TW201336951A - Thermal conductive adhesive composition, and adhesive sheet and thermal conductive dicing and die attach film using the same - Google Patents

Abstract

PURPOSE: A thermoconductive adhesive composition is provided to have excellent heat-radiating performance and good adhesion and to improve reliability after moisture resistance test. CONSTITUTION: A thermoconductive adhesive composition comprises 100.0 parts by weight of a polymer which contains an epoxy resin and reactive functional group in the polymer structure; 50-400 parts by weight of an epoxy resin which has two or more epoxy groups in a molecule; 1000-14000 parts by weight of inorganic filler which is surface-treated by a silicon compound with a number average molecular weight of 500-10,000 and represented by chemical formula 1: (HR^1SiO)_a(R^23SiO_1/2)_b(R^3_2SiO)_c(R^4SiO_3/2)_d, and has a thermal conductivity of 10W/mK or more. In chemical formula 1, each of R^1-R^4 is a substituted or unsubstituted monovalent hydrocarbon group which does not has aliphatic unsaturated group; a is an integer from 0.1-0.7; b is an integer from 0.01-0.2; c is a number from 0-0.9; and d is a number from 0-0.2; and a+b+c+d=1.

Description

Thermally conductive adhesive composition and subsequent use sheet and thermal cut/solid crystal film

The present invention relates to a thermally conductive adhesive composition which can be used for the manufacture of a semiconductor device, and is particularly suitable for use in a resin molded semiconductor package, which has high thermal conductivity and excellent heat dissipation characteristics, and is suitable for the beryllium and solder resist of the object. , with strong adhesion, and the use of the subsequent sheet and thermal cut / solid crystal film.

In the manufacturing process of the semiconductor device, a large-diameter germanium wafer on which an IC circuit is formed is cut into a semiconductor wafer in a cutting (cutting) step, and is thermocompression-bonded by a curable liquid adhesive (solid crystal material) or the like. Then, after mounting on the lead frame and performing bonding between the electrodes, it is sealed by sealing it for operability or isolation of external environmental protection. The seal is in the form of a hermetic seal such as a metal seal or a ceramic seal, and a non-hermetic seal type using a resin, and the latter is a transfer molding method by a resin, which is excellent in mass productivity and low in price. widely used. Although the resin molded package has the above-described advantages, it is disadvantageous in that it is inferior in moisture resistance, heat resistance, thermal stress relaxation, heat dissipation, and the like.

In addition, in recent years, miniaturization and multi-functionalization of electrical appliances and electronic machinery, electronic components have become highly functional, and the wiring of semiconductor devices has also been developed to be more refined and denser due to such demands, because of semiconductor wafers. Large size, and because of the same size configuration (CSP) or laminated wafer structure as the face array bonded wafer without the lead frame The emergence of semiconductor devices (Stacked CSP, Sip), the thermal stress (stress) encountered in the package (PKG) is also becoming more stringent.

Further, in the mounting procedure of mounting these semiconductor devices to the printed circuit board, the reflow resistance corresponding to the lead-free solder also needs to reach a high temperature (265 ° C), and the conditions become increasingly severe. Therefore, the materials used are increasingly required to be optimized and high performance. In particular, among the package constituent materials, in order to be able to control the characteristics of the solid crystal material within a relatively wide range to easily meet these requirements, the solid crystal material is required to have low elasticity which can correspond to severe thermal stress (stress). Rate, and is a high adhesion, high heat resistance material.

In addition, the supporting substrate on which the semiconductor wafer is mounted also needs to be miniaturized. When the semiconductor wafer is mounted, the liquid adhesive oozes from the wafer end, causing contamination of the electrode or uneven thickness of the bonding layer to cause tilting of the wafer, resulting in poor bonding of the bonding wire. In view of the situation, it is desirable to have a thin film of an adhesive capable of improving these disadvantages.

In such an adhesive, a low modulus material having a structure in which a polyimine or a polyamidoximine which is excellent in heat resistance is introduced into a siloxane structure has been developed. In the patent documents 1, 2 and the like, a decane-denatured polyamidoquinone imine is proposed, but the low elasticity and the adhesion to the object are insufficient.

Patent Document 3 proposes to blend a compound having two or more maleimine groups in a decane-modified polyamidoximine to improve high-temperature characteristics, but the resin composition has poor adhesion.

Further, in Patent Documents 4 and 5, heat resistance composed of polythene oxide polyether and epoxy resin excellent in adhesion, low elasticity, and heat resistance is proposed. The film followed by the film, although the adhesion was improved, was not sufficiently low in elasticity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 3-189127

[Patent Document 2] Japanese Patent Laid-Open No. Hei 4-264003

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-60111

[Patent Document 4] Japanese Patent Laid-Open No. Hei 7-224259

[Patent Document 5] Japanese Patent Laid-Open No. Hei 8-27427

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-193016

In recent years, due to the miniaturization of semiconductor wafers and high-speed switching (that is, high-speed operation), the amount of heat generated per unit area tends to increase, and in order to efficiently dissipate heat, a semiconductor-attached film having a high thermal conductivity is gradually becoming a market demand. .

A composition in which a filler having a high thermal conductivity is added simply to increase the thermal conductivity is very fragile and cannot be processed into a film, and is an unpractical composition. Further, when a low-viscosity component is added in a large amount in order to improve the processability of the film, the force is lowered before and after moisture absorption, and the reliability as a semiconductor package is lowered.

The present invention has been made in view of the above circumstances, and the object is to solve the above-mentioned shortcomings. Provided is a thermally conductive adhesive composition which has high thermal conductivity, excellent heat dissipation characteristics, good adhesion, and excellent reliability after moisture resistance test; and a subsequent use of a sheet and a thermally conductive cut/solid crystal film .

As a result of intensive review in order to achieve the above object, the present inventors have found that it is effective to treat a surface of a thermally conductive filler with a specific polyoxynitride, and the present invention has been completed.

That is, first, the present invention provides a thermally conductive adhesive composition comprising the following components (A) to (C):

(A) 100 parts by mass of a polymer having a functional group reactive with an epoxy resin in a polymer skeleton

(B) 50 to 400 parts by mass of an epoxy resin having at least 2 epoxy groups in one molecule

(C) 1000 to 4000 parts by mass of an inorganic filler having a surface treatment of a polyfluorene oxide compound having a number average molecular weight of 500 to 10,000 represented by the following average composition formula (1) and having a thermal conductivity of 10 W/mK or more

(HR ¹ SiO) _a (R ² ₂ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (1) (wherein R ¹ to R ⁴ are each independently, indicating that they do not have An unsubstituted or substituted monovalent hydrocarbon group of an aliphatic unsaturated bond, a is a positive number of 0.1 to 0.7, b is a positive number of 0.01 to 0.2, c is a number of 0 to 0.9, and d is a number of 0 to 0.2, but satisfies a+b+c+d=1).

