Resin compositions for wafer holders, sheet compositions, sheet hardeners, laminates, laminated components, wafer holders, and semiconductor manufacturing apparatus

Abstract

The object of the present invention is to provide a resin composition capable of manufacturing an adhesive sheet for an electrostatic chuck that exhibits excellent heat resistance, low elastic modulus, and can achieve close and followable adhesion by mitigating the thermal expansion differences of the substrate when used in a single layer. The present invention is a resin composition comprising (A) a polymer selected from polyimide and polyamide, and (B) a thermosetting resin, comprising residues of a diamine having a specific structure (hereinafter referred to as diamine residue (1)) and residues of an anhydride having a specific structure (hereinafter referred to as an anhydride residue (2)).

Description

[Technical Field]

[0001] This invention relates to a resin composition containing a thermoplastic resin and a thermosetting resin, as well as a sheet composition, a sheet-cured material, a laminate, a laminated component, a wafer holder, and a semiconductor manufacturing apparatus. [Previous Technology]

[0002] In a wafer holder formed by bonding a ceramic electrostatic chuck (electrostatic chuck heater, base) to a metal cooling plate, resin-based adhesive tape or adhesive material is generally used in the bonding of the electrostatic chuck and the cooling plate. As an adhesive composition for this purpose, 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). However, the operating temperature of such wafer holders to date is limited due to the heat resistance of the resin (especially thermoplastic resins) (generally below 100°C, and even if it can be used at high temperatures, it is at most below 150°C).

[0003] On the other hand, if heat-resistant resins such as polyimide are used, the resin has a high modulus of elasticity and cannot absorb the difference in thermal expansion between the ceramic and the cooling plate, which will cause deformation or cracking, making it difficult to use as a wafer holder. When bonding is performed by metal solder, if bonding is possible, it can be used even at high temperatures; however, if the thermal expansion of the ceramic and the cooling plate (metal) is not synchronized, deformation or cracking will occur during bonding.

[0004] In response to the above-mentioned requirements for heat resistance suitable for use at high temperatures such as 200°C, and for achieving close adhesion and conformability to the substrate while mitigating the thermal expansion of ceramics and cooling plates (metals), an adhesive sheet for electrostatic chucks has been proposed. This sheet is formed by laminating a silicone resin elastic phase capable of mitigating thermal expansion onto a polyimide-based adhesive layer that possesses both heat resistance and adhesion (Patent Document 2). [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. Hei 11-265960 [Patent Document 2] Japanese Patent Application Publication No. 2002-83862 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] However, in the device of Patent Document 2, since the silicone elastic phase is more flexible than the adhesive layer and there is a difference in elastic modulus, there is a risk of peeling between the silicone elastic phase and the adhesive layer. In addition, the polyimide of the adhesive layer described in Patent Document 2 contains a portion of a flexible silicone structure, but the elastic modulus is still high when it is monomeric, making it difficult to achieve the requirement of maintaining heat resistance while mitigating the difference in thermal expansion and adhering closely to the substrate when it is monomeric.

[0008] Therefore, the main objective of the present invention is to eliminate the aforementioned disadvantages and provide a resin composition capable of manufacturing an adhesive sheet for electrostatic chucks that exhibits excellent heat resistance, a low modulus of elasticity, and, when single-layered, mitigates the difference in thermal expansion of the substrate, enabling close and follow-up bonding. [Means for Solving the Problem]

[0009] To solve the aforementioned problem, the present invention has the following structure.

[0010] A resin composition comprising (A) a polymer selected from polyimide and polyamide having residues of a diamine having general formula (1) (hereinafter referred to as diamine residue (1)) and residues of an anhydride having general formula (2) (hereinafter referred to as anhydride residue (2)), and (B) a thermosetting resin.

[0011] [Chemical 1]

[0012] In general formula (1), R1 to R4 may be the same or different, representing alkyl, phenyl or phenoxy with 1 to 30 carbon atoms. Among them, phenyl and phenoxy may also be substituted by alkyl with 1 to 30 carbon atoms. m R1 and R3 may be the same or different.

[0013] In general formula (1), R5 and R6 may be the same or different, representing an alkyl group or an aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted by an alkyl group having 1 to 30 carbon atoms.

[0014] In general formula (1), m is an integer selected from 1 to 100.

[0015] [Chemical 2]

[0016] In general formula (2), R7 to R10 may be the same or different, representing alkyl, phenyl or phenoxy groups having 1 to 30 carbon atoms. Among them, phenyl and phenoxy groups may also be substituted by alkyl groups having 1 to 30 carbon atoms. n R7 and R9 may be the same or different.

[0017] In general formula (2), R11 and R12 may be the same or different, representing an alkyl or aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted by an alkyl group having 1 to 30 carbon atoms.

