RESIN COMPOSITION, SHEET-FORM COMPOSITION, SHEET CURED PRODUCT, LAMINATE, LAMINATE MEMBER, WAFER HOLDER, AND SEMICONDUCTOR MANUFACTURING DEVICE

Abstract

The purpose of the present invention is to provide a resin composition which enables manufacturing an adhesive sheet for a electrostatic chuck which has excellent heat resistance, low elastic modulus, mitigates the substrate thermal expansion difference with a single layer, and is capable of adhesion and following. The resin composition contains a polymer (A) selected from polyimide and polyamic acid that have a diamine residue of a specific structure (below, the diamine residue (1)) and an acid anhydride residue of a specific structure (below, the acid anhydride residue (2)), and a thermosetting resin (B).

Claims

1. A resin composition comprising: a polymer (A) selected from a polyimide and a polyamic acid having a diamine residue represented by General Formula (1) (hereinafter referred to as a diamine residue (1)) and an acid anhydride residue represented by General Formula (2) (hereinafter referred to as an acid anhydride residue (2)); and a thermosetting resin (B): ##STR00005## wherein, in General Formula (1), R.sup.1 to R.sup.4 may be same or different and each represent an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group, the phenyl group and the phenoxy group may be substituted with an alkyl group having 1 to 30 carbon atoms, m R.sup.1s and R.sup.3s may be same or different, in General Formula (1), R.sup.5 and R.sup.6 may be same or different and each represent an alkylene group having 1 to 30 carbon atoms or an arylene group, the arylene group may be substituted with an alkyl group having 1 to 30 carbon atoms, in General Formula (1), m is an integer selected from 1 to 100, ##STR00006## in General Formula (2), R.sup.7 to R.sup.10 may be same or different and each represent an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group, the phenyl group and the phenoxy group may be substituted with an alkyl group having 1 to 30 carbon atoms, n and R.sup.9 s may be same or different, in General Formula (2), R.sup.11 and R.sup.12 may be same or different and each represent an alkylene group having 1 to 30 carbon atoms or an arylene group, the arylene group may be substituted with an alkyl group having 1 to 30 carbon atoms, and in General Formula (2), n is an integer selected from 1 to 100.

2. The resin composition according to claim 1, wherein a total of the diamine residue (1) and the acid anhydride residue (2) is 55 mol % or more and 100 mol % or less with a total of all diamine residues and all acid anhydride residues in the polymer (A) being 100 mol %.

3. The resin composition according to claim 1, containing 60 mol % or more and 100 mol % or less of the diamine residue (1) with all diamine residues in the polymer (A) being 100 mol %.

4. The resin composition according to claim 1, containing 50 mol % or more and 100 mol % or less of the acid anhydride residue (2) with all acid anhydride residues in the polymer (A) being 100 mol %.

5. The resin composition according to claim 1, wherein the m is 3 or more and 40 or less, and the n is 3 or more and 40 or less.

6. The resin composition according to claim 1, wherein the polymer (A) has a glass transition temperature (Tg) of 150 C. or higher and 30 C. or lower.

7. The resin composition according to claim 1, wherein the thermosetting resin (B) is at least one selected from the group consisting of a polyimide resin, a bismaleimide resin, an epoxy resin, a phenol resin, a urethane resin, a silicone resin, an acrylic resin, and a poly(amide-imide) resin.

8. The resin composition according to claim 1, wherein the thermosetting resin (B) is at least one selected from the group consisting of an epoxy resin containing an aromatic skeleton, a flexible epoxy resin not containing a siloxane skeleton, and a crystalline epoxy resin.

9. The resin composition according to claim 1, comprising an inorganic filler (C).

10. The resin composition according to claim 1, comprising a curing agent or curing accelerator (D).

11. The resin composition according to claim 1, wherein a sheet cured product has a glass transition temperature (Tg) of 120 C. or higher and 0 C. or lower.

12. A sheet-form composition comprising the resin composition according to claim 1 formed into a sheet.

13. A sheet cured product comprising a cured product of the resin composition according to claim 1.

14. A laminate comprising: the resin composition according to claim 1; and a resin sheet.

15. A laminate member comprising in this order: a member A; the sheet cured product according to claim 13; and a member B, wherein linear expansion coefficients of the member A and the member B are different by one or more.