Secondly, the present invention provides a sheet for subsequent use, comprising: a substrate; and a substrate formed on the substrate and composed of the thermally conductive adhesive composition The layer of the agent.

Thirdly, the present invention provides a thermally conductive dicing/solid-state film comprising: a dicing film having a substrate and an adhesive layer disposed thereon, and the thermal conductivity provided on the adhesive layer of the dicing film The adhesive layer formed by the composition of the subsequent composition.

The adhesive composition of the present invention has high thermal conductivity, is excellent in heat dissipation characteristics, and is excellent in adhesion to a subject. By using the subsequent sheet and the thermally conductive cut/solid crystal film of the adhesive composition of the present invention, a highly reliable resin-packaged semiconductor device can be manufactured.

The invention is further described in detail below. Further, in the present specification, the weight average molecular weight and the number average molecular weight respectively refer to a weight average molecular weight and a number average molecular weight of polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions.

[Measurement conditions]

Developing solvent: tetrahydrofuran (THE)

Flow rate: 1mL/min.

Device: HLC-8320GPC (trade name, manufactured by Tosoh Corporation)

Detector: Differential Refractive Index Detector (RI)

Column: TSKgel GMH _XL -L+TSKgel G4000H _XL +TSKgel G2000H _XL +TSK gel G2000H _XL (trade name, manufactured by Tosoh Corporation)

Column temperature: 40 ° C

Sample injection amount: 100 μL (concentration 0.5% by mass of THF solution)

The adhesive composition of the present invention contains the components (A) to (C), and can maintain a shape at a normal temperature to form a flaky film which can be hardened by heating in a plastic state and exhibits excellent adhesion to the object. . The cured product of the adhesive composition of the present invention is excellent in thermal conductivity. A semiconductor package manufactured using a thermally conductive dicing/solid crystal film having an adhesive layer composed of the adhesive composition of the present invention is excellent in reliability.

[(A) a polymer having a functional group reactive with an epoxy resin in a polymer skeleton]

The reason why the adhesive composition of the present invention must have a polymer having a functional group reactive with an epoxy resin in a polymer skeleton is as follows. In the experiment, it was found that in the state of solid crystal, in order to make the gap between the film and the substrate small, the film must have a shear viscosity of at least 1 point at 130 to 170 ° C of 1 × 10 ³ to 1 × 10 ⁵ Pa‧ The scope of s. In order to maintain the aforementioned shear viscosity within a predetermined range, it is necessary to contain a polymer component having a higher viscosity than the monomer in the composition constituting the adhesive film. The component (A) may be used alone or in combination of two or more. Further, in order to form a strong matrix between the epoxy resin contained in the composition, it is necessary to have a functional group reactive with the epoxy resin.

The Tg of the polymer of the component (A) is preferably 40 ° C or higher. Making a bonding film using a polymer component having a Tg of 40 ° C or higher, and Then, the film is processed into a film for cutting the solid crystal film, and the adhesive film does not become too strong for the dicing film, and is not easily adhered to the dicing film, and the film is easily cut into a film in a short time. Since the peeling is performed, the production efficiency of the semiconductor device fabrication is easily improved.

The functional group reactive with the epoxy resin in the component (A) may, for example, be at least 1 selected from the group consisting of a carboxyl group, an amine group, an imine group, an epoxy group, a phenolic hydroxyl group, and a thiol group. a functional group.

The weight average molecular weight of the polymer of the component (A) in terms of polystyrene is preferably 10,000 to 200,000, preferably 20,000 to 100,000, more preferably 30,000 to 80,000. When the weight average molecular weight is within the above range, it is easy to form a coating film from the obtained composition, and it is also easy to obtain an adhesive film which is suitable for filling the unevenness of the surface of the substrate having a fine circuit pattern and having sufficient flexibility.

The polymer of the component (A) is exemplified by a polyimide resin. The polymer of the component (A) may also be a poly-proline which is a precursor of the polyimide resin. However, in the case of heat hardening in the solid phase step, water is formed by the imidization (dehydration ring closure). In the case where peeling of the adhesion surface occurs, etc., it is preferable to use a polyimine resin which is preliminarily imidized (dehydration ring closure). Examples of the polyamic acid include those represented by the following general formula (1). The polyimine resin may, for example, be a substance represented by the following general formula (2). The polyaminic acid and the polyimine resin may also contain a diorganopolyoxyalkylene bond, and it is preferred from the viewpoint of adhesion to have a phenolic hydroxyl group in the skeleton.

(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).

(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).

In the above general formula (1), q is an integer from 1 to 300, preferably an integer from 2 to 300, especially an integer from 5 to 300, and the polyamine having such a repeat number can be used The method is easily obtained. Further, the polyimine resin represented by the above general formula (2) can be obtained by dehydrating and ring-closing the polyamic acid represented by the above general formula (1) by a usual method.

The polyamic acid represented by the general formula (1) can be roughly obtained by subjecting the tetracarboxylic dianhydride represented by the following structural formula (3) to the diamine represented by the following structural formula (4) in accordance with a conventional method. The molar ratio is obtained by reacting in an organic solvent. (However, X means the same meaning as above).

H ₂ NY-NH ₂ (4) (however, Y represents the same meaning as described above).

Here, specific examples of the tetracarboxylic dianhydride represented by the above formula (3) include the following, but are not limited thereto.

In addition, one or two or more kinds of the tetracarboxylic dianhydrides represented by the above formula (3) may be used.

‧(a) Diamine oxirane compounds

The diamine represented by the above formula (4) is preferably from 1 to 80 mol%, more preferably from 1 to 60 mol%, and has solubility in an organic solvent, adhesion to a subject, and low From the viewpoint of elasticity and flexibility, it is desirable to be a diamine-based oxoxane compound represented by the following structural formula (5). (wherein R ¹ is a divalent organic group having 3 to 9 carbon atoms ^; and R ² and R ³ are each independently an unsubstituted or substituted one-valent hydrocarbon group having 1 to 8 carbon atoms, and r is 1 to 200. The integer).

In the alkoxyalkylene diamine (or α,ω-diaminopolyoxyalkylene) represented by the general formula (5), the divalent organic group having 3 to 9 carbon atoms represented by R ¹ may be exemplified. For example, an alkyl group of -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CH ₂ CH(CH ₃ )-, -(CH ₂ ) ₆ -, -(CH ₂ ) ₈ - or the like, An arylene group, an alkylene group having an alkyl group, an arylene group, a (CH ₂ ) ₃ —O—, —(CH ₂ ) ₄ —O— or the like, Oxyarylene or the like An isocratic alkyl group, an arylene group or the like may contain a divalent hydrocarbon group of an ether oxygen atom.