[0018] In general formula (2), n is an integer selected from 1 to 100. [Effects of the Invention]

[0019] By means of the resin composition of the present invention, an adhesive sheet for electrostatic chuck can be obtained, that is, it has excellent heat resistance, low elastic modulus, and can maintain good adhesion by mitigating the thermal expansion difference between ceramic and cooling plate (metal) for a long time, even at high temperatures above 200°C.

Implementation Method

[0021] The present invention is a resin composition comprising (A) a polymer selected from polyimide and polyamide having residues of diamine of general formula (1) (hereinafter referred to as diamine residue (1)) and residues of anhydride of general formula (2) (hereinafter referred to as anhydride residue (2)), and (B) a thermosetting resin.

[0022] [Chemical 3]

[0023] In general formula (1), R1 to R4 may be the same or different, representing alkyl, phenyl or phenoxy groups having 1 to 30 carbon atoms. Among them, phenyl and phenoxy groups may also be substituted by alkyl groups having 1 to 30 carbon atoms. m R1 and R3 may be the same or different.

[0024] In general formula (1), R5 and R6 may be the same or different, representing an alkyl or aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted by an alkyl group having 1 to 30 carbon atoms.

[0025] In general formula (1), m is an integer selected from 1 to 100.

[0026] [Chemical 4]

[0027] In general formula (2), R7 to R10 may be the same or different, representing alkyl, phenyl or phenoxy groups having 1 to 30 carbon atoms. Among them, phenyl and phenoxy groups may also be substituted by alkyl groups having 1 to 30 carbon atoms. n R7 and R9 may be the same or different.

[0028] In general formula (2), R11 and R12 may be the same or different, representing an alkyl group or an aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted by an alkyl group having 1 to 30 carbon atoms.

[0029] In general formula (2), n is an integer selected from 1 to 100.

[0030] Hereinafter, the forms in which the present invention is implemented will be described 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 indicated. The same applies to numerical values ​​and their ranges; the present invention is not limited thereto.

[0031] In this specification, the numerical range represented by “~” includes the numerical values ​​before and after “~” as the minimum and maximum values, respectively.

[0032] In this specification, the content rate of each component in the composition refers to the total content rate of the multiple substances present in the composition, unless otherwise specified, when multiple substances equivalent to each component are present in the composition. For example, if the composition contains component A and component B as thermosetting resin components, the content rate of the thermosetting resin components refers to the total content rate of component A and component B.

[0033] In this specification, the term "layer" includes not only the case where the layer is formed in the entire area when the area is observed, but also the case where it is formed only in a part of the area.

[0034] In this specification, the term "layering" means stacking layers, combining two or more layers, or having two or more layers that can be disassembled.

[0035] <Resin Composition> The resin composition of the present invention contains (A) a polymer selected from polyimide and polyamide having residues of diamine of general formula (1) (hereinafter referred to as diamine residue (1)) and residues of acid anhydride of general formula (2) (hereinafter referred to as acid anhydride residue (2)), and (B) a thermosetting resin.

[0036] <(A) Polymer> (A) Polymer has a diamine residue (1) and an anhydride residue (2), and is selected from polyimide and polyamide. Therefore, (A) Polymer is generally obtained mainly by the reaction of tetracarboxylic dianhydride with diamine, and has a tetracarboxylic dianhydride residue and a diamine residue.

[0037] When all diamine residues in polymer (A) are set to 100 mol%, polymer (A) preferably contains 60 mol% or more and 100 mol% or less of diamine residues (1). By containing 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 shape and reduced elastic modulus can be obtained. If the content of diamine residues (1) is less than 60 mol%, the elastic modulus of the sheet-cured product will be higher, and the adhesion and adhesion to the substrate may sometimes decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and conformability to the substrate, when all diamine residues in the polymer (A) are set to 100 mol%, it is preferable to contain 70 mol% or more and 100 mol% or less of diamine residues (1), and more preferably 85 mol% or more and 100 mol% or less of diamine residues (1).

[0038] In general formula (1), R1 to R4 may be the same or different, representing alkyl, phenyl, or phenoxy groups having 1 to 30 carbon atoms. The phenyl and phenoxy groups may also be substituted with alkyl groups having 1 to 30 carbon atoms. Here, the alkyl group may be linear 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. The m R1 and R3 groups may be the same or different.

[0039] In general formula (1), R5 and R6 may be the same or different, representing an alkyl group or an aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted with an alkyl group having 1 to 30 carbon atoms. Furthermore, both the alkyl group and the alkyl group may be linear or branched. Examples of alkyl groups having 1 to 30 carbon atoms include methylene, ethyl, propyl, and butyl. From the viewpoint of further improving heat resistance, the aryl group preferably has 12 or fewer carbon atoms. Examples of aryl groups include phenyl groups. The aryl group may also be a group formed by the bonding of these alkyl groups and the aryl group.

