−トリレンジイソシアネート

* 1: 2,2-bis [4- (4-aminophenoxy) phenyl] propane * 2: Jeffamine D-2000 (manufactured by Sun Techno Chemical Co., Ltd., trade name, amine equivalent 1000)
* 3: Reactive silicone oil (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) Amount of amine equivalent 1540
* 4: Trimetic anhydride * 5: N-methyl-2-pyrrolidone * 6: γ-butyrolactone * 7: 4,4'-diphenylmethane diisocyanate * 8: 2,4'-tolylene diisocyanate

(Examples 1-3 and Comparative Examples 1-2)
The components shown in Table 2 were blended in the resulting modified polyamideimide resin solutions (A-1 to A-3) at the blending ratios shown in the table and stirred for about 1 hour until uniform, and then room temperature for defoaming. And allowed to stand for 24 hours to obtain a thermosetting adhesive composition.

＊９：三井石油化学（株）商品名
＊１０：ＪＳＲ（株）製
＊１１：大日本インキ化学工業（株）商品名

* 9: Mitsui Petrochemical Co., Ltd. product name * 10: JSR Co., Ltd. * 11: Dainippon Ink Chemical Co., Ltd. product name

  The solution of the obtained thermosetting adhesive composition was applied to a 500 μm thick aluminum oxide sintered ceramic so that the film thickness after drying was 20 μm, and dried at 140 ° C. for 10 minutes to form an adhesive layer. Formed. Next, the roughened surface of a rolled copper foil having a thickness of 35 μm (manufactured by Nikko Gould foil Co., Ltd., trade name: BHY-22B-T) is bonded to the surface of the adhesive layer, and hot pressing is performed at a temperature of 180 ° C. and a pressure of 2 MPa. And temporarily bonded. Furthermore, it was made to harden | cure at 200 degreeC with a dryer for 60 minutes, and the sample A was obtained.

(Adhesiveness)
The sample A was obtained by cutting the adhesive layer of sample A into strips having a width of 10 mm. A peel test was performed on a normal sample, a sample left at 150 ° C. for 240 hours, a sample left at 121 ° C. and 2 atm, and saturated with steam for 30 hours. That is, the adhesiveness was peeled in a 90 ° direction with respect to the ceramic substrate under the following conditions, and the peel strength (KN / m) between the ceramic and the adhesive layer was measured. Adhesiveness was evaluated by peel strength. The evaluation results are shown in Table 3. In addition, when peeling from the interface of an adhesive bond layer and copper foil, the interface of a ceramic and an adhesive bond layer is peeled a little in advance, and a peeling test is done.
Conditions Measurement temperature: 25 ° C., peeling speed: 10 mm / min

(Solder heat resistance)
A sample was cut into a 20 × 20 mm square shape in the adhesive layer of Sample A to prepare a sample. It was immersed in a solder bath heated to 300 ° C. for 1 minute with the copper foil side down. Thereafter, the samples were examined for abnormal appearance such as blistering and peeling.

Further, after being left at 40 ° C. and a humidity of 90% for 8 hours, it was immersed in a solder bath heated to 300 ° C. and 280 ° C. for 1 minute with the copper foil side down. Thereafter, the presence of abnormal appearance such as blistering and peeling was examined. The presence or absence of abnormal appearance was evaluated according to the following criteria. The evaluation results are shown in Table 3. In addition, the direction without appearance abnormality means that solder heat resistance is favorable.
A: No abnormal appearance such as blistering or peeling B: There is abnormal appearance such as blistering or peeling

As shown in Table 3, the thermosetting adhesive compositions of Examples 1 to 3 exhibit excellent adhesion to ceramics and have good heat resistance when an adhesive layer is formed on the ceramic substrate. Is clear.
From the above results, according to the present invention, it is possible to provide a thermosetting adhesive composition and an adhesive film having excellent adhesion to ceramics while ensuring sufficient heat resistance.

Claims (6)

A diimide dicarboxylic acid mixture containing a diimide dicarboxylic acid represented by the following general formula (1), a diimide dicarboxylic acid represented by the following general formula (2) and a diimide dicarboxylic acid represented by the following general formula (3), and the following general formula (A) Polyamidoimide resin obtained by reacting with at least one aromatic diisocyanate represented by the formula (4a), (4b), (4c), (4d) or (4e), and (B) thermosetting Thermosetting adhesive composition for a ceramic substrate containing a functional resin.

[In the formula (1), R ¹ represents a group represented by the following general formula (1a), (1b), (1c), (1d), (1e), (1f), (1g) or (1h). Show. ]

[In General Formula (2), R ² represents a group represented by the following General Formula (2a), (2b), (2c), (2d), (2e), (2f), or (2g). ]

[In the general formula (2c), _{n 1} represents an integer of 1 to 70, in the general formula (2d), X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, halogenated aliphatic having 1-3 carbon atoms A hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group or a single bond, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or In general formula (2e), Y represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or a carbonyl group. In general formula (2f), Z represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a carbonyl group, or a single bond. ]

[In General Formula (3), R ⁹ and R ¹⁰ each independently represent a divalent organic group, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms or carbon The aryl group of number 6-18 is shown, m shows the integer of 1-50. ]

  The cured product obtained from the thermosetting adhesive composition has a storage elastic modulus at 25 to 250 ° C of 2000 MPa or less, a thermal expansion coefficient of 2000 ppm or less, and a glass transition temperature of 100 to 230 ° C. Thermosetting adhesive composition for ceramic substrates.   The thermosetting adhesive composition for a ceramic substrate according to claim 1 or 2, comprising 5 to 100 parts by mass of (B) a thermosetting resin with respect to 100 parts by mass of the (A) polyamideimide resin.   The diimide dicarboxylic acid represented by the general formula (2) is a reaction between polyoxypropylene diamine having an amine equivalent of 200 to 2500 g / mol or an alicyclic diamine having an amine equivalent of 50 to 200 g / mol and trimellitic anhydride. The diimide dicarboxylic acid represented by the general formula (3) is a compound obtained by reacting a siloxane diamine having an amine equivalent of 200 to 2500 g / mol with trimellitic anhydride, Item 4. The thermosetting adhesive composition for a ceramic substrate according to any one of Items 1 to 3.   The thermosetting adhesive composition for a ceramic substrate according to any one of claims 1 to 4, wherein the (B) thermosetting resin is an epoxy resin and further contains an epoxy resin curing accelerator or a curing agent. object.   The adhesive film which has the contact bonding layer which consists of a thermosetting resin composition for ceramic substrates in any one of Claims 1-5.