The unsubstituted or substituted one-carbon hydrocarbon group having 1 to 8 carbon atoms represented by R ² or R ³ may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a third butyl group. Alkenyl, phenyl, toluene of alkyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, etc. of a group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, an octyl group, etc. An aryl group such as an aryl group, a benzyl group or the like, an aralkyl group such as a benzyl group or a phenethyl group, or a part or all of a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom such as fluorine, bromine or chlorine. A group such as a halogen-substituted alkyl group such as a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group or the like, wherein a methyl group and a phenyl group are preferred.

Specific examples of the diaminocarboxane compound represented by the above formula (5) include the following:

These diamino sulfoxane compounds represented by the above formula (5) may be used alone or in combination of two or more kinds as desired.

‧(b) Diamine compounds without phenolic hydroxyl groups

Further, among the diamines represented by the above formula (4), examples of the diamine having no phenolic hydroxyl group other than the diaminocarboxane compound represented by the above formula (5) include, for example, p-phenylenediamine and Phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis(4-aminophenyl)propane, 4,4'-di Aminodiphenyl hydrazine, 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-aminophenyl sulfide)benzene , 1,4-bis(m-aminophenyl sulfide) 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, [3-Chloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[4 An aromatic ring such as -(4-aminophenoxy)phenyl]anthracene or 2,2-bis[4-(4-aminophenoxy)phenyl]perfluoropropane contains a diamine or the like, and is preferably 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-amine Phenoxy group) phenyl] propane and the like.

From the viewpoint of controlling the crosslinking point of the epoxy resin, adjusting the flexibility of the resin composition, and controlling the compatibility with the epoxy resin, it is desirable that 40 to 95 moles of the diamine represented by the above formula (4) is desired. % is a diamine compound not having the above phenolic hydroxyl group, more preferably 50 to 90 mol%.

‧(c) Diamine compounds with phenolic hydroxyl groups

Further, in the present invention, from the viewpoint of adhesion, it is preferred to have a phenolic hydroxyl group in the polymer skeleton of the polyimine resin, and the introduction of the hydroxyl group can be carried out by using a diamine compound having a phenolic hydroxyl group. Further, the phenolic hydroxyl group is highly reactive with an epoxy group, and the diamine can be exemplified by the following formula.

(wherein R ^{4 is} independently a hydrogen atom; a halogen atom such as a fluorine atom, a bromine atom or an iodine atom; or an unsubstituted or substituted carbon such as an alkyl group, an alkenyl group, an alkynyl group, a trifluoromethyl group or a phenyl group; The atomic number is 1 to 8 one-valent hydrocarbon group, n is an integer of 0 to 5, and A and B are respectively the same or different. R is independently a hydrogen atom, a halogen atom or an unsubstituted or substituted one-valent hydrocarbon group).

Here, the unsubstituted or substituted one-carbon hydrocarbon group having 1 to 8 carbon atoms of R ⁴ may be the same as the group exemplified as the above R ² or R ³ , and an ethynyl group, a propynyl group or a butyne group. An alkynyl group such as a hexenyl group or the like. Further, the unsubstituted or substituted one-valent hydrocarbon group of R may be the same as the group exemplified for the above R ⁴ .

In the present invention, among the diamine compounds having a phenolic hydroxyl group, a diamine compound represented by the following formula (6) is particularly preferable.

(wherein R ⁴ is the same as above).

Further, in the present invention, the blending amount of the diamine compound having a phenolic hydroxyl group is 5 to 60 mol% of the entire diamine compound, and particularly preferably 10 to 40 mol%. If the blending amount is too small, the adhesive strength may be lowered, and if it is too large, the flexibility of the adhesive layer may be insufficient.

‧(d) monoamine compounds with phenolic hydroxyl groups

Further, in order to introduce a phenolic hydroxyl group, a monoamine having a phenolic hydroxyl group may also be used, and the following structures may be exemplified: (In the formula, R ⁴ is the same as the above, and all or a part of the substituents to be bonded to the respective aromatic rings may be the same or may be different. D may be used alone or in combination of two or more. Further, p is 1 to 3 The integer).

In the case of using a monoamine having a phenolic hydroxyl group, the blending amount thereof is from 1 to 10 mol%, preferably from 2 to 8 mol%, based on the entire diamine compound.

The above-mentioned amine compound is not limited to these, and these amine compounds may be used singly or in combination of two or more kinds as desired.

When a specific example of the formation reaction of the polyaminic acid and the polyimine resin is exemplified, the starting material is dissolved in a solvent in an inert gas atmosphere, and usually reacted at 80 ° C or lower to synthesize a polylysine. , should be 0~40 °C. Further, the obtained polyaminic acid can be heated to a normal temperature of 100 to 200 ° C, preferably 150 to 200 ° C, to partially dehydrate the acid amide of poly-proline, thereby synthesizing the target polyimine. Resin.

The organic solvent used in the above reaction may be a solvent which is inactive to the obtained polyamic acid, and may be a solvent which does not completely dissolve the starting material. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Base carbamide and dimethyl hydrazine, preferably aprotic A polar solvent, particularly preferably N-methylpyrrolidone, cyclohexanone and γ-butyrolactone. These solvents may be used alone or in combination of two or more.

In order to facilitate the above-described dehydration ring closure, it is desirable to use an azeotropic dehydrating agent such as toluene or xylene. Alternatively, an anhydrous acetic acid/pyridine mixed solution can be used to carry out dehydration ring closure at a low temperature.

Further, in order to adjust the molecular weight of the polyamic acid and the polyimine resin, a dicarboxylic acid anhydride such as maleic anhydride or phthalic anhydride, aniline or n-butylamine, and the above-exemplified monoamine having a phenolic hydroxyl group may be added. One or both of the monoamines. However, the amount of the dicarboxylic acid anhydride added is usually 0 to 2 parts by mass per 100 parts by mass of the tetracarboxylic dianhydride, and the amount of the monoamine added is usually 0 to 2 parts by mass per 100 parts by mass of the diamine.