[0040] 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. Furthermore, from the viewpoint of further reducing the elastic modulus of the sheet-cured material, m is preferably 3 or more, and more preferably 5 or more. By setting m to 5 or more, the elastic modulus of the sheet-cured material can be reduced by the long and soft 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.

[0041] When all anhydride residues in polymer (A) are set to 100 mol%, polymer (A) of the present invention preferably contains 50 mol% or more and 100 mol% or less of anhydride residues (2). By containing 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 shape and reduced elastic modulus can be obtained. If the content of anhydride residues (2) is less than 50 mol%, the elastic modulus of the sheet-cured product will be higher, and the adhesion and adhesion to the substrate may sometimes decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and conformability to the substrate, when all anhydride residues in the polymer (A) are set to 100 mol%, it is preferable to contain 70 mol% or more and 100 mol% or less of anhydride residues (2), and more preferably 85 mol% or more and 100 mol% or less of anhydride residues (2).

[0042] In general formula (2), R7 to R10 may be the same or different, representing alkyl, phenyl, or phenoxy groups having 1 to 30 carbon atoms. The phenyl and phenoxy groups may also be substituted with alkyl groups having 1 to 30 carbon atoms. Furthermore, the alkyl group may be linear 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 number of carbon atoms in the alkyl group is preferably 12 or less. The n R7 and R9 groups may be the same or different.

[0043] In general formula (2), R11 and R12 may be the same or different, representing an alkyl group or an aryl group having 1 to 30 carbon atoms. The aryl group may also be substituted with an alkyl group having 1 to 30 carbon atoms. Furthermore, both the alkyl group and the alkyl group may be linear or branched. Examples of alkyl groups having 1 to 30 carbon atoms include methylene, ethyl, propyl, and butyl. From the viewpoint of further improving heat resistance, the aryl group preferably has 12 or fewer carbon atoms. Examples of aryl groups include phenyl groups. It may also be a group formed by the bonding of these alkyl groups and the aryl group.

[0044] In general formula (2), n represents a range of 1 to 100. 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. Furthermore, from the viewpoint of further reducing the elastic modulus of the sheet-cured material, n is preferably 3 or more, and more preferably 5 or more. By setting n to 5 or more, the elastic modulus of the sheet-cured material can be reduced by the 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.

[0045] In the polymer (A) of the present invention, when the total of all diamine residues and all anhydride residues in the polymer (A) is set to 100 mol%, the total of diamine residues (1) and anhydride residues (2) is preferably 55 mol% or more and 100 mol% or less. By using the polymer (A) containing a silicone backbone with high flexibility, 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 shape and reduced 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 will increase, and the adhesion and adhesion to the substrate may sometimes decrease. From the viewpoint of further reducing the elastic modulus and further improving the adhesion and conformability to the substrate, 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 preferably 70 mol% or more and 100 mol% or less, more preferably 85 mol% or more and 100 mol% or less.

[0046] (A) The glass transition temperature (Tg) of the polymer is preferably -150°C or higher and -30°C or lower. By setting the Tg of the polymer (A) to -30°C or lower, the elastic modulus of the sheet-cured material 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 the polymer (A) is preferably -150°C or higher and -50°C or lower, and more preferably -150°C or higher and -80°C or lower. In order to make the Tg of the polymer (A) of the present invention fall within the aforementioned range, methods for controlling the structure of the polymer (A), particularly the ratio of the siloxane backbone, can be listed.

[0047] (A) The weight average molecular weight of the polymer is preferably 1,000 or more, and more preferably 10,000 or more. By having a weight average molecular weight of 1,000 or more, the toughness of the sheet-hardened material can be improved, the elastic modulus can be reduced, and since it is a high molecular weight, the heat resistance can be further improved. On the other hand, (A) The weight average molecular weight of the polymer is preferably 1,000,000 or less, and more preferably 200,000 or less. By having a weight average molecular weight of 1,000,000 or less, the viscosity when the solution is prepared can be reduced, thereby further improving processability.

[0048] Here, the weight average molecular weight of polymer (A) can be calculated as a polystyrene conversion value by performing gel permeation chromatography (GPC) analysis on a solution of polymer (A) dissolved in N-methyl-2-pyrrolidone with a resin concentration of 0.1% by weight.

[0049] (A) The polymer is preferably solvent-soluble. If it is solvent-soluble, the viscosity can be kept low when preparing the resin composition, which can further improve the dispersibility of (C) the inorganic filler. Here, the term (A) polymer refers to solvent solubility, meaning that it dissolves at 25°C more than 1 g of any organic solvent selected from 100 g of any ether solvent selected from N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylmethamide, N-vinylpyrrolidone, N,N-diethylmethamide, etc.; 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, ethylene glycol diethyl ether, etc.

[0050] Commercially available diamines preferred as raw materials for polymers having diamine residues represented by the general formula (1) include, for example, X-22-161A, X-22-161B, KF8012, KF8010, KF8008, X-22-1660B-3, etc., manufactured by Shin-Etsu Chemical Co., Ltd. Two or more of these may also be used.

