Resin composition, sheet-shaped composition, sheet cured product, laminate, laminated member, wafer holder, and semiconductor manufacturing apparatus

Abstract

The present invention aims to provide a resin composition capable of producing an adhesive sheet for an electrostatic chuck which is excellent in heat resistance, low in elastic modulus, and capable of adhering to and following a difference in thermal expansion of a base material in a single layer. The present invention is a resin composition comprising (A) a polymer selected from the group consisting of polyimide and polyamide acid having a residue of a specific structure of a diamine (hereinafter, diamine residue (1)) and a residue of a specific structure of an acid anhydride (hereinafter, acid anhydride residue (2)), and (B) a thermosetting resin.

Description

Technical Field

[0001] This invention relates to resin compositions and sheet compositions containing thermoplastic resins and thermosetting resins, sheet cured products, laminates, laminated components, wafer holders, and semiconductor manufacturing apparatus. Background Technology

[0002] In wafer holders where a ceramic electrostatic chuck (electrostatic chuck heater, base) is bonded to a metal cooling plate, resin-based adhesive tapes and adhesive materials are generally used for bonding the electrostatic chuck to the cooling plate. As an adhesive composition for such applications, an adhesive sheet for semiconductor devices containing thermoplastic resins such as acrylic copolymers and thermosetting resins such as epoxy resins has been proposed (Patent Document 1). Such wafer holders to date have limited operating temperatures due to the heat resistance of the resins (especially thermoplastic resins) (generally below 100°C, and even for substances that can be used at high temperatures, the maximum is below 150°C).

[0003] On the other hand, if heat-resistant resins such as polyimide are used, the high elastic modulus of the resin cannot absorb the thermal expansion difference between the ceramic and the cooling plate, resulting in deformation and cracking, making it difficult to use as a wafer holder. When using metal solder for bonding, it is uncertain whether the bonding can be successful at high temperatures; if the thermal expansion of the ceramic and the cooling plate (metal) is not matched, deformation and cracking will occur during bonding.

[0004] For the requirements of having heat resistance that can be used at high temperatures such as 200°C, and for mitigating the thermal expansion of ceramics and cooling plates (metals) to achieve tight adhesion and follow-up with the substrate, an adhesive sheet for electrostatic chucks was proposed (Patent Document 2) in which an adhesive layer based on polyimide with both heat resistance and adhesion is laminated with an elastic phase of silicone resin that can mitigate thermal expansion.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 11-265960

[0008] Patent Document 2: Japanese Patent Application Publication No. 2002-83862 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, in the device of Patent Document 2, the silicone elastic phase is more flexible than the adhesive layer, and their elastic moduli differ, which may cause peeling between the silicone elastic phase and the adhesive layer. Furthermore, while the polyimide in the adhesive layer described in Patent Document 2 contains a portion of a flexible siloxane structure, its elastic modulus remains high on its own, making it difficult to achieve the requirement of maintaining heat resistance while mitigating thermal expansion differences and ensuring a tight bond and conformity with the substrate.

[0011] Therefore, the main objective of this invention is to eliminate the above-mentioned disadvantages and provide a resin composition capable of manufacturing an adhesive sheet for an electrostatic chuck that has excellent heat resistance, low elastic modulus, and can be used to mitigate and seal the thermal expansion difference of the substrate in a single layer.

[0012] Methods for solving problems

[0013] To address the aforementioned issues, the present invention has the following configuration.

[0014] A resin composition comprising (A) a polymer and (B) a thermosetting resin, wherein the (A) polymer is selected from polyimide and polyamic acid having residues of diamine having general formula (1) (hereinafter referred to as diamine residue (1)) and residues of acid anhydride having general formula (2) (hereinafter referred to as acid anhydride residue (2)).

[0015]

[0016] In general formula (1), R 1 ~R 4 These can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted by alkyl groups with 1 to 30 carbon atoms. m R 1 and R 3 They can be the same or different.

[0017] In general formula (1), R 5 and R 6 These can be the same or different, representing alkylene or arylene groups with 1 to 30 carbon atoms. The aryl group can be substituted by an alkyl group with 1 to 30 carbon atoms.

[0018] In general formula (1), m is an integer selected from 1 to 100.

[0019]

[0020] In general formula (2), R 7 ~R 10 These can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted by alkyl groups with 1 to 30 carbon atoms. n R groups 7and R 9 They can be the same or different.

[0021] In general formula (2), R 11 and R 12 These can be the same or different, representing alkylene or arylene groups with 1 to 30 carbon atoms. The aryl group can be substituted by an alkyl group with 1 to 30 carbon atoms.

[0022] In general formula (2), n is an integer selected from 1 to 100.

[0023] The effects of the invention

[0024] The resin composition of the present invention provides an adhesive sheet for electrostatic chucks that exhibits excellent heat resistance, low elastic modulus, and maintains good adhesion even at high temperatures above 200°C while mitigating the thermal expansion difference between the ceramic and the cooling plate (metal) over a long period. Detailed Implementation

[0025] The present invention is a resin composition comprising: (A) a polymer selected from polyimide and polyamic acid having residues of diamine having general formula (1) (hereinafter referred to as diamine residue (1)) and residues of acid anhydride having general formula (2) (hereinafter referred to as acid anhydride residue (2)); and (B) a thermosetting resin.

[0026]

[0027] In general formula (1), R 1 ~R 4 These can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted by alkyl groups with 1 to 30 carbon atoms. m R 1 and R 3 They can be the same or different.

[0028] In general formula (1), R 5 and R 6 These can be the same or different, representing alkylene or arylene groups with 1 to 30 carbon atoms. The aryl group can be substituted by an alkyl group with 1 to 30 carbon atoms.

[0029] In general formula (1), m is an integer selected from 1 to 100.

[0030]

[0031] In general formula (2), R 7 ~R 10These can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted by alkyl groups with 1 to 30 carbon atoms. n R groups 7 and R 9 They can be the same or different.

[0032] In general formula (2), R 11 and R 12 These can be the same or different, representing alkylene or arylene groups with 1 to 30 carbon atoms. The aryl group can be substituted by an alkyl group with 1 to 30 carbon atoms.

[0033] In general formula (2), n is an integer selected from 1 to 100.

[0034] The following describes specific embodiments of the present invention in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements are not essential unless specifically stated otherwise. The same applies to numerical values ​​and their ranges; the present invention is not limited thereto.

[0035] In this specification, the numerical range represented by “~” includes the minimum and maximum values ​​recorded before and after “~”, respectively.

[0036] Regarding the content of each component in the composition described in this specification, in the case where multiple substances equivalent to each component are present in the composition, unless otherwise specified, it refers to the total content of the multiple substances present in the composition. For example, if the composition contains component A and component B as thermosetting resin components, the content of the thermosetting resin components refers to the total content of component A and component B.

[0037] In this specification, the term "layer" refers to the presence of a layer in an area, including not only the layer that forms in the entire area but also the layer that forms in only a part of the area.

[0038] In this specification, the term "stacked" means that layers are stacked together, and two or more layers may be combined or detachable.

[0039] <Resin Composition>

[0040] The resin composition of the present invention contains: (A) a polymer selected from polyimide and polyamic acid having residues of diamine having general formula (1) (hereinafter referred to as diamine residue (1)) and residues of acid anhydride having general formula (2) (hereinafter referred to as acid anhydride residue (2)); and (B) a thermosetting resin.

[0041] <(A) Polymer>

[0042] (A) The polymer is selected from polyimides and polyamic acids having diamine residues (1) and anhydride residues (2). Therefore, (A) polymer is generally obtained mainly by the reaction of tetracarboxylic dianhydride with diamine, having tetracarboxylic dianhydride residues and diamine residues.