The polymer of the component (A) may be a phenoxy resin in addition to the polyimide resin. Such a phenoxy resin may, for example, be a bisphenol type epoxy resin derived from epichlorohydrin, bisphenol A or F or the like. Examples of such phenoxy resins include PKHC, PKHH, and PKHJ (all of which are manufactured by Ba Chemical Co., Ltd.); and bisphenol A and bisphenol F mixed products such as Epikote 4250, Epikote 4275, and Epikote 1255HX30. Epikote 5580BPX40 (all of which is manufactured by Nippon Kayaku Co., Ltd.), which is a brominated epoxy compound; bisphenol A type products such as YP-50, YP-50S, YP-55, and YP-70 (all of which are Dongdu Chemical Co., Ltd.); JER E1256, E4250, E4275, YX6954BH30, YL7290BH30 (all of which are manufactured by Japan Epoxy Resin Co., Ltd.).

[(B) Epoxy resin having at least 2 epoxy groups in one molecule]

The molecular structure, molecular weight, and the like of the epoxy resin of the component (B) are not particularly limited. The epoxy resin of the component (B) preferably has a weight average molecular weight in terms of polystyrene of from 100 to 10,000, preferably from 100 to 1,000. The component (B) may be used alone or in combination of two or more.

Examples of such an epoxy compound include bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane or a diglycidyl ether of the halide and the like. Bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc.), butadiene diepoxide, vinyl cyclohexene dioxide, resorcinol diglycidyl ether, 1,4-double (2,3-epoxypropoxy)benzene, 4,4'-bis(2,3-epoxypropoxy)diphenyl ether, 1,4-bis(2,3-epoxypropoxy) Cyclohexene, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 1,2-dioxybenzene or resorcinol, polyvalent phenol or polyol and epichlorohydrin Epoxy phenolic aldehyde obtained by condensation of a phenolic phenol resin (or a halogenated novolac type phenol resin) such as epoxy glycidyl ether or polyglycidyl ester obtained by alcohol condensation, phenol novolac, cresol novolac, and epichlorohydrin That is, a novolac type epoxy resin, an epoxidized polyolefin epoxidized by a peroxidation method, an epoxidized polybutadiene, a naphthalene ring containing an epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl type ring An oxygen resin, a biphenyl aralkyl type epoxy resin, a cyclopentadiene type epoxy resin, or the like.

Further, an epoxy compound having at least two of the above epoxy groups in one molecule may be suitably used in combination with a monoepoxy compound, which may be exemplified by phenylethylene oxide, epoxycyclohexane, and propylene oxide. , methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, octylene oxide, epoxy dodecane, and the like. Monoepoxy compounds can be used alone One type or two or more types may be used in combination.

The blending amount of the component (B) is usually 50 to 400 parts by mass, particularly preferably 80 to 300 parts by mass, per 100 parts by mass of the polymer of the component (A). When the blending amount of the epoxy resin is too small, there is a case where the adhesion is poor. If the amount is too large, in the case of the liquid epoxy resin, the film may exhibit excessive adhesion and is difficult to handle. In the case of a solid epoxy resin, there is a case where the adhesive layer is in a non-thin film state.

[(C) An inorganic filler having a surface treatment of a polyfluorene oxide having a number average molecular weight of 500 to 10,000 represented by the above average composition formula (1) and having a thermal conductivity of 10 W/mK or more]

The thermal conductivity of the inorganic filler of the component (C) is usually 10 W/mK or more, preferably 20 W/mK or more, and particularly preferably 30 W/mK or more. Further, in the present specification, the thermal conductivity is a value at 25 °C. When the thermal conductivity is less than 10 W/mK, heat dissipation may be insufficient, and the temperature of the semiconductor element and the substrate may increase. Further, the upper limit of the thermal conductivity is not particularly limited, and is typically below 500 W/mK. Specific examples of the inorganic filler to be surface-treated with the polyfluorene oxide compound include oxide powders such as alumina powder, zinc oxide powder, and magnesium oxide powder; aluminum nitride, hexagonal boron nitride, and cubic crystal nitrogen; a nitride such as boron or tantalum nitride; a metal powder such as an aluminum powder, a copper powder, a silver powder, a gold powder or a metal tantalum powder; a carbon powder such as a diamond powder or a carbon nanotube; or two or more of these The combination. The component (C) may be used alone or in combination of two or more. The average particle diameter of the component (C) is preferably 0.05 to 50 μm.

The polyxanthoxy compound which is surface-treated with the inorganic filler of the component (C) as a polyxanthene surface treatment agent is a polyoxonium compound having a number average molecular weight of 500 to 10,000 represented by the following average composition formula (1): (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (1) (wherein R ¹ to R ⁴ are each independently, indicating that they do not have An unsubstituted or substituted monovalent hydrocarbon group of an aliphatic unsaturated bond, a is a positive number of 0.1 to 0.7, b is a positive number of 0.01 to 0.2, c is a number of 0 to 0.9, and d is a number of 0 to 0.2, but satisfies a+b+c+d=1)

The polydecane oxide compound is a surface treatment agent as an inorganic filler, and has a function of a secondary auxiliary agent capable of reacting with a body. For the present invention, it is necessary to use the inorganic compound of the poly(oxygen) compound for the (C) component. The filler is subjected to a surface treatment. That is, when the surface-treated inorganic filler is heat-treated at a high temperature in the presence of the polyfluorene oxide compound, the hydroxyl group and the inorganic acid (surface treatment agent residue) remaining on the surface of the inorganic filler are mixed with the polymer. Dehydrogenation of the oxime compound whereby the surface is modified by the polyoxo compound. Further, in the polyoxynitride compound which modifies the surface, the remaining hydrogen atoms react with the host, and thus exhibit a strong adhesion. From these viewpoints, it is necessary for the present invention to carry out surface treatment of the component (C). The polyfluorene oxide compound is not particularly limited as long as it satisfies the above requirements, and can be synthesized by a conventionally known method. These polyoxygen compounds may be used alone or in combination of two or more.

In order to produce the component (C), it is preferred to heat-treat the inorganic filler in the presence of the polyfluorene oxide, and the temperature is preferably from 100 to 180 ° C, preferably from 110 to 170 ° C, more preferably from 120 to 160 ° C. Time should be 10 minutes or more, preferably 30 to 300 minutes, more preferably 50 minutes to 180 minutes. When the heat treatment temperature is in the range of 100 to 180 ° C, the reaction of the hydroxyl group remaining on the surface of the surface-treated inorganic filler and the reaction of the inorganic acid with the polyfluorene oxide compound tends to be fast, and the polyfluorene oxide compound is not easily obtained. Deterioration. In addition, when the heat treatment time is 10 minutes or more, the reaction of the hydroxyl group remaining on the surface of the surface-treated inorganic filler and the inorganic acid with the polyfluorene oxide compound is sufficiently performed.