[0051] The diamine residues constituting polymer (A) preferably have hydroxyl and / or carboxyl groups. By containing diamine residues having hydroxyl or carboxyl groups, the reaction with the thermosetting resin (B) can be promoted, thereby improving the toughness of the sheet-cured material. 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 having hydroxyl and / or carboxyl groups. On the other hand, from the viewpoint of further reducing the elastic modulus of the sheet-cured material and further improving its flexibility, it is preferable that the total diamine residues contain at least 40 mol% of diamine residues having hydroxyl and / or carboxyl groups, and more preferably at least 30 mol%.

[0052] Commercially available anhydrides that are preferably used as raw materials for polymers having anhydride residues represented by the general formula (2) include, for example, X-22-168AS, X-22-168A, X-22-168B, X-22-168-P5-B manufactured by Shin-Etsu Chemical Co., Ltd. Two or more of these may also be used.

[0053] <(B) Thermosetting Resin> The (B) thermosetting resin contained in the resin composition of the present invention is not particularly limited. Preferably, the (B) thermosetting resin is at least one selected from the group consisting of 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.

[0054] In addition, the content of (B) thermosetting resin is not particularly limited. From the viewpoint of improving the toughness of the resin composition and its heat resistance at high temperatures, it is preferably 0.1 parts by weight or more relative to 100 parts by weight of (A) polymer. From the viewpoint of improving the flexibility of the composition, it is preferably 15 parts by weight or less.

[0055] <Epoxy Resin> There are no particular limitations on the epoxy resin used as the thermosetting resin (B) of the present invention. From the viewpoint of improving heat resistance at high temperatures above 200°C, preventing brittleness of the composition after long-term use at 200°C, and improving adhesion, an epoxy resin containing an aromatic backbone is preferred. Since the aromatic backbone is rigid, it is preferred. Examples of aromatic backbones include benzene rings or naphthalene rings. Examples of such epoxy resins include Mitsubishi Chemical (stock)'s jER828 containing a bisphenol backbone, jER1032H60 containing a triphenylmethane backbone, and DIC (stock)'s EPICLON HP-4700 or EPICLON HP-4032SS having a naphthalene ring.

[0056] Furthermore, from the same point of view, epoxy resins containing a triazine backbone can also be 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.

[0057] Furthermore, from the viewpoint of reducing the elastic modulus of the hardened composition, improving flexibility, and reducing the 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.

[0058] Furthermore, from the same perspective and from the perspective of compatibility with (A) polymers, (C) inorganic fillers, and (D) curing agents or curing accelerators, a silicone-free and flexible epoxy resin is preferred. A silicone-free and flexible epoxy resin refers to an epoxy resin containing 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 epoxy alkyl adducts, and polyglycidyl esters of aliphatic long-chain polyacids are preferred. Examples of silicone-free and flexible epoxy resins include YX7400, YX7110, YX7180, and YX7105 manufactured by Mitsubishi Chemical Co., Ltd.

[0059] From the viewpoint of improving thermal conductivity, the epoxy resin used in this invention is preferably a crystalline epoxy resin. Crystalline epoxy resin refers to an epoxy resin having a liquid crystal proto-backbone such as a biphenyl, naphthalene, anthracene, phenyl benzoate, or 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.

[0060] 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 Gas Chemicals (Co., Ltd.).

[0061] Furthermore, from the viewpoint that it has a high affinity for polyimide, which can increase the crosslinking density with polyimide and 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.

[0062] Furthermore, from the viewpoint of reducing the 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 one that exhibits a viscosity of 150 Pa·s or less at 25°C and 1.013 × 10⁵ N / m², such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy alkane modified epoxy resin, glycidylamine type epoxy resin, etc. Examples of products corresponding to this type of epoxy resin include: JER827, JER828, JER806, JER807, JER801N, JER802, YX7400, JER604, JER630, and JER630LSD manufactured by Mitsubishi Chemical Co., Ltd., or EPICLON 840S, EPICLON 850S, and EPICLON manufactured by DIC Co., Ltd. 830S, EPICLON 705, EPICLON 707, or YD127, YD128, PG207N, PG202 manufactured by Nippon Steel Chemical Co., Ltd., or TEPIC-PASB26L, TEPIC-PASB22, TEPIC-VL, TEPIC-FL, TEPIC-UC, etc. manufactured by Nissan Chemical Co., Ltd.

[0063] In the resin composition of the present invention, from the viewpoint of balancing the coating stability, the toughness of the resin composition, and the heat resistance at high temperatures, at least one selected from the group consisting of epoxy resins containing an aromatic backbone, soft epoxy resins without a silicone backbone, and crystalline epoxy resins can be preferably used. 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 means of the epoxy resin composition, epoxy resins containing an aromatic backbone or crystalline epoxy resins can be preferably used; when low elasticity is desired by means of the epoxy resin composition, soft epoxy resins without a silicone backbone can be preferably used.