[0043] The polymer (A) preferably contains 60 mol% or more and 100 mol% or less of diamine residue (1) when all diamine residues in the polymer (A) are set to 100 mol%. By containing the polymer (A) with a highly flexible siloxane backbone, the heat resistance of the sheet-cured product obtained by curing the resin composition of the present invention can be improved, and a sheet-cured product with excellent adhesion to the substrate and reduced elastic modulus can be obtained. If the content of diamine residue (1) is less than 60 mol%, the elastic modulus of the sheet-cured product may become higher, and the adhesion and adhesion to the substrate may decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and adhesion to the substrate, it is preferable that the polymer (A) contains 70 mol% or more and 100 mol% or less of diamine residue (1) when all diamine residues in the polymer (A) are set to 100 mol%, more preferably 85 mol% or more and 100 mol% or less.

[0044] In general formula (1), R 1 ~R 4 The terms can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted with alkyl groups with 1 to 30 carbon atoms. The alkyl group can be linear or branched. Examples of alkyl groups with 1 to 30 carbon atoms include methyl, ethyl, propyl, and butyl. From the viewpoint of further improving heat resistance, the alkyl group preferably has 12 or fewer carbon atoms. 1 and R 3 They can be the same or different.

[0045] In general formula (1), R 5 and R 6 The terms "alkylene" and "arylene" can be the same or different, representing alkylene or aryl groups with 1 to 30 carbon atoms. The aryl group can be substituted with an alkyl group with 1 to 30 carbon atoms. Furthermore, both the alkylene and alkyl groups can be linear or branched. Examples of alkylene groups with 1 to 30 carbon atoms include methylene, ethylene, propylene, and butylene. From the viewpoint of further improving heat resistance, the aryl group preferably has 12 or fewer carbon atoms. Examples of aryl groups include phenylene. These groups can also be formed by combining alkylene and aryl groups.

[0046] In general formula (1), m represents a range of 1 or more and 100 or less. m is an integer in each polymer chain, but the average value obtained by measuring the polymer as a whole is sometimes not an integer. In addition, from the viewpoint of further reducing the elastic modulus of the sheet-cured product, m is preferably 3 or more, and more preferably 5 or more. By making m 5 or more, the elastic modulus of the sheet-cured product can be reduced through long and flexible siloxane chains, thereby improving the adhesion and conformability to the substrate. On the other hand, from the viewpoint of improving compatibility with (B) thermosetting resin, m is preferably 40 or less. That is, in general formula (1), m is preferably 3 or more and 40 or less.

[0047] The polymer (A) of the present invention preferably contains 50 mol% or more and 100 mol% or less of anhydride residue (2) when all anhydride residues in the polymer (A) are set to 100 mol%. By containing the polymer (A) with a highly flexible siloxane backbone, the heat resistance of the sheet-cured product obtained by curing the resin composition of the present invention can be improved, and a sheet-cured product with excellent adhesion that reduces the elastic modulus and follows the shape of the substrate can be obtained. If the content of anhydride residue (2) is less than 50 mol%, the elastic modulus of the sheet-cured product may become higher, and the adhesion and conformability to the substrate may decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and conformability to the substrate, it is preferable that the polymer (A) contains 70 mol% or more and 100 mol% or less of anhydride residue (2) when all anhydride residues in the polymer (A) are set to 100 mol%, more preferably 85 mol% or more and 100 mol% or less.

[0048] In general formula (2), R 7 ~R 10 The terms can be the same or different, representing alkyl, phenyl, or phenoxy groups having 1 to 30 carbon atoms. Phenyl and phenoxy groups can be substituted with alkyl groups having 1 to 30 carbon atoms. Furthermore, the alkyl group can be straight-chain or branched. Examples of alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, propyl, and butyl. From the viewpoint of further improving heat resistance, the alkyl group preferably has 12 or fewer carbon atoms. 7 and R 9 They can be the same or different.

[0049] In general formula (2), R 11 and R 12The terms "alkylene" and "arylene" can be the same or different, representing alkylene or aryl groups with 1 to 30 carbon atoms. The aryl group can be substituted with an alkyl group with 1 to 30 carbon atoms. Furthermore, both the alkylene and alkyl groups can be linear or branched. Examples of alkylene groups with 1 to 30 carbon atoms include methylene, ethylene, propylene, and butylene. From the viewpoint of further improving heat resistance, the aryl group preferably has 12 or fewer carbon atoms. Examples of aryl groups include phenylene. These groups can be formed by combining alkylene and aryl groups.

[0050] In general formula (2), n represents a range of 1 or more and 100 or less. n is an integer in each polymer chain, but the average value obtained by measuring the polymer as a whole is sometimes not an integer. In addition, from the viewpoint of further reducing the elastic modulus of the sheet-cured product, n is preferably 3 or more, and more preferably 5 or more. By making n 5 or more, the elastic modulus of the sheet-cured product can be reduced through long and flexible siloxane chains, thereby improving the adhesion and conformability to the substrate. On the other hand, from the viewpoint of improving compatibility with (B) thermosetting resin, n is preferably 40 or less. That is, in general formula (2), n is preferably 3 or more and 40 or less.

[0051] The polymer (A) of the present invention preferably has a total of 55 mol% and 100 mol% or less of diamine residues (1) and anhydride residues (2) when the total of all diamine residues and all anhydride residues in the polymer (A) is set to 100 mol%. By containing a polymer (A) with a highly flexible siloxane backbone, the heat resistance of the sheet-cured product obtained by curing the resin composition of the present invention can be improved, and a sheet-cured product with excellent adhesion to the substrate by reducing the elastic modulus can be obtained. If the total of diamine residues (1) and anhydride residues (2) is less than 55 mol%, the elastic modulus of the sheet-cured product may increase, and the adhesion and adhesion to the substrate may decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and conformability to the substrate, it is preferable that when the total of all diamine residues and anhydride residues in polymer (A) is set to 100 mol%, the total of diamine residues (1) and anhydride residues (2) is 70 mol% or more and 100 mol% or less, more preferably 85 mol% or more and 100 mol% or less.

[0052] The glass transition temperature (Tg) of polymer (A) is preferably -150°C or higher and -30°C or lower. By setting the Tg of polymer (A) to -30°C or lower, the elastic modulus of the sheet-cured product can be reduced over a wider temperature range. From the viewpoint of reducing the elastic modulus over a wider temperature range, expanding the usable temperature range, and further improving versatility, the glass transition temperature (Tg) of polymer (A) is more preferably -150°C or higher and -50°C or lower, and even more preferably -150°C or higher and -80°C or lower. To achieve such a Tg range for the polymer (A) of the present invention, methods for controlling the structure of polymer (A), particularly the ratio of the siloxane backbone, can be cited.

[0053] (A) The weight-average molecular weight of the polymer is preferably 1000 or more, more preferably 10000 or more. By having a weight-average molecular weight of 1000 or more, the toughness of the cured sheet is improved while the elastic modulus is reduced. Furthermore, due to its high molecular weight, heat resistance can be further improved. On the other hand, the weight-average molecular weight of (A) polymer is preferably 1,000,000 or less, more preferably 200,000 or less. By having a weight-average molecular weight of 1,000,000 or less, the viscosity when prepared as a solution can be reduced, and processability can be further improved.

[0054] Here, the weight-average molecular weight of polymer (A) can be calculated as a polystyrene equivalent by performing gel permeation chromatography (GPC) analysis on a solution in which polymer (A) is dissolved in N-methyl-2-pyrrolidone resin at a concentration of 0.1% by weight.