16. A wafer holder comprising the laminate member according to claim 15.

17. A semiconductor manufacturing device comprising the wafer holder according to claim 16.

Description

EXAMPLES

[0111] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. First, evaluation methods performed in Examples 1 to 17 and Comparative Examples 1 and 2 will be described.

[0112] <Production of Evaluation Sample>

[0113] A sheet-form composition produced in each of Examples and Comparative Examples described later was cut into 50 mm square, one protective film of an adhesive agent sheet having an adhesive agent layer with a thickness of 50 m was further peeled off, and the adhesive agent layers were laminated to each other under the conditions of 120 C. and 0.4 MPa to perform lamination. This procedure was repeated to form an adhesive agent layer having a thickness of 200 m, and then the product was heated and cured at 180 C. for 6 hours to provide a sheet cured product sample for evaluation.

[0114] (1) Elastic Modulus at 25 C.:

[0115] The sheet cured product sample for evaluation was cut into a size of 5 mm20 mm to produce a sheet cured product sample for evaluation of the elastic modulus at 25 C.

[0116] The elastic modulus of the sample for evaluation of the elastic modulus at 25 C. was measured with a dynamic viscoelasticity measuring apparatus DMS6100 manufactured by Seiko Instruments Inc. The storage elastic modulus at each temperature in the range from 130 C. to 300 C. was measured under the measurement conditions of a temperature rise rate of 5 C./min and a measurement frequency of 1 Hz, and the value of the storage elastic modulus at 25 C. was taken as the elastic modulus at 25 C.

[0117] (2) Glass Transition Temperature (Tg)

[0118] Using the sheet cured product sample for evaluation cut into 5 mm20 mm, dynamic viscoelasticity measurement was performed to determine the glass transition temperature (Tg). The measurement was performed using a dynamic viscoelasticity measuring apparatus DMS6100 manufactured by Seiko Instruments Inc. at temperatures of 70 to 300 C., a temperature rise rate of 5 C./min, a tensile mode, and a frequency of 1 Hz. The temperature of the peak value of tan 5 of the obtained curve was defined as Tg.

[0119] (3) Shear Strain

[0120] A sheet-form composition described later was cut into 10 mm10 mm, and a PET film on one side was peeled off, and then the sheet composition was attached to an aluminum plate having a length of 50 mma width of 15 mma thickness of 0.5 mm. Further, a PET film on the other side was peeled off, and the surface was attached to another aluminum plate in a shifted state to produce a test piece for a shear test.

[0121] The test piece for the shear test was heated and cured at 180 C. for 6 hours and then subjected to a tensile test with a tensile and compression testing machine Technograph TG-1 kN manufactured by MinebeaMitsumi Inc., and the displacement at the breaking point was measured. The measurement was carried out at a load cell of 1 kN and a pulling rate of 5 mm/min. The value obtained by dividing the displacement at the breaking point by the thickness of the sheet-form composition was taken as the shear strain.

[0122] (4) Heat Resistance

[0123] The test piece for the shear test obtained by the above method was heated and cured at 180 C. for 6 hours and further heated at 250 C. for 1,000 hours under vacuum, and the test piece was subjected to a tensile test with a tensile and compression testing machine Technograph TG-1 kN manufactured by MinebeaMitsumi Inc. to calculate the shear strain. The measurement was carried out at a load cell of 1 kN and a pulling rate of 5 mm/min. A sample in which the change rate between the shear strain after heat curing at 180 C. for 6 hours and the shear strain after further heating under vacuum at 250 C. for 1,000 hours was less than 30% was rated as good, and a sample in which the change rate was 30% or more was rated as poor.

[0124] (5) Imidization Rate of Synthesized Polymer (A)

[0125] First, the infrared absorption spectrum of the polymer (A) was measured to confirm the presence of absorption peaks (near 1780 cm.sup.1 and near 1377 cm.sup.1) of the imide structure attributed to the polyimide. Next, the polymer (A) was subjected to a heat treatment at 350 C. for 1 hour, an infrared spectrum was measured again, and then peak intensities near 1,377 cm.sup.1 before the heat treatment and after the heat treatment were compared. Assuming that the imidization rate of the polymer (A) after the heat treatment was 100%, the imidization rate of the polymer (A) before the heat treatment was determined.