[0064] Furthermore, the epoxy resin used in this invention may be a single type or a combination of two or more types. From the viewpoint of improving the toughness of the composition and its heat resistance at high temperatures, the content of epoxy resin is preferably 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.

[0065] <(D) Hardener or Hardening Accelerator> The resin composition of the present invention may also contain (D) hardener or hardening accelerator as needed.

[0066] By incorporating a curing accelerator or curing agent into a (B) thermosetting resin such as an epoxy resin, the curing of the (B) thermosetting resin such as an epoxy resin can be promoted and cured in a short time. As a curing agent or curing accelerator, imidazoles, polyphenols, acid anhydrides, amines, acehydrides, polythiols, Lewis acid-amine complexes, latent curing agents, etc., can be used.

[0067] As imidazoles, examples include: Curezol C17Z, Curezol 2MZ, Curezol 2PZ, Curezol 2MZ-A, Curezol 2MZ-OK (these are trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), etc. Examples of polyphenols include: Sumilite Resin PR-HF3, Sumilite Resin PR-HF6 (trade names, manufactured by Sumitomo Bakerite Co., Ltd.), Kayahard KTG-105, Kayahard NHN (trade names, manufactured by Nippon Kayaku Co., Ltd.), Phenolite TD2131, Phenolite TD2090, Phenolite VH-4150, Phenolite KH-6021, Phenolite KA-1160, Phenolite KA-1165 (trade names, manufactured by DIC Co., Ltd.), and H-1 (manufactured by Meiwa Kasei Co., Ltd.). Examples of amines include aromatic amines such as SEIKACURE-S, BAPS, DPE / ODA, and Bis Amine A (trade names, manufactured by Wakayama Seika Kogyo Co., Ltd.), and amines with a siloxane skeleton such as KF-8010 and X-22-161A (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, examples of potential curing agents include: dicyandiamine-type potential curing agents, amine adduct-type potential curing agents, organic acid acehydrazine-type potential curing agents, aromatic strontium salt-type potential curing agents, microencapsulated potential curing agents, and photocuring potential curing agents.

[0068] Examples of potential curing agents of the dicyandiamine type include: DICY 7, DICY 15, DICY 50 (trade names, manufactured by Japan Epoxy Resins Co., Ltd.), Amicure AH-154, Amicure AH-162 (trade names, manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc. Examples of potential curing agents of the amine adduct type include: Amicure PN-23, Amicure PN-40, Amicure MY-24, Amicure MY-H (trade names, manufactured by Ajinomoto Fine-Techno Co., Ltd.), FUJICURE FXR-1030 (trade name, manufactured by Fuji Chemical Co., Ltd.), etc. Examples of potential curing agents in the organic acid acehydrazine type include Amicure VDH and Amicure UDH (trade names, manufactured by Ajinomoto Fine-Techno Co., Ltd.). Examples of potential curing agents in the aromatic strontium salt type include San-Aid SI100, San-Aid SI150, and San-Aid SI180 (trade names, manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of potential curing agents in the microencapsulation type include those encapsulated by vinyl compounds, urea compounds, or thermoplastic resins. Among these, microencapsulated latent curing agents obtained by treating amine adduct-type latent curing agents with isocyanates include: Novacure HX-3941HP, Novacure HXA3922HP, Novacure HXA3932HP, and Novacure HXA3042HP (all trade names, manufactured by Asahi Kasei Chemicals, Ltd.). Additionally, light-curing latent curing agents include Optomer SP and Optomer CP (manufactured by ADEKA, Ltd.).

[0069] When the resin composition of the present invention contains (D) a curing agent or a curing accelerator, the content of (B) a thermosetting resin is preferably 0.1 parts by weight or more and 35 parts by weight or less.

[0070] <(C) Inorganic Filler Material> The resin composition of the present invention preferably includes (C) an inorganic filler material. The inorganic filler material is not particularly limited as long as it does not impair the properties of the adhesive. Specific examples include silicon dioxide, alumina, silicon nitride, aluminum hydroxide, gold, silver, copper, iron, nickel, silicon carbide, aluminum nitride, titanium nitride, and titanium carbide. Among these, silicon dioxide, alumina, silicon nitride, silicon carbide, and aluminum hydroxide are preferred in terms of cost. Furthermore, from the viewpoint of balancing cost and thermal conductivity, silicon dioxide and alumina are particularly preferred. Here, silicon dioxide can be either amorphous or crystalline, and is not limited to being used separately according to their respective properties. Surface treatment of these inorganic filler materials may also be performed using silane coupling agents or the like to improve heat resistance, adhesion, etc.