[0055] (A) The polymer is preferably solvent-soluble. If it is solvent-soluble, the viscosity can be kept low when preparing the resin composition, and the dispersibility of the inorganic filler (C) can be further improved. Here, the solvent-soluble nature of (A) polymer means that it dissolves at 25°C more than 100g of any organic solvent selected from amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N-vinylpyrrolidone, and N,N-diethylformamide; γ-butyrolactone; monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methyl monoethylene glycol dimethyl ether, methyl diethylene glycol dimethyl ether, methyl triethylene glycol dimethyl ether, ethyl monoethylene glycol dimethyl ether, ethyl diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

[0056] Examples of commercially available diamines that are preferred as raw materials for polymers of (A) having diamine residues as shown in the above general formula (1) include, for example, X-22-161A, X-22-161B, KF8012, KF8010, KF8008, and X-22-1660B-3 manufactured by Shin-Etsu Chemical Co., Ltd. Two or more of these may be used.

[0057] The diamine residues constituting polymer (A) preferably have hydroxyl and / or carboxyl groups. Having diamine residues containing hydroxyl or carboxyl groups promotes the reaction with the thermosetting resin (B), thereby improving the toughness of the sheet-cured product. From the viewpoint of improving the toughness of the thermally conductive sheet, it is preferable that the total diamine residues contain at least 1 mol% of diamine residues containing hydroxyl and / or carboxyl groups. On the other hand, from the viewpoint of further reducing the elastic modulus of the sheet-cured product and further improving its flexibility, it is preferable that the total diamine residues contain at least 40 mol% of diamine residues containing hydroxyl and / or carboxyl groups, more preferably at least 30 mol%.

[0058] Commercially available anhydrides that are preferred as raw materials for polymers having anhydride residues as shown in the above general formula (2) include, for example, X-22-168AS, X-22-168A, X-22-168B, and X-22-168-P5-B manufactured by Shin-Etsu Chemical Co., Ltd. Two or more of these may be used.

[0059] <(B) Thermosetting Resins>

[0060] The (B) thermosetting resin included in the resin composition of the present invention is not particularly limited, but preferably includes at least one selected from polyimide resin, bismaleimide resin, epoxy resin, phenolic resin, urethane resin, silicone resin, acrylic resin, and polyamide-imide resin. In particular, epoxy resin is preferred from the viewpoint of excellent heat resistance and curing reactivity.

[0061] Furthermore, the content of (B) thermosetting resin is not particularly limited, but from the viewpoint of improving the toughness and heat resistance of the resin composition at high temperatures, it is preferable to be 0.1 parts by weight or more relative to 100 parts by weight of (A) polymer, and from the viewpoint of improving the softness of the composition, it is preferable to be 15 parts by weight or less.

[0062] <Epoxy Resin>

[0063] There are no particular limitations on the epoxy resin used as the thermosetting resin (B) of the present invention, but from the viewpoint of improving heat resistance at high temperatures above 200°C, preventing brittleness of the composition after prolonged use at 200°C, and improving adhesion, epoxy resins containing an aromatic backbone are preferred. Aromatic backbones are preferred because they are rigid. Examples of aromatic backbones include benzene rings and naphthalene rings. Examples of such epoxy resins include Mitsubishi Kemikal Co., Ltd.'s jER828 containing a bisphenol backbone, jER1032H60 containing a triphenylmethane backbone, and DIC Co., Ltd.'s EPICLON HP-4700 and EPICLON HP-4032SS containing a naphthalene ring.

[0064] Furthermore, from the same perspective, epoxy resins containing a triazine backbone are preferred. Examples of such epoxy resins include TEPIC-PAS B26L, TEPIC-PAS B22, TEPIC-S, TEPIC-VL, TEPIC-FL, and TEPIC-UC manufactured by Nissan Chemical Co., Ltd.

[0065] Furthermore, from the viewpoint of resulting in a low elastic modulus of the cured composition, improved flexibility, and reduced contact thermal resistance at the contact interface, epoxy resins containing a siloxane backbone are preferred. Examples of such epoxy resins include X-40-2695B and X-22-2046 manufactured by Shin-Etsu Chemical Co., Ltd.

[0066] Furthermore, from the same perspective, and considering compatibility with (A) polymers, (C) inorganic fillers, and (D) curing agents or curing accelerators, a flexible epoxy resin without a siloxane backbone is more preferable. A flexible epoxy resin without a siloxane backbone refers to an epoxy resin formed from acyclic carbon compounds, whose carbon chains can be straight or branched, and whose bonds can be saturated or unsaturated. Specifically, epoxy resins such as monoglycidyl ethers of aliphatic alcohols, glycidyl esters of alkyl carboxylic acids, polyglycidyl ethers of aliphatic polyols or their oxidized olefin adducts, and polyglycidyl esters of aliphatic long-chain polyacids are preferred. Examples of flexible epoxy resins without a siloxane backbone include YX7400, YX7110, YX7180, and YX7105 manufactured by Mitsubishi Chemical Co., Ltd.

[0067] From the viewpoint of improving thermal conductivity, the epoxy resin used in this invention is preferably a crystalline epoxy resin. A crystalline epoxy resin is an epoxy resin having a mesocrystalline skeleton such as a biphenyl, naphthalene, anthracene, phenylbenzoate, or N-benzoylaniline group. Examples of such epoxy resins include JERYX4000, JERYX4000H, JERYX8800, JERYL6121H, JERYL6640, JERYL6677, and JERYX7399 manufactured by Mitsubishi Chemical Co., Ltd.; NC3000, NC3000H, NC3000L, and CER-3000L manufactured by Nippon Chemical Co., Ltd.; YSLV-80XY and YDC1312 manufactured by Nippon Steel Chemical Co., Ltd.; and HP4032, HP4032D, and HP4700 manufactured by DIC Co., Ltd.

[0068] Furthermore, from the viewpoint of improving the dispersibility of inorganic filler materials and increasing thermal conductivity, the epoxy resin used in this invention is preferably an epoxy resin having a fluorene skeleton. Examples of such epoxy resins include PG100, CG500, CG300-M2, EG200, and EG250 manufactured by Osaka Gaskemikar Co., Ltd.

[0069] Furthermore, from the viewpoint that high affinity with polyimide and increased crosslinking density with polyimide can improve heat resistance, the epoxy resin used in this invention is preferably a glycidylamine type epoxy resin. Examples of such epoxy resins include JER630, JER630LSD, and JER604 manufactured by Mitsubishi Chemical Co., Ltd.

[0070] Furthermore, from the viewpoint of achieving low viscosity when dispersing inorganic filler materials, the epoxy resin used in this invention is preferably a liquid epoxy resin. Here, liquid epoxy resin refers to epoxy resin that is in a state of viscosity of 1.013 × 10⁻⁶ at 25°C. 5 N / m 2Examples of substances with a viscosity of less than 150 Pa·s include bisphenol A type epoxy resin, bisphenol F type epoxy resin, olefin-modified epoxy resin, and glycidylamine type epoxy resin. Examples of products corresponding to such epoxy resins include JER827, JER828, JER806, JER807, JER801N, JER802, YX7400, JER604, JER630, JER630LSD manufactured by Mitsubishi Chemical Co., Ltd.; Epicron 840S, Epicron 850S, Epicron 830S, Epicron 705, Epicron 707 manufactured by DIC Co., Ltd.; YD127, YD128, PG207N, PG202 manufactured by Nippon Steel Chemical Co., Ltd.; and TEPIC-PASB26L, TEPIC-PASB22, TEPIC-VL, TEPIC-FL, TEPIC-UC manufactured by Nissan Chemical Co., Ltd.

[0071] In the resin composition of the present invention, from the viewpoint of the stability of the coating of the composition, and the combination of the toughness of the resin composition and heat resistance at high temperatures, at least one selected from epoxy resins containing an aromatic backbone, soft epoxy resins without a siloxane backbone, and crystalline epoxy resins is particularly preferred. From the viewpoint of balancing the elastic modulus of the sheet-cured product with the other components in the resin composition, when high elasticity is desired by utilizing the epoxy resin component, epoxy resins containing an aromatic backbone or crystalline epoxy resins are preferred; when low elasticity is desired by utilizing the epoxy resin component, soft epoxy resins without a siloxane backbone are preferred.