The polyfluorene oxide compound is preferably a unit having at least two hydrogen atoms represented by the chemical formula HR ¹ SiO, having a hydrogen atom bonded to a ruthenium atom, located in the middle of the molecular chain (D ^H unit), and having one molecule At least two units which are represented by the chemical formula R ² ₃ SiO _1/2 and which do not have a hydrogen atom bonded to a ruthenium atom. That is, among the polyoxo compounds, the hydrogen atom bonded to the deuterium atom exists only in the middle of the molecular chain (that is, only in the (HR ¹ SiO) unit), and does not exist at the end of the molecular chain, and the end of the molecular chain _Preferably , it is blocked by a (R ² ₃ SiO _1/2 ) unit.

In the above average composition formula (1), when a is less than 0.1, it is difficult to obtain an excellent adhesion force to the object, and when it exceeds 0.7, a void is likely to be formed in the cured product. The situation in which the adhesion is reduced.

When b is less than 0.01, voids are likely to occur in the cured product, and when the adhesion force to the object is lowered, when it exceeds 0.2, it is difficult to obtain an excellent adhesion force to the object.

When c exceeds 0.9, the compatibility of the polyfluorene oxide compound and the epoxy resin matrix is liable to be lowered, and it is difficult to obtain an excellent connection to the object. Focus on.

When d exceeds 0.2, the viscosity is likely to rise, and it is difficult to obtain an excellent adhesion to the object.

The polyanthracene compound has a number average molecular weight of usually 500 to 10,000, preferably 500 to 7,500, preferably 1,000 to 5,000, and it is desirable to make the polysiloxane compound liquid at room temperature (25 ° C). When the number average molecular weight is less than 500, the volatility of the polyfluorene oxide tends to be high. Therefore, when the surface of the inorganic filler is subjected to heat treatment, it is difficult to heat at a high temperature, the surface treatment rate is lowered, and there is an adhesion force. Reduced concerns. When the number average degree of polymerization is more than 10,000, the polyoxynitride compound tends to be highly viscous, and it is difficult to ensure the wettability to the inorganic filler, and the surface treatment rate is lowered. Further, a large amount of residual polyoxosiloxane having no chemical bond is likely to be generated between the inorganic filler and the inorganic filler, and there is a concern that the adhesion force is lowered.

The viscosity of the polyfluorene compound at 25 ° C is preferably from 0.1 to 1000 mPa ‧ s, preferably from 0.5 to 500 mPa ‧ s, more preferably from 0.5 to 300 mPa ‧ s The polyoxynitride is desirably liquid at room temperature (25 ° C).

In the above average composition formula (1), the number of carbon atoms of R ¹ to R ⁴ is preferably from 1 to 10, preferably from 1 to 6. Specific examples of R ¹ to R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, a decyl group, and the like. An alkyl group such as a fluorenyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a fluorenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; a group in which a part or all of a hydrogen atom of a hydrocarbon group is substituted with a halogen atom such as a fluorine atom or a chlorine atom, for example, a 3,3,3-trifluoropropyl group or the like, preferably an alkyl group, an aromatic group, or a 3,3,3 group. -Trifluoropropyl, preferably methyl, phenyl, 3,3,3-trifluoropropyl.

Specific examples of the polyfluorene oxide compound include a copolymer composed of a (CH ₃ )HSiO unit, a (CH ₃ ) ₂ SiO unit, and a (CH ₃ ) ₃ SiO _1/2 unit; and a (CH ₃ )HSiO unit; (CH ₃ ) ₃ SiO _1/2 unit, (C ₆ H ₅ ) ₂ SiO unit, (CH ₃ ) ₂ SiO unit, CH ₃ SiO _3/2 unit copolymer; by (C ₆ H ₅ )HSiO a copolymer of a unit, a (CH ₃ ) ₃ SiO _1/2 unit, a (CH ₃ ) ₂ SiO unit, and a CH ₃ SiO _3/2 unit; a (CH ₃ )HSiO unit, a (CH ₃ ) ₂ SiO unit, a copolymer composed of C ₆ H ₅ SiO _3/2 units; from (CF ₃ C ₂ H ₄ )HSiO units, (CH ₃ ) ₃ SiO _1/2 units, (CH ₃ ) (CF ₃ C ₂ H ₄ ) a copolymer composed of a SiO unit and a CH ₃ SiO _3/2 unit; a (CH ₃ )HSiO unit, a (CH ₃ ) ₃ SiO _1/2 unit, a (CH ₃ )(CF ₃ C ₂ H ₄ )SiO unit, (CH ₃ ) ₂ SiO unit, copolymer of CH ₃ SiO _3/2 unit; (CH ₃ ) ₂ HSiO _1/2 unit, (CH ₃ ) (CF ₃ C ₂ H ₄ ) SiO unit, CH ₃ a copolymer composed of SiO _3/2 units; (CH ₃ )HSiO unit, (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ )(CF ₃ C ₂ H ₄ )SiO unit, (CH ₃ ) ₂ a copolymer composed of SiO units; by (CH ₃ ) HSiO unit, (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) (CF ₃ C ₂ H ₄ ) SiO unit, (CH ₃ ) ₂ SiO unit, CF ₃ C ₂ H ₄ SiO _3/2 unit a copolymer composed of (CH ₃ )HSiO unit, (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) ₂ SiO unit, CH ₃ SiO _3/2 a copolymer composed of units; consisting of (CH ₃ )HSiO units, (CH ₃ ) ₃ SiO _1/2 units, (CH ₃ ) ₃ SiO _1/2 units, (C ₆ H ₅ ) ₂ SiO units, (CH ₃ a copolymer composed of ₂ SiO units and CH ₃ SiO _3/2 units; (C ₆ H ₅ )HSiO units, (CH ₃ ) ₃ SiO _1/2 units, (CH ₃ ) ₂ SiO units, CH ₃ SiO A copolymer composed of _3/2 units.

In the case where the surface treatment of the inorganic filler is carried out with the polyfluorene oxide compound, the amount of the polyfluorene oxide compound used is preferably in the range of 0.05 to 5% by mass, preferably 0.1 to 3% by mass based on the inorganic filler. . When the amount used is in the range of 0.05 to 5% by mass, a large amount of voids are less likely to occur, and it is easy to sufficiently obtain the adhesion to the object.

The blending amount of the component (C) is usually 1,000 to 4,000 parts by mass, preferably 1,000 to 2,000 parts by mass, per 100 parts by mass of the polymer of the component (A). When the blending amount of the component (C) is too small, there is a case where a cured product having an industrially required thermal conductivity cannot be obtained. When the blending amount of the component (C) is too large, the obtained composition cannot be formed into a film shape, and it is difficult to use it as a film-like adhesive.