[0126] (6) Glass Transition Temperature (Tg) of Synthesized Polymer (A)

[0127] After removing the solvent of the polymer (A), differential scanning calorimetry was performed to determine the glass transition temperature (Tg). The measurement was performed using a differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Inc. at temperatures of 150 to 300 C. and a temperature rise rate of 10 C./min. The onset temperature of the obtained DSC curve was defined as the Tg of the polymer (A).

[0128] (7) Weight Average Molecular Weight of Synthesized Polymer (A)

[0129] A solution having a polyimide concentration of 0.1 wt % obtained by dissolving the polymer (A) obtained by the method described in each of Examples and Comparative Examples in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was subjected to measurement as a measurement sample using a GPC apparatus Waters 2690 (manufactured by Waters Corporation) having the following structure to calculate the weight average molecular weight in terms of polystyrene.

[0130] The GPC measurement conditions were as follows: a moving bed was NMP in which LiCl and phosphoric acid were dissolved at concentrations of 0.05 mol/L each, and the development rate was 0.4 ml/min. [0131] Detector: Waters 996 [0132] System controller: Waters 2690 [0133] Column oven: Waters HTR-B [0134] Thermocontroller: Waters TCM [0135] Column: TOSOH guard column (placed to capture coarse particles mixed in the object to be measured and prevent clogging of the column) [0136] Column: TOSOH TSK-GEL -4000 (a column with an exclusion limit molecular weight of 1,000,000) [0137] Column: TOSOH TSK-GEL -2500 (a column with an exclusion limit molecular weight of 10,000)

[0138] These three columns were connected in series in this order.

[0139] The details of the raw materials indicated by abbreviations in each Example are shown below.

[0140] <Resin>

[0141] The polymer (A) selected from polyimides and polyamic acids

[0142] <Raw Material of Polymer (A)> [0143] X-22-168 AS: (manufactured by Shin-Etsu Chemical Co., Ltd.) (number average molecular weight: 1,000, both-end acid-anhydride-modified polysiloxane of General Formula (2), n=9) (R.sup.7 to R.sup.10 are methyl groups) [0144] X-22-168 A: (manufactured by Shin-Etsu Chemical Co., Ltd.) (number average molecular weight: 2,000, both-end acid-anhydride-modified polysiloxane of General Formula (2), n=19) (R.sup.7 to R.sup.10 are methyl groups) [0145] ODPA: 4,4-oxydiphthalic dianhydride (manufactured by Manac Incorporated) [0146] BPDA: 3,3-4,4-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation) [0147] KF 8010: diaminopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) (number average molecular weight: 860, diaminopolysiloxane of General Formula (1), m=9) (R.sup.1 to R.sup.4 are methyl groups, and R.sup.5 and R.sup.6 are trimethylene groups) [0148] X-22-161 A: diaminopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) (number average molecular weight: 1,600, diaminopolysiloxane of General Formula (1), m=19) (R.sup.1 to R.sup.4 are methyl groups, and R.sup.5 and R.sup.6 are trimethylene groups) [0149] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoroisopropylidene (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0150] <Synthesis of Polymer (A)>

[0151] Polymer (A) A

[0152] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 47.27 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 3.66 g of BAHF and 77.40 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) A (solid content concentration: 80.0 wt %). The weight average molecular weight of the polymer (A) A was measured and found to be 45,600, and the imidization rate was measured and found to be 99%.

[0153] Polymer (A) B

[0154] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 102.24 g of dimethylacetamide, 98.00 g of X-22-168AS, and 7.45 g of ODPA were charged thereto under a nitrogen atmosphere and stirred and dissolved at Thereafter, while stirring at 120 C., 4.40 g of BAHF and 89.64 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) B (solid content concentration: 60.0 wt %). The weight average molecular weight of the polymer (A) B was measured and found to be 57,320, and the imidization rate was measured and found to be 99%.