[0072] Furthermore, the epoxy resin used in this invention can be a single type or a combination of two or more types. From the viewpoint of improving the toughness and heat resistance of the composition at high temperatures, it is preferable that the content of epoxy resin is 0.1 parts by weight or more relative to 100 parts by weight of polymer (A), and from the viewpoint of improving the flexibility of the composition, it is preferably 15 parts by weight or less.

[0073] <(D) Curing agent or curing accelerator>

[0074] The resin composition of the present invention may contain (D) a curing agent or a curing accelerator as needed.

[0075] By combining curing accelerators and curing agents with (B) thermosetting resins such as epoxy resins, the curing of (B) thermosetting resins such as epoxy resins can be accelerated and cured in a short time. As curing agents and curing accelerators, imidazoles, polyphenols, acid anhydrides, amines, acylhydrazides, polythiols, Lewis acid-amine coordination compounds, latent curing agents, etc., can be used.

[0076] Examples of the imidazoles include Korra C17Z, Korra 2MZ, Korra 2PZ, and Korraアゾール2MZ-A, キュアゾール2MZ-OK (the above trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), etc. Examples of the polyhydric phenols include Sumitomo Chemical PR-HF3 and Sumitomo Chemical PR-HF6 (the above trade names, Sumitomo Chemical Co., Ltd. KTG-105, KTG-105, KTG-105, manufactured by Nippon Kayaku Co., Ltd., NHN (the above trade names, manufactured by Nippon Kayaku Co., Ltd.), Fukuro T D2131, Fenolight TD2090, Fenolight VH-4150, Fenolight KH-6021, Fenolight KA-1160, Fenolight KA-1165 (all trade names, manufactured by DIC Co., Ltd.), H-1 (manufactured by Meiwa Kasei Co., Ltd.), etc. Examples of amines include aromatic amines such as SEIKACURE-S, BAPS, DPE / ODA, Bis Amine A (all trade names, manufactured by Wakayama Seika Kogyo Co., Ltd.), and amines with a siloxane skeleton such as KF-8010, X-22-161A (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, examples of latent curing agents include dicyandiamide-type latent curing agents, amine adduct-type latent curing agents, organic acid hydrazide-type latent curing agents, aromatic sulfonium salt-type latent curing agents, microencapsulated latent curing agents, and photocurable latent curing agents.

[0077] Examples of the dicyandiamide-type latent curing agent include DICY7, DICY15, and DICY50 (the above trade names are: (manufactured by Ajinomoto Co., Ltd.), Amikon AH-154, Amikon AH-162 (the above trade names, manufactured by Ajinomoto Chemical Co., Ltd.), etc. Examples of the amine adduct type latent curing agent include AMicro PN-23, AMicro PN-40, AMicro MY-24, and AMicro PN-23. MY-H (trade name above, manufactured by Ajinomoto Chemical Co., Ltd.), Fukusuga FXR-1030 (trade name, manufactured by Fuji Chemical Co., Ltd.), etc. Examples of organic acid hydrazide-type latent curing agents include AMicroVDH and AMicroAUDH (the above trade names, manufactured by Ajinomoto Chemical Co., Ltd.). Examples of aromatic sulfonium salt-type latent curing agents include Sandeid SI100, Sandeid SI150, and Sandeid SI180 (all trade names, manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of microencapsulated latent curing agents include substances in which the above-mentioned curing agents are encapsulated with vinyl compounds, urea compounds, or thermoplastic resins. Among these, examples of microencapsulated latent curing agents that treat amine adduct-type latent curing agents with isocyanate include Nobachua HX-3941HP, Nobachua HXA3922HP, Nobachua HXA3932HP, and Nobachua HXA3042HP (all trade names, manufactured by Asahi Kasei Kemikazu Co., Ltd.). Furthermore, examples of light-curing latent curing agents include Optomar SP and Optomar CP (manufactured by ADEKA Co., Ltd.).

[0078] When the resin composition of the present invention contains (D) a curing agent or a curing accelerator, its content is preferably 0.1 parts by weight or more and 35 parts by weight or less relative to 100 parts by weight of (B) thermosetting resin.

[0079] <(C) Inorganic filler materials>

[0080] The resin composition of the present invention preferably includes (C) an inorganic filler. The inorganic filler is not particularly limited as long as it does not impair the properties of the adhesive; specific examples include silica, alumina, silicon nitride, aluminum hydroxide, gold, silver, copper, iron, nickel, silicon carbide, aluminum nitride, titanium nitride, and titanium carbide. From a cost perspective, silica, alumina, silicon nitride, silicon carbide, and aluminum hydroxide are preferred. Furthermore, from the viewpoint of balancing cost and thermal conductivity, silica and alumina are particularly preferred. Here, silica can be either amorphous or crystalline, and is not limited to being used separately according to their respective properties. To improve heat resistance, adhesion, etc., these inorganic fillers can be surface-treated using silane coupling agents or the like.

[0081] Furthermore, the shape of the inorganic filler material is not particularly limited, and fragmented, spherical, or flake-shaped materials can be used, but spherical shapes are preferred from the perspective of dispersibility in coatings. The particle size of the inorganic filler material is not particularly limited, but from the perspective of dispersibility, coatability, thermal cycling, and other reliability, an average particle size of 3 μm or less and a maximum particle size of 10 μm or less are preferred, preferably an average particle size of 1 μm or less and a maximum particle size of 6 μm or less, and more preferably an average particle size of 0.7 μm or less and a maximum particle size of 2 μm or less. The average and maximum particle sizes referred to here were measured using a Horiba LA500 laser diffraction particle size analyzer. Furthermore, to improve reliability, it is preferable that the particle purity exceeds 99%, preferably exceeds 99.8%, and more preferably exceeds 99.9%. If the purity is below 99%, soft errors in semiconductor elements are more likely to occur due to alpha rays emitted from radioactive impurities such as uranium and thorium.

[0082] Furthermore, (C) the content of inorganic filler is not particularly limited, but when the total amount of the resin composition of the present invention is set to 100% by weight, it is preferably 0 to 80% by weight, more preferably 0 to 70% by weight, and even more preferably 2 to 60% by weight.

[0083] <Organic Solvents>

[0084] The resin composition of the present invention may further comprise at least one organic solvent. By comprising an organic solvent, the resin composition can be adapted to various molding processes. As the organic solvent, substances commonly used in resin compositions can be used. Specifically, examples include alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents, etc. Examples of solvents that can be used include methyl isobutyl ketone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, and methyl ethyl ketone. These organic solvents may be used individually or in combination of two or more.

[0085] <Other Ingredients>

[0086] In addition to the components described above, the resin composition of the present invention may also contain other components as needed. Examples of other components include dispersants, plasticizers, etc. Examples of dispersants include, for example, the DISPERBYK series manufactured by Bickkemi Japan Co., Ltd. ("DISPERBYK" is a registered trademark), the Ajisper series manufactured by Ajinomoto Chemical Co., Ltd. ("Ajisper" is a registered trademark), the HIPLAAD series manufactured by Kusunomoto Chemical Co., Ltd. ("HIPLAAD" is a registered trademark), and the Homogenol series manufactured by Kao Corporation ("Homogenol" is a registered trademark). These dispersants may be used individually or in combination of two or more.

[0087] <Flake Composition>

[0088] The so-called sheet composition of the present invention is a substance in which the resin composition of the present invention is sheeted, thereby making the resin composition into a sheet form.

[0089] The sheet composition can be manufactured, for example, by coating the resin composition of the present invention onto a support and removing at least a portion of the solvent to be contained as needed. The sheet composition, formed from the resin composition of the present invention, can produce a sheet-cured product with excellent flexibility and heat resistance when the sheet composition is cured.