[(D) hardening catalyst]

The epoxy resin curing catalyst (D) used in the present invention is not particularly limited, and examples thereof include a phosphorus-based catalyst and an amine-based catalyst. The component (D) may be used alone or in combination of two or more.

Here, examples of the phosphorus-based catalyst include triphenylphosphine, triphenylsulfonium triphenylborate, tetraphenylphosphonium tetraphenylborate, or a compound as shown below: (wherein R ⁶ to R ¹³ are a hydrogen atom or a halogen atom such as fluorine, bromine or iodine; or an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an alkynyl group or an alkoxy group having 1 to 8 carbon atoms; An unsubstituted or substituted one-valent hydrocarbon group of a group, a trifluoromethyl group, a phenyl group or the like, all of which may be the same or different).

Here, examples of the one-valent hydrocarbon group of R ⁶ to R ¹³ include the same groups as those exemplified above for R ⁴ , and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butyl group. An alkoxy group such as an oxy group.

Further, examples of the amine-based catalyst include dicyanodiamide, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, and 2-phenyl-4. An imidazole derivative such as 5-dimethylol imidazole or the like.

The blending amount of the component (D) may be a catalyst amount (that is, an effective amount as a catalyst).

[(E) Epoxy Resin Hardener]

As the adhesive composition of the present invention, (E) a hardener of an epoxy resin can be used. As the curing agent, various curing agents for conventionally known epoxy resins can be used, and examples thereof include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, N-amineethylpiperazine, and bis(4-amine). 3-methylcyclohexyl)methane, m-decanediamine, montananediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro (5,5) An amine compound such as undecane; a denatured aliphatic polyamine such as an epoxy resin-diethylenetriamine adduct, an amine-ethylene oxide adduct or a cyanoethylated polyamine; bisphenol A, Trimethylol allyloxyphenol, low polymerization degree phenol novolac resin, epoxidized or butylated phenol resin or trade name "Super Beckcite" 1001 [made by Japan Reichhold Chemical Industry Co., Ltd.], "Hitanol" 4010 Phenol containing at least two phenolic hydroxyl groups in molecules such as phenol resin known in the world, such as manufactured by Hitachi, Ltd., Scado form L.9 (manufactured by Scado Zwoll Co., Ltd., and Methylon 75108 (manufactured by General Electric Company, USA) Resin; trade name "Beckamine" P.138 [made by Japan Reichhold Chemical Industry Co., Ltd.], "MELAN" [made by Hitachi, Ltd.], "U-Van" 10R [Toyo Takaya Industries, Ltd.] and the like well known carbon resin; amino resin a melamine resin, an aniline resin and the like; represented by the formula in one molecule and having at least two mercapto groups of the polysulfide resin HS (C ₂ H ₄ OCH ₂ OC ₂ H ₄ SS) _s C ₂ H ₄ OCH ₂ OC ₂ H ₄ SH (s = 1 to 10 integers); phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyrogallite anhydride, methyl nadic An organic acid such as an acid, dodecyl succinic anhydride or chloric anhydride or an anhydride thereof (anhydride). Among the above-mentioned curing agents, the phenol resin (phenol phenol resin) is suitable because it can impart good moldability, excellent moisture resistance, and no toxicity to the composition of the present invention. The hardening agent of the component (E) is not limited to one type at the time of use, and two or more types may be used in combination with the curing property.

Regarding the amount of the hardener to be used, the suitable blending amount may vary depending on the specific kind thereof, generally speaking, relative to the aforementioned epoxy resin. The range of 100 parts by mass to 0 to 100 parts by mass is preferably in the range of 5 to 50 parts by mass. When the amount of the hardener used is less than 1 part by mass, there is a case where it is difficult to harden the composition of the present invention. On the contrary, if it exceeds 100 parts by mass, the economic efficiency is deteriorated, and the epoxy resin is diluted. Hardening becomes a long time, and even an unfavorable situation in which the physical properties of the hardened material are lowered may occur.

Further, in the case where the component (A) is a polyimine resin having a phenolic hydroxyl group in the skeleton, the blending ratio of the epoxy resin to the phenol resin hardener is important. In this case, the curing reaction is carried out by the reaction of a phenolic hydroxyl group and an epoxy group. However, if the epoxy group is too small, there is a concern that the adhesion to the object is insufficient, and if it is too large, there is an epoxy resin. When the modulus of elasticity is increased, it is not suitable for producing a soft adhesive sheet. Therefore, the blending amount of the epoxy resin and the phenol resin hardener is desirably 1 to 900 parts by mass, preferably 5 to 400 parts by mass, per 100 parts by mass of the polyimine resin.

Here, the sum of the phenolic resin curing agent and the polyimine resin having a phenolic hydroxyl group in the skeleton is not particularly limited with respect to the chemical equivalent ratio of the epoxy resin, and is preferably in the range of 0.7 to 1.3. Good is 0.8~1.2. If it exceeds this range, there will be a situation in which the characteristics change over time.

Further, even in the case where the phenol resin is not used as the epoxy resin hardener, the blending amount and the equivalent ratio of the polyimide resin and the epoxy resin may be set to be the same as described above.

[Other ingredients]

Further, in the resin composition of the present invention, it is possible to add a filler other than the component (C) such as cerium oxide fine powder, titanium oxide, carbon black, or conductive particles in accordance with the purpose within the range that does not impair the effects of the present invention. Additives such as a coloring agent such as a pigment, an inorganic or organic pigment, a dye, a wetting agent, an antioxidant, a heat stabilizer, and the like.

[Preparation method and use of adhesive composition]

The adhesive composition of the present invention can be prepared by mixing the above components (A) to (C) and, if necessary, the component (D), the component (E), and other components in accordance with a usual method.

The method of using the adhesive composition of the present invention obtained above is as follows. For example, the adhesive composition is dissolved in toluene, an aprotic polar solvent such as cyclohexanone or NMP at an appropriate concentration, applied to a substrate, dried, pressure-bonded to the object, and heat-cured. Further, an adhesive composition which is dissolved in a solvent at an appropriate concentration may be applied onto a support substrate (hereinafter referred to as a substrate for short) and dried to obtain a substrate and provided on the substrate. The subsequent adhesive layer (formed into a film-like composition, which will be referred to as a bonding film hereinafter) is laminated on the film, and the film is sandwiched between the substrate and the object to be crimped. Heat hardened to continue. The foregoing substrate may be polyethylene, polypropylene, polyester, polyamine, polyimine, polyamidimide, polyetherimine, polytetrafluoroethylene, paper, metal foil, etc., or The surface of the surface is subjected to mold release treatment.