[0155] Polymer (A) C

[0156] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 113.92 g of dimethylacetamide, 77.25 g of X-22-168AS, and 23.27 g of ODPA were charged thereto under a nitrogen atmosphere and stirred and dissolved at Thereafter, while stirring at 120 C., 5.49 g of BAHF and 112.05 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) C (solid content concentration: 60.0 wt %). The weight average molecular weight of the polymer (A) C was measured and found to be 69,750, and the imidization rate was measured and found to be 99%.

[0157] Polymer (A) D

[0158] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 92.93 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 11.72 g of BAHF and 41.28 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) D (solid content concentration: 80.0 wt %). The weight average molecular weight of the polymer (A) D was measured and found to be 60,350, and the imidization rate was measured and found to be 99%.

[0159] Polymer (A) E

[0160] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 132.70 g of triethylene glycol dimethyl ether and 121.00 g of X-22-168A were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 2.01 g of BAHF and 76.23 g of X-22-161A were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) E (solid content concentration: 60.0 wt %). The weight average molecular weight of the polymer (A) E was measured and found to be 48,020, and the imidization rate was measured and found to be 99%.

[0161] Polymer (A) F

[0162] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 39.86 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., g of BAHF and 25.80 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) F (solid content concentration: 80.0 wt %). The weight average molecular weight of the polymer (A) F was measured and found to be 55,680, and the imidization rate was measured and found to be 99%.

[0163] Polymer (A) G

[0164] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 33.79 g of triethylene glycol dimethyl ether, 32.40 g of X-22-168AS, and 21.72 g of ODPA were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 3.66 g of BAHF and 77.40 g of KF8010 were added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) G (solid content concentration: 80.0 wt %). The weight average molecular weight of the polymer (A) G was measured and found to be 59,790, and the imidization rate was measured and found to be 99%.

[0165] Polymer (A) H

[0166] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 300-ml four-necked flask, and 88.39 g of triglyme and 14.56 g of BPDA were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 1.83 g of BAHF and 72.00 g of X-22-161A were added thereto, and the mixture was further stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) F (solid content concentration: 50.0 wt %). The weight average molecular weight of the polymer (A) F was measured and found to be 45,300, and the imidization rate was measured and found to be 99%.

[0167] Polymer (A) I

[0168] A stirrer, a thermometer, a nitrogen introducing tube, and a dropping funnel were installed on a 500-ml four-necked flask, and 77.13 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were charged thereto under a nitrogen atmosphere and stirred and dissolved at 60 C. Thereafter, while stirring at 120 C., 29.30 g of BAHF was added thereto, and the mixture was stirred for 1 hour. Thereafter, the mixture was heated to 200 C., stirred for 3 hours, and then cooled to room temperature to provide a polymer (A) G (solid content concentration: 80.0 wt %). The weight average molecular weight of the polymer (A) G was measured and found to be 74,270, and the imidization rate was measured and found to be 99%.

[0169] The monomer components and properties of the synthesized polymers (A) are shown in Tables 1 and 2.

[0170] Acrylic Rubber: epoxy group-containing acrylic rubber having a weight average molecular weight of 850,000, Tg: 32 C., monomer copolymerization ratio: ethyl acrylate:butyl acrylate:glycidyl acrylate=65:35:1, functional group (epoxy group) content: 0.09 eq/kg.

[0171] Aromatic Polyimide

[0172] <Synthesis of Aromatic Polyimide>

[0173] Under a dry nitrogen stream, 24.54 g (0.067 mol) of BAHF, 4.97 g (0.02 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.18 g (0.02 mol) of 3-aminophenol as an end-capping agent were dissolved in 80 g of N-methylpyrrolidone (hereinafter referred to as NMP). To this solution, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, and the solution was allowed to react for 1 hour at 20 C. and then stirred for 4 hours at Subsequently, 15 g of xylene was added to the reaction solution, and the resultant mixture was stirred at 180 C. for 5 hours while azeotropically boiling water together with xylene. After the completion of the stirring, the solution was introduced into 3 L of water to produce a polymer as a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried with a vacuum dryer at 80 C. for 20 hours. The infrared absorption spectrum of the resulting polymer solid was measured, and absorption peaks corresponding to imide structures derived from the polyimide were detected around 1780 cm.sup.1 and 1377 cm.sup.1. In this manner, an aromatic polyimide that had a functional group capable of reacting with an epoxy group was obtained.