[0090] There is no particular limitation on the thickness of the sheet composition, and it can be appropriately selected according to the purpose. For example, the thickness can be 50 μm to 500 μm, and from the viewpoint of thermal conductivity, electrical insulation and flexibility, it is preferred to be 80 μm to 400 μm.

[0091] The sheet composition of the present invention can be manufactured, for example, by applying a coating (hereinafter also referred to as "composition coating") of the composition prepared by adding organic solvents such as triethylene glycol dimethyl ether and cyclohexanone to the composition of the present invention onto a support to form a coating layer (composition layer), and then removing at least a portion of the organic solvent from the coating layer and drying it. Examples of supports include, for example, polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film. The bonding surface between the support and the heat-conducting sheet can be surface-treated with silicone, silane coupling agents, aluminum chelating agents, polyurea, etc., which can improve the adhesion and peelability with the sheet composition. From a workability point of view, the thickness of the support is preferably 10 to 200 μm.

[0092] The application of the composition coating can be carried out by known methods. Specifically, it can be done by comma coating, mold coating, lip coating, gravure coating, screen printing, spraying, etc. As methods for forming a composition layer of a specified thickness, examples include comma coating, in which the coated material passes through the gaps, and mold coating, in which the flow rate of the composition coating is adjusted from the nozzle. For example, when the thickness of the coating layer (composition layer) before drying is 50 μm to 500 μm, comma coating or lip coating is preferred.

[0093] There are no particular limitations on the drying method as long as it can remove at least a portion of the organic solvent contained in the coating composition. A commonly used drying method can be appropriately selected based on the organic solvent contained in the coating composition. Generally, a method involving heat treatment at around 80°C to 150°C can be cited.

[0094] In the case where the sheet composition (composition layer) of the present invention contains (B) a thermosetting resin, this refers to the state from which the sheet composition (composition layer) has not undergone a complete curing reaction to a state in which a partial curing reaction has occurred. Therefore, the sheet composition, especially in the state where the curing reaction has not occurred, although it has softness, lacks the strength of a sheet. Therefore, it lacks sheet self-supporting properties when the support such as the PET film has been removed, and is sometimes difficult to handle.

[0095] Therefore, from the viewpoint of improving operability, the sheet composition is preferably a substance in which the composition layer constituting it has undergone a semi-cured treatment. That is, the sheet composition is preferably a semi-cured composition that is further heat-treated until the composition layer becomes a semi-cured state (B-stage state) to form a B-stage sheet. By semi-curing the composition layer, a sheet composition with excellent thermal conductivity and electrical insulation, as well as excellent self-support and service life as a B-stage sheet, can be obtained.

[0096] There are no particular limitations on the conditions for heat treatment of the sheet composition, as long as the composition layer can be in a B-stage state. These conditions can be appropriately selected based on the composition. Regarding heat treatment, to reduce voids (pores) in the composition layer generated during coating, it is preferable to use a method selected from hot vacuum pressing, hot roller lamination, etc. This allows for the efficient production of B-stage sheets with flat surfaces.

[0097] Specifically, for example, the composition layer can be semi-cured up to stage B by heating and pressurizing under reduced pressure (e.g., 1 kPa) at a temperature of 100°C to 200°C for 1 to 3 minutes with a pressing pressure of 1 MPa to 20 MPa.

[0098] Alternatively, it is preferable to laminate two sheets of the resin composition, which have been coated and dried on a support, and then subject them to the aforementioned heating and pressurization treatment to semi-cur them until stage B. At this point, it is desirable to laminate the coated surfaces of the composition layers (the surfaces of the composition layers not in contact with the support) together. If the composition layers are laminated in a manner that ensures they are in contact with each other, both sides of the resulting stage B sheet composition (i.e., the surfaces that appear when the support is peeled off) become flatter, resulting in good adhesion to the bonded parts. Heat dissipation components and electronic components manufactured using such sheet compositions exhibit high thermal conductivity.

[0099] The thickness of the B-stage sheet can be appropriately selected according to the purpose. For example, it can be 50 μm to 500 μm, and from the viewpoints of thermal conductivity, electrical insulation and flexibility, it is preferably 80 μm to 300 μm. In addition, it can also be manufactured by laminating two or more sheet compositions while hot pressing.

[0100] From the viewpoint of suppressing bubble formation caused by gas release during curing of the composition layer, the residual rate of volatile components in the B-stage sheet is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.8% by mass or less. The solvent residual rate is determined by drying a sample obtained by cutting the B-stage sheet into 40mm × 40mm pieces in a constant temperature bath preheated to 190°C for 2 hours, and measuring the mass change before and after drying.

[0101] <Sheet Cured Products>

[0102] The sheet-cured product of the present invention is a substance obtained by curing the resin composition or sheet composition of the present invention, i.e., their cured product.

[0103] Sheet-cured products can be manufactured by curing an uncured composition, a sheet composition, a B-stage composition, or a B-stage sheet composition. The curing method can be appropriately selected based on the composition's structure, purpose, etc., but heating and pressurization are preferred. For example, the heating temperature is preferably 120°C or higher, more preferably 150°C or higher, and even more preferably 180°C or higher. On the other hand, the heating temperature is preferably 400°C or lower, more preferably 300°C or lower, and even more preferably 250°C or lower. Furthermore, the heating time is preferably 5 minutes to 5 hours. The heating temperature can be increased in stages or continuously within a selected temperature range. Examples include methods such as heating at 130°C and 200°C for 30 minutes each, or linearly increasing the temperature from room temperature to 250°C over 2 hours. Examples of heating apparatus include, for example, an oven, a hot plate, and infrared radiation. When the curing temperature exceeds 180°C, curing under a nitrogen atmosphere and vacuum is preferred.

[0104] Furthermore, the sheet-cured product of the present invention preferably has an elastic modulus of 0.1 to 100 MPa at 25°C, more preferably 0.3 to 50 MPa, and even more preferably 0.5 to 15 MPa. To achieve an elastic modulus of 0.5 to 15 MPa at 25°C in the sheet-cured product of the present invention, methods can be employed such as appropriately adjusting the composition of (A) the polymer, (B) the thermosetting resin, (D) the curing agent or curing accelerator, and (C) the inorganic filler, particularly controlling the ratio of the siloxane backbone in (A) the polymer.

[0105] The elastic modulus of the sheet-cured product of the present invention at -70°C is preferably 0.01 to 1000 MPa, more preferably 0.1 to 90 MPa, and even more preferably 1 to 85 MPa. To achieve an elastic modulus of 0.01 to 100 MPa at -70°C for the sheet-cured product of the present invention, methods can be employed such as appropriately adjusting the composition of (A) the polymer, (B) the thermosetting resin, (D) the curing agent or curing accelerator, and (C) the inorganic filler, particularly controlling the ratio of the siloxane backbone in (A) the polymer.

[0106] In this invention, the elastic modulus of the sheet-cured material is the storage modulus value obtained by dynamic viscoelasticity measurement. The dynamic viscoelasticity measurement is performed according to JIS K 7244 (1998) in tensile mode. Examples of dynamic viscoelasticity measuring devices include, for example, the DMS6100 manufactured by Seiko Instrument Ments Co., Ltd., and the DVA-200 manufactured by Ity Co., Ltd.

[0107] The glass transition temperature (Tg) of the sheet-cured product of the present invention is preferably below 0°C, more preferably below -20°C, and even more preferably below -50°C. Furthermore, it is preferable that the glass transition temperature (Tg) of the sheet-cured product is above -120°C. To achieve a glass transition temperature (Tg) of -120°C or higher and -50°C or lower for the sheet-cured product, methods can be employed such as appropriately adjusting the composition of the resin composition (A) polymer, (B) thermosetting resin, (D) curing agent or curing accelerator, and (C) inorganic filler, particularly controlling the ratio of the siloxane backbone in the (A) polymer.