When the adhesive composition is formed into a film shape to obtain a film, It is dried at room temperature ~200 °C, especially at 80~150 °C for 1 minute to 1 hour, especially 3 to 10 minutes.

The film thickness of the film is not particularly limited, and may be selected from 5 to 100 μm, particularly preferably from 5 to 40 μm, depending on the purpose. In addition, after the film is pressure-bonded at a pressure of 0.01 to 10 MPa, it is cured at a temperature of 100 to 200 ° C for 30 minutes to 5 hours, and particularly preferably after curing at 0.1 to 2 MPa for 1 to 4 hours at 120 to 180 ° C.

The method of using the thermally conductive cut/solid crystal film using the adhesive composition of the present invention as an adhesive layer is as follows. The base film on the side of the adhesive layer is peeled off as necessary. The wafer is thermocompression bonded to the adhesive layer of the dicing/solidifying film and fixed on the dicing/solid crystal film. The thermocompression bonding conditions can be variously selected depending on the composition of the adhesive layer, and are usually 40 to 120 ° C and 0.01 to 0.2 MPa. Next, after being fixed to the dicing apparatus for dicing, the wafer adhering to the adhesive layer is peeled off from the adhesive layer and picked up, and the wafer is thermocompression-bonded to the lead frame, and is cured by heating. The thermocompression bonding conditions may be set to be the same as the thermocompression bonding conditions of the wafer and the adhesive layer. Further, the heat curing conditions may be variously selected depending on the composition of the adhesive layer, and are usually 120 to 250 °C.

The adhesive composition of the present invention can be used not only as a dicing/solid-crystal film but also in various subsequent steps in the manufacture of electronic parts.

[Examples]

The embodiments and comparative examples are disclosed below to specifically illustrate the present invention. However, the invention is not limited by the following examples.

[material] (A) a polymer having a functional group Tg reactive with an epoxy resin in a polymer skeleton of 45 ° C or higher

‧ Polyimine resin having a phenolic hydroxyl group obtained in the following Synthesis Example 1

‧jER (registered trademark) 1256 (trade name, phenoxy resin with epoxy group, manufactured by JER Co., Ltd., weight average molecular weight: 50,000, Tg: 100 ° C)

(B) an epoxy resin having at least 2 epoxy groups in one molecule

‧RE-310S: Bisphenol A type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight: 600)

(C) an inorganic filler which is subjected to surface treatment and has a thermal conductivity of 10 W/mK or more by a polyfluorene oxide compound having a number average molecular weight of 500 to 10,000 represented by the above average composition formula (1)

‧ (C1) AO-502 (trade name, manufactured by Admatechs Co., Ltd., alumina, thermal conductivity: 27 W/mK, the same applies below) which is surface-treated with polyoxyl compound C1 of the following formula:

That is, the polyoxo compound represented by the following average composition formula: (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (formula In the above, R ¹ to R ⁴ represent a methyl group, a is 0.167, b is 0.167, c is 0.667, and d is 0). Number average molecular weight: 700

‧(C2) AO-502 surface-treated with polyoxyl compound C2 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average molecular weight of 8400, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _{3 /2} ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.409, b is 0.013, c is 0.579, and d is 0).

‧(C3) AO-502 surface-treated with polyoxyl compound C3 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average molecular weight of 1,700, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _{3 ) /2} ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.469, b is 0.063, c is 0.469, and d is 0).

‧(C4) AO-502 surface treated with polyoxyl compound C4 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average molecular weight of 3400, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _{3 /2} ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.691, b is 0.029, c is 0.279, and d is 0).

(C') (comparative) inorganic having a surface treatment and a thermal conductivity of 10 W/mK or more, which is a polyfluorene oxide compound having a number average molecular weight of 500 to 10,000 represented by the above average composition formula (1) filling Or an inorganic filler which is not surface treated with a polyoxynitride and has a thermal conductivity of 10 W/mK or more.

‧ (C5) AO-502 surface-treated with polyoxyl compound C5 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average molecular weight of 1400, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _{3 /2} ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.083, b is 0.083, c is 0.833, and d is 0).

‧ (C6) AO-502 surface-treated with polyoxyl compound C6 of the following formula

That is, the polyoxonium compound represented by the average composition formula has a number average degree of polymerization: 39800, (HR ¹ SiO) _a (R ² sSiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _{3/2 d} (wherein R ¹ to R ⁴ represent a methyl group, a is 0.154, b is 0.003, c is 0.843, and d is 0).

‧(C7) AO-502 surface treated with polyoxyl compound C7 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average degree of polymerization: 400, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.500, b is 0.333, c is 0.167, and d is 0).

‧(C8) AO-502 surface treated with polyoxyl compound C8 of the following formula

That is, the polyoxonium compound represented by the following average composition formula has a number average degree of polymerization: 900, (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (wherein R ¹ to R ⁴ represent a methyl group, a is 0.889, b is 0.111, c is 0, and d is 0).

‧(C9) AO-502 without surface treatment with polyoxyl compounds

Further, the components (C1) to (C8) are heat-treated at 150 ° C by mixing 1.7 parts by mass of the above polysiloxane compound corresponding to the components (C1) to (C8) with 100 parts by mass of AO-502. Minutes to modulate.

(D) hardening catalyst

‧DICY-7 (trade name, manufactured by JER Co., Ltd., dicyandiamide)

[Synthesis of Polyimine Resin] [Synthesis Example 1]

In a 1 L separable flask equipped with a 25 ml moisture-containing receiving tube, a thermometer, and a stirrer connected to a reflux condenser, a diamine-based oxirane having the following structural formula as a diamine was charged (trade name: 44.03 parts by mass of KF-8010 and Shin-Etsu Chemical Co., Ltd., and 100 parts by mass of 2-methylpyrrolidone as a reaction solvent were stirred at 80 ° C to disperse the diamine in the reaction solvent. A solution of 38.72 parts by mass of 6FDA (2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride) as an acid anhydride and 100 parts by mass of 2-methylpyrrolidone was added dropwise thereto. The acid is stirred for 2 hours to react the diamine with the acid anhydride, thereby synthesizing an acid anhydride-rich proline oligomer.