[0174] Thermosetting Resin (B) [0175] jER 1032 H 60: tris(hydroxyphenyl)methane epoxy resin (manufactured by Mitsubishi Chemical Corporation) [0176] HP 4700: naphthalene type polyfunctional epoxy resin (manufactured by DIC Corporation).

[0177] Inorganic Filler (C) [0178] AA-3: high-purity alumina (average particle size: 3 m) (manufactured by Sumitomo Chemical Co., Ltd.) [0179] AA-04: high-purity alumina (average particle size: m) (manufactured by Sumitomo Chemical Co., Ltd.) [0180] SO-E1: high-purity synthetic spherical silica (average particle size: 0.3 m) (manufactured by Admatechs Co., Ltd.).

[0181] Curing Agent or Curing Accelerator (D) [0182] SEIKACURE-S: 4,4-diaminodiphenylsulfone (manufactured by Wakayama Seika Kogyo Co., Ltd.) [0183] C17Z: 2-heptadecylimidazole (manufactured by Shikoku Chemicals Corporation)

Examples 1 to 17 and Comparative Examples 1 to 4

[0184] In each of Examples 1 to 17 and Comparative Examples 1 to 4, blending was performed so as to achieve the composition shown in Tables 3 to 5, triethylene glycol dimethyl ether was added thereto, and the mixture was stirred with a rotation-revolution mixer (manufactured by Thinky Corporation) at 1,800 rpm for 10 minutes to prepare a composition solution.

[0185] The composition solution was applied to a 38 m-thick polyethylene terephthalate film (RF2PETcs000 manufactured by I'm Corporation) with a silicone release agent using a bar coater so as to have a dry thickness of 50 m (hereinafter referred to as a composition coating film). The product was dried at 120 C. for 30 minutes, and the protective film was bonded at 120 C. and 0.4 MPa to produce a sheet-form composition. The results of various evaluations subsequently performed are shown in Tables 3 to 5.

TABLE-US-00001 TABLE 1 Item Polymer A Polymer B Polymer C Polymer D Polymer E Tetracarboxylic X-22-168AS 100 80 50 100 acid dianhydride X-22-168A 100 (mol %) ODPA 20 50 BPDA Diamine (mol %) KF8010 90 90 90 60 X-22-161A 90 BAHF 10 10 10 40 10 Properties Imidization 99 99 99 99 99 rate (%) Tg ( C.) 95 75 36 65 120 Weight average 45600 57320 69750 60350 48020 molecular weight

TABLE-US-00002 TABLE 2 Polymer Polymer Polymer Polymer Item F G H I Tetracarboxylic X-22-168AS 100 30 100 acid dianhydride X-22-168A (mol %) ODPA 70 BPDA 100 Diamine (mol %) KF8010 30 90 X-22-161A 90 BAHF 70 10 10 100 Properties Imidization 99 99 99 99 rate (%) Tg ( C.) 51 48 30 30 Weight 55680 59790 45300 74270 average molecular weight

TABLE-US-00003 TABLE 3 Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Thermoplastic Polymer A 8.08 8.08 8.08 resin (in terms Polymer B 8.08 of solid content) Polymer C 8.08 (g) Polymer D 8.08 Polymer E 8.08 Polymer F Polymer G Polymer H Polymer I Acrylic rubber Aromatic polyimide Thermosetting jER1032H60 0.91 resin (g) HP4700 0.9 0.9 0.9 0.9 0.9 0.9 Inorganic AA-3 22.4 22.4 22.4 22.4 22.4 22.4 filler (g) AA-04 2.8 2.8 2.8 2.8 2.8 2.8 SO-E1 Curing agent SEIKACURE-S 0.34 0.34 0.34 0.34 0.34 0.34 0.33 (g) C17Z Evaluation Elastic modulus 3.7 11 14 35 36 6.4 11 result (MPa) Tg ( C.) 69.6 63.6 51.8 12.4 31.6 67.2 61.6 Shear strain 3.47 2.07 1.88 1.95 1.78 2.35 2.04 Heat resistance Good Good Good Good Good Good Good