[0108] <Laminated Body>

[0109] The laminate of the present invention is a substance on which a resin sheet is further laminated onto the resin composition, sheet composition, or sheet cured product of the present invention. That is, the laminate of the present invention is a sheet comprising an adhesive layer and two or more layers of the resin composition, sheet composition, or sheet cured product of the present invention. Furthermore, the laminate of the present invention preferably has an adhesive layer on at least a portion of one or both sides of the resin composition, sheet composition, or sheet cured product of the present invention. Here, the adhesive layer in the laminate can be in direct contact with the resin composition, sheet composition, or sheet cured product of the present invention, or a layer such as a metal layer can be provided between the resin composition, sheet composition, or sheet cured product and the adhesive layer.

[0110] The type and material of the adhesive layer are not particularly limited, but the adhesive layer preferably includes at least one selected from epoxy resin, phenolic resin, urethane resin, silicone resin, acrylic resin, polyimide resin and polyamide-imide resin. From the point of view of adhesive strength, it is more preferable to include at least one selected from epoxy resin, urethane resin, acrylic resin and polyimide resin.

[0111] There are no particular restrictions on the method of fabricating the laminate; for example, it can be carried out by methods selected from hot vacuum pressing, hot roll lamination, etc.

[0112] <Laminated Components>

[0113] The laminated component of the present invention is a laminated component having component A, the sheet cured product of the present invention, and component B in sequence, and the coefficients of linear expansion of component A and component B differ by more than 1.

[0114] The types and materials of components A and B are not particularly limited as long as their coefficients of linear expansion differ by more than 1. Examples of materials that can be used for components A and B include alumina, zirconium oxide, aluminum nitride, silicon carbide, silicon nitride, glass, aluminum, copper, and titanium. The combination of components A and B is not particularly limited as long as their coefficients of linear expansion differ by more than 1, but a combination of ceramic and metal is preferred. More specifically, combinations of components A and B are preferred, for example, alumina and aluminum, aluminum nitride and aluminum, alumina and titanium, and silicon carbide and aluminum. By selecting alumina and aluminum, or aluminum nitride and aluminum, the coefficients of linear expansion of components A and B can differ by more than 1, which is particularly preferred.

[0115] <Chip Holder>

[0116] The wafer holder of the present invention comprises the laminated member of the present invention. More specifically, the wafer holder of the present invention comprises a laminated member in which a ceramic Coulomb force-type electrostatic chuck, which serves as member A and has the function of adsorbing and holding the adsorbed object, and a metal cooling plate, which has the sheet-cured material of the present invention disposed between them. The wafer holder of the present invention preferably has a temperature regulating function, which has the function of uniformly and constantly regulating the temperature of the adsorbed object. Since the wafer holder is used in a wide temperature range from low temperatures below 0°C to high temperatures above 150°C, it is required that the electrostatic chuck and the cooling plate do not peel off even after repeated thermal cycling. By providing the sheet-cured material of the present invention therebetween, the thermal stress in thermal cycling can be mitigated, and the adhesive state can be maintained well over a long period of time over a wide temperature range. In particular, by providing the sheet-cured material of the present invention, the adhesive state can be well maintained in a region from low temperatures below 0°C to high temperatures above 200°C.

[0117] Semiconductor Manufacturing Equipment

[0118] The semiconductor manufacturing apparatus of the present invention includes the wafer holder of the present invention. Therefore, the semiconductor manufacturing apparatus of the present invention preferably includes a wafer holder having a plasma source and a temperature control mechanism. In the semiconductor manufacturing apparatus, a substrate to be processed, such as a semiconductor wafer, is placed on a wafer holder provided in a processing chamber, and a high-frequency voltage is applied to the processing chamber in a vacuum environment to generate plasma, thereby performing a dry etching process on the substrate to be processed. Since the processing accuracy required in the dry etching process is higher, the temperature of the substrate to be processed is adjusted to be constant in order to improve the uniformity of the in-plane plasma processing of the substrate to be processed. As previously described, by providing the wafer curing material of the present invention, the bonding state can be maintained well over a wide temperature range for a long period of time, thereby maintaining the uniformity of the in-plane plasma processing of the substrate to be processed well.

[0119] Example

[0120] The present invention will now be described in detail based on embodiments, but the invention is not limited thereto. First, the evaluation methods performed in Examples 1 to 17 and Comparative Examples 1 to 2 will be described.

[0121] <Preparation of Evaluation Samples>

[0122] The sheet compositions prepared in the examples and comparative examples described later were cut into 50 mm squares. The protective film on one side of the adhesive sheet, each with a 50 μm thick adhesive layer, was further peeled off. The adhesive layers were then laminated together at 120°C and 0.4 MPa. This process was repeated until an adhesive layer with a thickness of 200 μm was formed. The resulting cured sheet was then cured at 180°C for 6 hours to obtain a sample of the cured sheet for evaluation.

[0123] (1) Elastic modulus at 25℃:

[0124] The above-mentioned evaluation sheet-cured material samples were cut into 5mm×20mm pieces and used as the sheet-cured material samples for evaluating the elastic modulus at 25℃.

[0125] The elastic modulus of a sample for evaluating elastic modulus at 25°C was determined using a DMS6100 dynamic viscoelasticity measuring apparatus manufactured by Seiko Instrument Ments Co., Ltd. The measurement conditions were as follows: a heating rate of 5°C / min and a measurement frequency of 1Hz. The storage modulus was measured at each temperature within the range of -130°C to 300°C, and the storage modulus at 25°C was taken as the elastic modulus at 25°C.

[0126] (2) Glass transition temperature (Tg)

[0127] The glass transition temperature (Tg) was determined by cutting the cured sample of the above-mentioned evaluation sheet into 5mm × 20mm pieces and performing dynamic viscoelasticity measurements. A DMS6100 dynamic viscoelasticity measuring apparatus manufactured by Seiko Instrument Ments Co., Ltd. was used, set to temperature: -70~300℃, heating rate: 5℃ / min, tensile mode, and frequency: 1Hz. The temperature at the peak of the tanδ value of the obtained curve was defined as Tg.

[0128] (3) Shear strain

[0129] The sheet composition described later is cut into 10mm × 10mm pieces. After peeling off one side of the PET film, it is adhered to an aluminum plate measuring 50mm in length, 15mm in width, and 0.5mm in thickness. The PET film on the other side is then peeled off and adhered to another aluminum plate in a staggered manner to produce a test piece for shear testing.

[0130] After the test pieces for shear testing were heat-cured at 180°C for 6 hours, tensile tests were conducted using a Technograf TG-1kN tensile-compression testing machine manufactured by Minebea Mitsumi Co., Ltd., and the displacement of the fracture point was measured. Measurements were performed using a 1kN force sensor and a tensile speed of 5 mm / min. The value obtained by removing the fracture point and considering the thickness of the sheet composition was defined as the shear strain.

[0131] (4) Heat resistance

[0132] The materials obtained by heating and curing the test pieces for shear testing using the above method at 180°C for 6 hours, and the materials further heated at 250°C under vacuum for 1000 hours, were subjected to tensile tests using a Technograf TG-1kN tensile-compression testing machine manufactured by Minebea Mitsumi Co., Ltd., and the shear strain was calculated. Measurements were performed using a 1kN force sensor and a tensile speed of 5 mm / min. A change rate of less than 30% between the shear strain after heating and curing at 180°C for 6 hours and the shear strain after further heating at 250°C under vacuum for 1000 hours was defined as "good," while a change rate of more than 30% was defined as "bad."

[0133] (5) Imidification rate of the synthesized (A) polymer

[0134] First, the infrared absorption spectrum of polymer (A) was measured, confirming the absorption peak (1780 cm⁻¹) originating from the imide structure of the polyimide. -1 Nearby, 1377cm -1 The presence of (nearby). Next, regarding polymer (A), after heat treatment at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the 1377 cm⁻¹ values ​​before and after heat treatment were compared. -1 The intensity of nearby peaks was compared. The imidization rate of polymer (A) after heat treatment was set to 100%, and the imidization rate of polymer (A) before heat treatment was calculated.