[0071] Furthermore, the shape of the inorganic filler material is not particularly limited, and fragmented, spherical, or flake-shaped materials can be used. Spherical materials are preferred for dispersibility in coatings. The particle size of the inorganic filler material is not particularly limited. For dispersibility, coatability, thermal cycling performance, and other reliability aspects, an average particle size of 3 μm or less and a maximum particle size of 10 μm or less are preferred, more preferably an average particle size of 1 μm or less and a maximum particle size of 6 μm or less, and even more preferably an average particle size of 0.7 μm or less and a maximum particle size of 2 μm or less. Furthermore, the average and maximum particle sizes mentioned here are measured using a Horiba LA500 laser diffraction particle size analyzer. Additionally, to improve reliability, the particle purity is preferably greater than 99%, more preferably greater than 99.8%, and even more preferably greater than 99.9%. If it is less than 99%, soft errors in semiconductor devices are easily generated due to alpha rays emitted from radioactive impurities such as uranium and thorium.

[0072] In addition, (C) the content of inorganic filler is not particularly limited. 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 more preferably 2% to 60% by weight.

[0073] <Organic Solvent> The resin composition of the present invention may further include at least one organic solvent. By including an organic solvent, the resin composition can be made suitable for various molding processes. As an organic solvent, solvents 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. For example, methyl isobutyl ketone, dimethyl acetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclobutane, cyclohexanone, and methyl ethyl ketone can be used. These organic solvents can be used alone or in combination of two or more.

[0074] <Other Components> 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 BYK-Chemie Japan Co., Ltd. ("DISPERBYK" is a registered trademark), the Ajisper series manufactured by Ajinomoto Fine-Techno Co., Ltd. ("Ajisper" is a registered trademark), the HIPLAAD series manufactured by Kusunoki Chemical Co., Ltd. ("HIPLAAD" is a registered trademark), and the Homogenol series manufactured by Kao Corporation ("Homogenol" is a registered trademark). These dispersants can be used alone or in combination of two or more.

[0075] <Sheet Composition> The sheet composition of the present invention refers to a resin composition that is made into a sheet form by sheeting the resin composition of the present invention.

[0076] 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 contained solvent as needed. The sheet composition is formed from the resin composition of the present invention, thereby producing a sheet-cured material with excellent flexibility and heat resistance when the sheet composition is made into a cured material.

[0077] There is no particular limitation on the thickness of the sheet-like composition, and it can be appropriately selected according to the purpose. For example, the thickness can be set to 50 μm to 500 μm, and from the viewpoint of thermal conductivity, electrical insulation and flexibility, 80 μm to 400 μm is preferred.

[0078] The sheet-like 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, forming a coating layer (composition layer), removing at least a portion of the organic solvent from the coating layer, and then drying. Examples of supports include polyethylene terephthalate (PET) films, polyphenylene sulfide films, and polyimide films. 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., to improve adhesion and peelability to the sheet-like composition. From a workability point of view, the thickness of the support is preferably 10 μm to 200 μm.

[0079] The coating of the composition coating can be carried out by known methods. Specifically, it can be carried out by methods such as corner wheel coating, mold coating, lip coating, gravure coating, screen printing, and spraying. As a method for forming a composition layer of a specified thickness, examples include corner wheel coating, in which the object to be coated passes through the gap, and mold coating, in which the flow rate of the composition coating is adjusted by applying it from a nozzle. For example, when the thickness of the coating layer (composition layer) before drying is 50 μm to 500 μm, corner wheel coating or lip coating is preferred.

[0080] There are no particular limitations on the drying method as long as it can remove at least a portion of the organic solvents contained in the coating composition. The drying method can be appropriately selected from commonly used drying methods according to the amount of organic solvents contained in the coating composition. Generally speaking, methods involving heat treatment at around 80°C to 150°C can be cited.

[0081] When the sheet composition (composition layer) of the present invention contains (B) a thermosetting resin, the sheet composition (composition layer) refers to a state in which a partial curing reaction has occurred, even if the self-curing reaction has not yet occurred. Therefore, although the sheet composition in the state in which the curing reaction has not yet occurred is flexible, it lacks sufficient strength as a sheet. Therefore, when the support such as the PET film is removed, the sheet sometimes lacks self-support, making operation difficult.

[0082] Therefore, from the viewpoint of improving operability, the sheet composition is preferably obtained by semi-curing the composition layer constituting it. That is, the sheet composition is preferably a semi-cured composition as a B-order sheet obtained by further heating until the composition layer becomes a semi-cured state (B-order state). By semi-curing the composition layer, a sheet composition with excellent thermal conductivity and electrical insulation, excellent self-support as a B-order sheet, and excellent service life can be obtained.

[0083] The conditions for heat treatment of the sheet composition are not particularly limited as long as they enable the composition layer to reach a B-order state. These conditions can be appropriately selected based on the structure of the composition. To reduce voids (pores) in the composition layer generated during coating, the heat treatment is preferably performed by a method selected from hot vacuum pressing, hot roller lamination, etc. This allows for the efficient and good production of B-order sheets with flat surfaces.