TABLE-US-00004 TABLE 4 Item Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Thermoplastic Polymer A 8.08 8.08 8.08 8.08 8.08 8.08 resin (in terms Polymer B of solid content) Polymer C (g) Polymer D 8.08 Polymer E Polymer F Polymer G Polymer H Polymer I Acrylic rubber Aromatic polyimide Thermosetting jER1032H60 0.91 0.91 1.24 1.24 1.24 1.24 1.24 resin (g) HP4700 Inorganic AA-3 11.9 4.9 22.4 11.9 4.9 filler (g) AA-04 1.49 0.61 2.8 1.49 0.61 SO-E1 3.08 3.08 Curing agent SEIKACURE-S 0.33 0.33 (g) C17Z 0.062 0.062 0.062 0.036 0.036 Evaluation Elastic modulus 4.3 1.6 43 23 11 6.6 36 result (MPa) Tg ( C.) 64.8 66.7 64.7 64.9 68.6 69.4 32.1 Shear strain 2.84 3.49 2.36 2.15 2.03 3.14 2.41 Heat resistance Good Good Good Good Good Good Good

TABLE-US-00005 TABLE 5 Comparative Comparative Comparative Comparative Item Example 15 Example 16 Example 17 Example 1 Example 2 Example 3 Example 4 Thermoplastic Polymer A 8.08 resin (in terms Polymer B of solid content) Polymer C (g) Polymer D Polymer E Polymer F 8.08 Polymer G 8.08 Polymer H 8.08 Polymer I 8.08 Acrylic 8.08 rubber Aromatic 8.08 polyimide Thermosetting jER1032H60 1.24 resin (g) HP4700 0.9 0.9 0.9 0.9 0.9 0.9 Inorganic AA-3 filler (g) AA-04 SO-E1 Curing agent SEIKACURE-S 0.34 0.34 0.34 0.34 0.34 0.34 (g) C17Z 0.036 Evaluation Elastic modulus 0.7 64 72 3.3 4500 110 120 result (MPa) Tg ( C.) 72.1 26.8 24.1 28.5 315 11.4 10.9 Shear strain 4.21 1.68 1.56 4.12 0.31 1.14 1.02 Heat resistance Good Good Good Poor Good Good Good

[0186] From Tables 3 to 5, Examples 1 to 17 in which the polymers (A) A to G containing polysiloxane skeletons in both a diamine residue and an acid anhydride residue were used each provide a sheet having an elastic modulus of less than 100 MPa and a shear strain of 1.5 or more and having sufficient flexibility, adhesion to an adherend, and followability. In addition, the sheet has good heat resistance and can maintain a good adhesion state for a long period of time. In particular, in Examples 1 to 15 using the polymers (A) A to E containing 60 mol % or more of the diamine residue (1) in all diamine residues and 50 mol % or more of the acid anhydride residue (2) in all acid anhydride residues, the elastic modulus tends to be lower, and the shear strain tends to increase. By containing a large amount of the siloxane skeleton, the flexibility, the adhesion to an adherend, and the followability can be improved.

[0187] On the other hand, as can be seen from Table 5, Comparative Example 1 in which acrylic rubber was used as the thermoplastic resin had poor heat resistance, and the shear strain was significantly reduced by heating under vacuum at 250 C. for 1,000 hours from an initial value of 4.12. In Comparative Example 2 in which an aromatic polyimide was used as the thermoplastic resin, the heat resistance was good, but the elastic modulus was as very high as 4,500 MPa, and the shear strain was as very small as less than 0.5, so that flexibility, adhesion to an adherend, and followability were insufficient. In Comparative Example 3 in which the polymer (A) H containing a polysiloxane structure only in a diamine residue was used as the thermoplastic resin and Comparative Example 4 in which the polymer (A) I containing a polysiloxane structure only in an acid anhydride residue was used as the thermoplastic resin, the elastic modulus was reduced, and the shear strain was also increased as compared with Comparative Example 2. However, the elastic moduli were still as high as 110 MPa (Comparative Example 3) and 120 MPa (Comparative Example 4), the shear strain was less than 1.5, and flexibility, adhesion to an adherend, and followability are insufficient.