[0135] (6) Glass transition temperature (Tg) of the synthesized (A) polymer

[0136] After removing the solvent from polymer (A), differential scanning calorimetry (DSC) was performed to determine the glass transition temperature (Tg). A Seiko Instrumentation Co., Ltd. DSC6200 differential scanning calorimetry apparatus was used, set to a temperature range of -150 to 300°C and a heating rate of 10°C / min. The onset temperature of the obtained DSC curve was taken as the Tg of polymer (A).

[0137] (7) The weight-average molecular weight of the synthesized (A) polymer

[0138] The polymer (A) obtained by the methods described in the various examples and comparative examples was dissolved in a solution of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) with a polyimide concentration of 0.1% by weight. The solution was used as the test sample and was measured using a Waters 2690 GPC apparatus (manufactured by Waters Corporation) with the configuration shown below. The weight-average molecular weight converted from polystyrene was calculated.

[0139] The GPC determination conditions were as follows: the mobile phase consisted of NMP dissolved in LiCl and phosphoric acid at a concentration of 0.05 mol / L, and the development rate was 0.4 ml / min.

[0140] Detector: Waters996

[0141] System controller: Waters2690

[0142] Column oven: Waters HTR-B

[0143] Temperature controller: Waters TCM

[0144] Column: TOSOH guard column (set up to prevent column clogging caused by the capture of large particles mixed in with the analyte)

[0145] Column: TOSOH TSK-GELα-4000 (a column with an exclusion limit molecular weight of 1,000,000)

[0146] Column: TOSOH TSK-GELα-2500 (a column with an exclusion limit molecular weight of 10,000)

[0147] The three columns above were connected in series.

[0148] In addition, details of the raw materials represented by abbreviations in each embodiment are shown below.

[0149] <Resin>

[0150] • Polymers selected from polyimide and polyamic acid (A)

[0151] <(A) Raw materials for polymers>

[0152] X-22-168AS: (Shin-Etsu Chemical Co., Ltd.) (Number average molecular weight 1000: Two-terminal anhydride modified polysiloxane of general formula (2): n=9) (R 7 ~R 10 (methyl)

[0153] X-22-168A: (Shin-Etsu Chemical Co., Ltd.) (Number average molecular weight 2000: Two-terminal anhydride modified polysiloxane of general formula (2): n=19) (R 7 ~R 10 (methyl)

[0154] ODPA: 4,4'-O-diphthalic anhydride (manufactured by Manak Corporation)

[0155] BPDA: 3,3'-4,4'-Biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Co., Ltd.)

[0156] KF8010: Diaminopolysiloxane (Shin-Etsu Chemical Co., Ltd.) (Number average molecular weight 860: Diaminopolysiloxane of general formula (1): m = 9) (R 1 ~R 4 It is methyl, R 5 and R 6 (1,3-Propylene)

[0157] X-22-161A: Diaminopolysiloxane (Shin-Etsu Chemical Co., Ltd.) (Number average molecular weight 1600: Diaminopolysiloxane of general formula (1): m = 19) (R 1 ~R 4 It is methyl, R 5 and R 6 (1,3-Propylene)

[0158] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoroisopropylidene (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0159] <(A) Polymer Synthesis>

[0160] ·(A) Polymer A

[0161] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 47.27 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were added and stirred at 60 °C until dissolved. Then, 3.66 g of BAHF and 77.40 g of KF8010 were added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) A (solid content concentration 80.0 wt%). The weight-average molecular weight of polymer (A) A was determined to be 45,600, and the imidization rate was determined to be 99%.

[0162] • (A) Polymer B

[0163] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 102.24 g of dimethylacetamide, 98.00 g of X-22-168AS, and 7.45 g of ODPA were added and dissolved by stirring at 60 °C. Then, 4.40 g of BAHF and 89.64 g of KF8010 were added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) B (solid content concentration 60.0 wt%). The weight-average molecular weight of polymer (A) B was determined to be 57,320, and the imidization rate was determined to be 99%.

[0164] (A) Polymer C

[0165] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 113.92 g of dimethylacetamide, 77.25 g of X-22-168AS, and 23.27 g of ODPA were added and dissolved by stirring at 60 °C. Then, 5.49 g of BAHF and 112.05 g of KF8010 were added while stirring at 120 °C for 1 hour. The mixture was then heated to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) C (solids concentration 60.0 wt%). The weight-average molecular weight of polymer (A) C was determined to be 69,750, and the imidization rate was determined to be 99%.

[0166] ·(A) Polymer D

[0167] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 92.93 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were added and dissolved by stirring at 60 °C. Then, 11.72 g of BAHF and 41.28 g of KF8010 were added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) D (solids concentration 80.0 wt%). The weight-average molecular weight of polymer (A) D was determined to be 60,350, and the imidization rate was determined to be 99%.

[0168] (A) Polymer E

[0169] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 132.70 g of triethylene glycol dimethyl ether and 121.00 g of X-22-168A were added and stirred at 60 °C until dissolved. Then, 2.01 g of BAHF and 76.23 g of X-22-161A were added while stirring at 120 °C for 1 hour. The mixture was then heated to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) E (60.0 wt% solids). The weight-average molecular weight of polymer (A) E was determined to be 48,020, and the imidization rate was determined to be 99%.

[0170] (A) Polymer F

[0171] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 39.86 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were added and stirred at 60 °C until dissolved. Then, 25.64 g of BAHF and 25.80 g of KF8010 were added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) F (solids concentration 80.0 wt%). The weight-average molecular weight of polymer (A) F was determined to be 55,680, and the imidization rate was determined to be 99%.

[0172] (A) Polymer G

[0173] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 33.79 g of triethylene glycol dimethyl ether, 32.40 g of X-22-168AS, and 21.72 g of ODPA were added and dissolved by stirring at 60 °C. Then, 3.66 g of BAHF and 77.40 g of KF8010 were added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) G (solids concentration 80.0 wt%). The weight-average molecular weight of polymer (A) G was determined to be 59,790, and the imidization rate was determined to be 99%.

[0174] (A) Polymer H

[0175] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 300 ml four-necked flask. Under a nitrogen atmosphere, 88.39 g of triethylene glycol dimethyl ether and 14.56 g of BPDA were added and stirred at 60 °C until dissolved. Then, 1.83 g of BAHF and 72.00 g of X-22-161A were added while stirring at 120 °C, and the mixture was stirred for another hour. The temperature was then raised to 200 °C and stirred for 3 hours, after which the mixture was cooled to room temperature to obtain polymer (A) F (solids concentration 50.0 wt%). The weight-average molecular weight of polymer (A) F was determined to be 45,300, and the imidization rate was determined to be 99%.

[0176] (A) Polymer I

[0177] A stirrer, thermometer, nitrogen inlet tube, and dropping funnel were set up in a 500 ml four-necked flask. Under a nitrogen atmosphere, 77.13 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were added and dissolved by stirring at 60 °C. Then, 29.30 g of BAHF was added while stirring at 120 °C for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain polymer (A) G (solids concentration 80.0 wt%). The weight-average molecular weight of polymer (A) G was determined to be 74,270, and the imidization rate was determined to be 99%.

[0178] The monomer composition and properties of the synthesized (A) polymer are shown in Tables 1 and 2.

[0179] • Acrylic rubber: Acrylic rubber with an average molecular weight of 850,000 containing epoxy groups, Tg-32℃, monomer copolymerization ratio of ethyl acrylate: butyl acrylate: glycidyl acrylate = 65:35:1, functional group (epoxy group) content 0.09 equivalents / kg.