[0084] Specifically, for example, the constituent layer can be partially hardened to the B-stage state by heating and pressurizing at a temperature of 100°C to 200°C for 1 to 3 minutes under reduced pressure (e.g., 1 kPa) and a pressing pressure of 1 MPa to 20 MPa.

[0085] Furthermore, it is preferable to: coat the resin composition onto the support, bond two sheet-like compositions in a dry state, and then perform the aforementioned heating and pressurizing treatment until it is semi-cured to the B-stage state. Ideally, the coated surfaces of the composition layers (the surfaces of the composition layers not in contact with the support) should be bonded together. If the composition layers are bonded together in a bonded manner, both sides of the obtained B-stage sheet-like composition (i.e., the surfaces exposed when the support is peeled off) become flatter, resulting in better adhesion to the bonded material. Heat dissipation components and electronic components manufactured using this sheet-like composition exhibit high thermal conductivity.

[0086] The thickness of the B-type sheet can be appropriately selected according to the purpose. For example, it can be set to 50 μm to 500 μm, but from the point of view of thermal conductivity, electrical insulation and flexibility, 80 μm to 300 μm is preferred. Alternatively, it can be manufactured by hot pressing one side of two or more sheet-like components together.

[0087] From the viewpoint of suppressing the formation of bubbles caused by the generation of escaping gas during the hardening of the constituent layer, the residual rate of volatile components in the B-grade 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. A sample obtained by cutting the B-grade sheet into 40 mm × 40 mm pieces is dried in a constant temperature bath preheated to 190°C for 2 hours, and the solvent residual rate is determined based on the mass change before and after drying.

[0088] <Sheet Hardener> The sheet hardener of the present invention is a substance formed by hardening the resin composition or sheet composition of the present invention, i.e., the hardener of such substances.

[0089] The sheet-cured material can be manufactured by curing an uncured composition, a sheet-like composition, a B-grade composition, or a B-grade sheet-like composition. The curing method can be appropriately selected according to the structure and purpose of the composition, and heating and pressurizing 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. In addition, the heating time is preferably 5 minutes to 5 hours. Regarding the heating temperature, the temperature can be increased in stages, or a certain temperature range can be selected for continuous heating. For example, 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, can be used. Examples of heating devices include ovens, heating plates, and infrared lamps. When the curing temperature exceeds 180°C, curing is preferably carried out in a nitrogen atmosphere or under vacuum.

[0090] Furthermore, the elastic modulus of the sheet-cured material of the present invention at 25°C is preferably 0.1 MPa to 100 MPa, more preferably 0.3 MPa to 50 MPa, and even more preferably 0.5 MPa to 15 MPa. In order to make the elastic modulus of the sheet-cured material of the present invention at 25°C 0.5 MPa to 15 MPa, the following methods can be used, namely, appropriately adjusting the composition of (A) polymer, (B) thermosetting resin, (D) curing agent or curing accelerator, and (C) inorganic filler material, especially controlling the ratio of the siloxane skeleton in (A) polymer.

[0091] The elastic modulus of the sheet-cured material of the present invention at -70°C is preferably 0.01 MPa to 1000 MPa, more preferably 0.1 MPa to 90 MPa, and even more preferably 1 MPa to 85 MPa. In order to make the elastic modulus of the sheet-cured material of the present invention at -70°C 0.01 MPa to 100 MPa, the following methods can be used, namely, appropriately adjusting the composition of (A) polymer, (B) thermosetting resin, (D) curing agent or curing accelerator, and (C) inorganic filler material, especially controlling the ratio of siloxane skeleton in (A) polymer.

[0092] In this invention, the elastic modulus of the sheet-hardened material is set as the value of the stored elastic modulus obtained by dynamic viscoelasticity measurement. The dynamic viscoelasticity measurement is performed according to Japanese Industrial Standards (JIS) K 7244 (1998) in a tensile mode. Examples of dynamic viscoelasticity measuring devices include the DMS6100 manufactured by Seiko Instruments Ltd. or the DVA-200 manufactured by IT Measurement & Control Ltd.

[0093] The glass transition temperature (Tg) of the sheet-cured material of the present invention is preferably below 0°C, more preferably below -20°C, and even more preferably below -50°C. Furthermore, the glass transition temperature (Tg) of the sheet-cured material is preferably above -120°C. To make the glass transition temperature (Tg) of the sheet-cured material above -120°C and below -50°C, methods 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 material, particularly controlling the ratio of the siloxane backbone in the (A) polymer, can be employed.

[0094] <Laminated Body> The laminated body of the present invention is formed by further laminating resin sheets onto the resin composition, sheet composition, or sheet-cured material of the present invention. That is, the laminated body of the present invention is a sheet comprising two or more layers, including an adhesive layer and the resin composition, sheet composition, or sheet-cured material of the present invention. Moreover, the laminated body 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 material of the present invention. Here, the adhesive layer in the laminated body may be directly bonded to the resin composition, sheet composition, or sheet-cured material of the present invention, or a layer such as a metal layer may be present between the resin composition, sheet composition, or sheet-cured material and the adhesive layer.