However, t=10

Next, the following formula will be: 17.25 parts by mass of the aromatic diamine having a phenolic hydroxyl group and 100 parts by mass of 2-methylpyrrolidone are separated into 1 L which is equipped with a moisture metering receiving tube, a thermometer and a stirrer provided with a 25 ml cocked plug connected to a reflux condenser. In the flask, the aromatic diamine was dispersed in 2-methylpyrrolidone. After the above-described acid anhydride-rich phthalic acid oligomer was dropped thereinto, the mixture was stirred at room temperature for 16 hours to synthesize a polyaminic acid solution. Then, after adding 25 ml of xylene to this solution, the temperature was raised to reflux at about 180 ° C for 2 hours. It was confirmed that a predetermined amount of water was accumulated in the moisture distillation receiving tube, and no outflow of water was observed, and the effluent accumulated in the moisture distillation receiving tube was removed, and the xylene was removed at 180 °C. After completion of the reaction, the obtained reaction was dropped into a large excess of methanol to precipitate a polymer, and dried under reduced pressure to obtain a polyimine resin having a phenolic hydroxyl group in the skeleton. The content of the phenolic hydroxyl group was 20 mol% relative to the amine unit. Further, the weight average molecular weight was 50,000.

As a result of measuring the infrared absorption spectrum of the obtained polyimine resin, the absorption by polyamine which still has an unreacted functional group did not occur, and a quinone imine group was confirmed at 1780 cm ^-1 and 1720 cm ^{-1 .} The absorption produced was confirmed to have an absorption by a phenolic hydroxyl group at 3,500 cm ^-1 .

The obtained polyimine resin was cast on a Teflon (registered trademark) film to prepare a polyimide film having a thickness of 100 μm. The Tg of the polyimide film was measured by a thermomechanical analysis (TMA) method using a thermomechanical tester TM-7000 manufactured by Vacuum Technology Co., Ltd. under a load of 10 g and a temperature increase rate of 10 ° C/min. °C.

[Evaluation of Modulation and Characteristics of Adhesive Compositions] [Examples 1 to 7 and Comparative Examples 1 to 7]

The component (A) was dissolved in a polymer diluent solvent (cyclohexanone) by the blending amount shown in the following Table 1 or 2, and added in the obtained solution in the amount shown in the following Table 1 or 2. The component (B), the component (C), the component (C), the component (D), and the solvent to be added are mixed and mixed to prepare an adhesive composition.

[Following the production of sheets]

The adhesive composition obtained above was applied onto a PET film coated with a fluoropolyoxymethylene release agent and having a thickness of 38 μm, and dried by heating at 110 ° C for 10 minutes to prepare an adhesive layer having a thickness of about 25 μm. Hereinafter, it is referred to as a subsequent sheet of the film.

[260 ° C shearing force]

A 3 mm x 3 mm follow-up film was obtained from the subsequent sheet produced as described above. In addition, a 3 mm × 3 mm × 725 μm thick tantalum wafer was prepared and coated with AUS308 (trade name, solder resist, manufactured by Sun Ink Co., Ltd.). A BT substrate (15 mm × 15 mm) having a surface roughness of 5 μm or less. The bonding film and the germanium wafer are sequentially stacked on the BT substrate, and the lower surface of the germanium wafer is entirely covered by the adhesive film, and solid crystallizing is performed at 170 ° C, 0.67 MPa, and 2 sec. The laminate composed of the tantalum wafer, the adhesive film, and the BT substrate was heated at 175 ° C / 4 hrs, and after curing the adhesive film, at a temperature of 260 ° C, a height of 50 μm from the BT substrate was 200 μm / The shear rate of sec was measured to obtain the adhesion of the cured film followed by the film. The results are disclosed in Table 1 or 2.

[Shear adhesion at 260 ° C after JEDEC L2]

The laminate consisting of a tantalum wafer ‧ a film and a BT substrate is stored under JEDEC L2 conditions (168 hrs at 85 ° C, 60% RH), and then passed through an IR reflow device having a maximum temperature of 260 ° C. After 3 times, the adhesion of the cured film to the film was measured under the same conditions as described above. The results are disclosed in Table 1 or 2.

[Thermal conductivity]

A plurality of the above-mentioned adhesive films were laminated, and a disk-shaped laminate having a thickness of 50 μm and a diameter of 12.5 mm composed of the adhesive film was produced. The laminate was sandwiched between two 1 mm thick Al plates, heated to 175 ° C, and after curing the adhesive film, the thermal conductivity of the cured film was measured by a laser flash method using a NETZSCH strontium flash analyzer LFA447. . The results are disclosed in Table 1 or 2.

Claims (7)

A thermally conductive adhesive composition comprising the following components (A) to (C): (A) 100 parts by mass of a polymer having a functional group reactive with an epoxy resin in a polymer skeleton (B) 50 to 400 parts by mass of the epoxy resin having at least two epoxy groups in the molecule (C) is subjected to surface treatment and thermal conductivity by a polyfluorene oxide having a number average molecular weight of 500 to 10,000 represented by the following average composition formula (1) Inorganic filler of 10 W/mK or more 1000 to 4000 parts by mass (HR ¹ SiO) _a (R ² ₃ SiO _1/2 ) _b (R ³ ₂ SiO) _c (R ⁴ SiO _3/2 ) _d (1) ( In the formula, R ¹ to R ⁴ are each independently, and represent an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, a is a positive number of 0.1 to 0.7, b is a positive number of 0.01 to 0.2, and c is 0 to 0.9. The number, d is the number from 0 to 0.2, but satisfies a+b+c+d=1). The thermally conductive adhesive composition according to claim 1, wherein the component (A) contains at least one polymer selected from the group consisting of polyimine resins, which are polyamines. a ring-closing derivative of an acid which is a reaction product of a tetracarboxylic dianhydride and a diamine compound containing a diamine represented by the following formula (5), (wherein R ¹ is a divalent organic group having 3 to 9 carbon atoms ^; and R ² and R ³ are each independently an unsubstituted or substituted one-valent hydrocarbon group having 1 to 8 carbon atoms, and r is 1 to 200. The integer). The thermally conductive adhesive composition of claim 2, wherein the diamine compound further contains a diamine represented by the following formula (6'), Wherein R ^{4 is} independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted one-carbon hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 0 to 5, and A is independently (wherein R ⁴ is the same as above, R is independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted monovalent hydrocarbon group), and B is independently (wherein R ⁴ is the same as above)]. The thermally conductive adhesive composition of claim 3, wherein the diamine represented by the above formula (6') is a diamine represented by the following formula (6), (wherein R ⁴ is the same as above). The thermally conductive adhesive composition according to any one of claims 1 to 4, which is formed into a film shape. A subsequent sheet comprising: a substrate and an adhesive layer comprising the thermally conductive adhesive composition according to any one of claims 1 to 5 disposed on the substrate. A thermally conductive cutting/solid-crystal film comprising: a dicing film having a substrate and an adhesive layer disposed thereon, and an adhesive layer disposed on the dicing film by any one of claims 1 to 5 An adhesive layer composed of a thermally conductive adhesive composition.