[0180] Aromatic polyimide

[0181] <Synthesis of Aromatic Polyimides>

[0182] 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 a capping agent were dissolved in 80 g of N-methylpyrrolidone (hereinafter referred to as NMP). 31.02 g (0.1 mol) of ODPA and 20 g of NMP were added together, and the mixture was reacted at 20 °C for 1 hour, followed by stirring at 50 °C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 180 °C for 5 hours while azeotropically reacting water with xylene. After stirring, the solution was added to 3 L of water, yielding a white precipitated polymer. The precipitate was recovered by filtration, washed three times with water, and dried using a vacuum dryer at 80 °C for 20 hours. The infrared absorption spectrum of the obtained polymer solid was measured, and the results showed that the precipitate was at 1780 cm⁻¹. -1 Nearby, 1377cm -1 An absorption peak originating from the imide structure of the polyimide was detected nearby. This operation yielded an aromatic polyimide with functional groups capable of reacting with epoxy groups.

[0183] (B) Thermosetting resins

[0184] jER1032H60: Tris(hydroxyphenyl)methane type epoxy resin (manufactured by Mitsubishi Kemikal Co., Ltd.)

[0185] HP4700: Naphthalene-type multifunctional epoxy resin (manufactured by DIC Corporation).

[0186] • (C) Inorganic filler materials

[0187] AA-3: High-purity alumina (average particle size: 3μm) (manufactured by Sumitomo Chemical Co., Ltd.)

[0188] AA-04: High-purity alumina (average particle size: 0.4 μm) (manufactured by Sumitomo Chemical Co., Ltd.)

[0189] SO-E1: High-purity synthetic spherical silica (average particle size: 0.3μm) (manufactured by Admadex Corporation).

[0190] (D) Curing agent or curing accelerator

[0191] SEIKACURE-S: 4,4-Diaminodiphenyl sulfone (manufactured by Wakayama Seika Kogyo Co., Ltd.)

[0192] C17Z: 2-Heptadecanylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)

[0193] <Examples 1-17, Comparative Examples 1-4>

[0194] Examples 1-17 and Comparative Examples 1-4 were mixed in the manner shown in Tables 3-5, and triethylene glycol dimethyl ether was added. The mixture was stirred at 1800 rpm for 10 minutes using a self-rotating mixer (Shinki Corporation) to prepare a composition solution.

[0195] The composition solution was coated onto a 38 μm thick polyethylene terephthalate film (Immu Corporation RF2·PETcs000) with a silicone release agent using a rod coater to achieve a dry thickness of 50 μm (hereinafter referred to as the composition coating). After drying at 120°C for 30 minutes, the protective film was laminated at 120°C and 0.4 MPa to produce a sheet composition. The results of various evaluations are shown in Tables 3 to 5.

[0196]

[0197] Table 2

[0198]

[0199]

[0200]

[0201]

[0202] According to Tables 3-5, Examples 1-17, which use polymers (A) A-G containing both diamine residues and anhydride residues in a polysiloxane backbone, all have an elastic modulus of less than 100 MPa and a shear strain of 1.5 or more, exhibiting sufficient flexibility, adhesion to the adherend, and conformability. Furthermore, they have "good" heat resistance, indicating that they can maintain a good bond over a long period. In particular, Examples 1-15, which use polymers (A) A-E containing more than 60 mol% of diamine residues (1) and more than 50 mol% of anhydride residues (2) in all diamine residues, show a tendency towards lower elastic modulus and higher shear strain. By incorporating a large amount of the siloxane backbone, flexibility, adhesion to the adherend, and conformability can be further improved.

[0203] On the other hand, according to Table 5, Comparative Example 1, which used acrylic rubber as the thermoplastic resin, had a "poor" heat resistance, and its shear strain decreased significantly from the initial 4.12 after heating at 250°C under vacuum for 1000 hours. Furthermore, Comparative Example 2, which used aromatic polyimide as the thermoplastic resin, had a "good" heat resistance, but its elastic modulus was very high at 4500 MPa, and its shear strain was very low at less than 0.5, resulting in insufficient flexibility, adhesion to the adhered object, and conformability. Comparative Example 3, which used (A) polymer H containing only a polysiloxane structure in the diamine residues, and Comparative Example 4, which used (A) polymer I containing only a polysiloxane structure in the anhydride residues, showed a decrease in elastic modulus and an increase in shear strain compared to Comparative Example 2. However, the elastic modulus remained high at 110 MPa (Comparative Example 3) and 120 MPa (Comparative Example 4), respectively, and the shear strain was less than 1.5, indicating insufficient flexibility, adhesion to the adhered object, and conformability.

Claims

1. A resin composition comprising (A) a polymer and (B) a thermosetting resin, wherein the (A) polymer is selected from polyimides and polyamic acids having residues of a diamine having general formula (1) and residues of an anhydride having general formula (2), hereinafter referred to as diamine residues of general formula (1) and anhydride residues of general formula (2) as anhydride residues (2). The thermosetting resin (B) contains a soft epoxy resin that does not contain a siloxane backbone. When the total of all diamine residues and all anhydride residues in polymer (A) is set to 100 mol%, the total of diamine residues (1) and anhydride residues (2) is 55 mol% or more and 100 mol% or less. When all anhydride residues in polymer (A) are set to 100 mol%, the content of anhydride residues (2) is more than 50 mol% and less than 100 mol%. In general formula (1), R 1 ~R 4 They can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms; among them, Phenyl and phenoxy groups can be substituted by alkyl groups having 1 to 30 carbon atoms; m R 1 and R 3 They can be the same or different; In general formula (1), R 5 and R 6 They can be the same or different, representing alkylene or arylene with 1 to 30 carbon atoms; wherein, arylene can be replaced by alkyl with 1 to 30 carbon atoms; In general formula (1), m is an integer selected from 1 to 100; In general formula (2), R 7 ~R 10 These can be the same or different, representing alkyl, phenyl, or phenoxy groups with 1 to 30 carbon atoms; among them, phenyl and phenoxy groups can be substituted by alkyl groups with 1 to 30 carbon atoms; n R 7 and R 9 They can be the same or different; In general formula (2), R 11 and R 12 They can be the same or different, representing alkylene or arylene with 1 to 30 carbon atoms; wherein, arylene can be replaced by alkyl with 1 to 30 carbon atoms; In general formula (2), n is an integer selected from 1 to 100.

2. The resin composition according to claim 1, wherein, When all diamine residues in the polymer (A) are set to 100 mol%, the polymer contains more than 60 mol% and less than 100 mol% of diamine residues (1).

3. The resin composition according to claim 1 or 2, wherein m is 3 or more and 40 or less, and n is 3 or more and 40 or less.

4. The resin composition according to claim 1 or 2, wherein the glass transition temperature Tg of the polymer (A) is above -150°C and below -30°C.

5. The resin composition according to claim 1 or 2, wherein the (B) thermosetting resin is a soft epoxy resin that does not contain a siloxane backbone.

6. The resin composition according to claim 1 or 2, comprising (C) an inorganic filler.

7. The resin composition according to claim 1 or 2, comprising (D) a curing agent or a curing accelerator.

8. The resin composition according to claim 1 or 2, wherein the glass transition temperature Tg of the cured sheet is above -120°C and below 0°C.

9. A sheet composition obtained by sheeting the resin composition according to any one of claims 1 to 8.

10. A sheet-cured product obtained by curing the resin composition of any one of claims 1 to 8, or the sheet composition of claim 9.

11. A laminate obtained by further laminating resin sheets onto the resin composition of any one of claims 1 to 8, the sheet composition of claim 9, or the sheet-cured product of claim 10.

12. A laminated component comprising, in sequence, a component A, a sheet-cured material as described in claim 10, and a component B, wherein the coefficients of linear expansion of component A and component B differ by more than 1.

13. A wafer holder comprising the stacked member of claim 12.

14. A semiconductor manufacturing apparatus comprising the wafer holder of claim 13.

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