[0095] There are no particular limitations on the type or raw materials of the adhesive layer. The adhesive layer is preferably at least one selected from the group consisting of epoxy resin, phenolic resin, urethane resin, silicone resin, acrylic resin, polyimide resin and polyamide-imide resin. From the point of view of adhesion, it is more preferably at least one selected from the group consisting of epoxy resin, urethane resin, acrylic resin and polyimide resin.

[0096] There are no particular limitations on the method of manufacturing the laminate, for example, it can be carried out by a method selected from hot vacuum pressing, hot roll lamination, etc.

[0097] <Laminated Member> The laminated member of the present invention is a laminated member having member A, the sheet hardened material of the present invention, and member B in sequence, wherein the coefficients of linear expansion of member A and member B differ by more than 1.

[0098] The types and raw materials of components A and B are not particularly limited as long as the coefficients of linear expansion of components A and B differ by more than 1. For example, alumina, zirconium oxide, aluminum nitride, silicon carbide, silicon nitride, glass, aluminum, copper, and titanium can be used as components A or B. The combination of components A and B is not particularly limited as long as the coefficients of linear expansion of these components differ by more than 1. A combination of ceramic and metal is preferred. More specifically, combinations of components A and B are preferably alumina and aluminum, aluminum nitride and aluminum, alumina and titanium, silicon carbide and aluminum, etc. 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.

[0099] <Wafer Holder> The wafer holder of the present invention includes the laminated member of the present invention. More specifically, the wafer holder of the present invention includes a laminated member comprising the sheet hardener of the present invention between a ceramic Coulomb force-type electrostatic chuck (as member A) which has the function of adsorbing and holding the adsorbed object, and a metal cooling plate (as member B). The wafer holder of the present invention preferably has a temperature regulating function and a 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 hardener of the present invention between them, the thermal stress during thermal cycling can be mitigated, and the bonding state can be maintained well over a long period of time in a wide temperature range. In particular, by providing the sheet hardener of the present invention, the bonding state can be well maintained in a region from low temperatures below 0°C to high temperatures above 200°C.

[0100] <Semiconductor Manufacturing Apparatus> 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 semiconductor wafer or other substrate to be processed is placed on a wafer holder disposed in a processing chamber. A high-frequency voltage is applied to the processing chamber in a vacuum environment to generate plasma, thereby performing a dry etching step on the substrate to be processed. Since the processing accuracy required for the dry etching step is higher, the temperature of the substrate to be processed is adjusted to keep it constant in order to improve the uniformity of the in-plane plasma processing of the substrate to be processed. As described above, by providing the wafer hardener of the present invention, the adhesion state can be maintained well for a long time over a wide temperature range, thereby maintaining the uniformity of the in-plane plasma processing of the substrate to be processed well. [Example]

[0101] Hereinafter, the present invention will be specifically described based on embodiments, but the present invention is not limited thereto. First, the evaluation methods performed in Examples 1 to 17 and Comparative Examples 1 to 2 will be described.

[0102] <Preparation of Evaluation Samples> The sheet composition prepared in the examples and comparative examples described later was cut into 50 mm squares. One of the protective films of the adhesive sheet having an adhesive layer of 50 μm thickness was then peeled off. The adhesive layers were laminated together at 120°C and 0.4 MPa. The operation was repeated to form an adhesive layer with a thickness of 200 μm. The layer was then heat-cured at 180°C for 6 hours to obtain the cured sheet sample for evaluation.

[0103] (1)25℃ modulus of elasticity The sample obtained by cutting the evaluation sheet hardening sample into 5 mm × 20 mm is used as the 25℃ modulus of elasticity evaluation sheet hardening sample.

[0104] The elastic modulus of the sample used for evaluating the elastic modulus at 25°C was determined using a dynamic viscoelasticity measuring apparatus DMS6100 manufactured by Seiko Instruments (Co., Ltd.). The measurement conditions were as follows: a heating rate of 5°C / min and a measurement frequency of 1 Hz were used. The stored elastic modulus at each temperature was measured within the range of -130°C to 300°C, and the stored elastic modulus at 25°C was taken as the elastic modulus at 25°C.

[0105] (2) Glass transition temperature (Tg) The glass transition temperature (Tg) was determined by dynamic viscoelasticity measurement using samples obtained by cutting the evaluation sheet hardened sample into 5 mm × 20 mm pieces. The apparatus used was a dynamic viscoelasticity measuring device DMS6100 manufactured by Seiko Instruments, set to temperature: -70℃~300℃, heating rate: 5℃ / min, tensile mode, and frequency: 1 Hz. The temperature of the peak value of tanδ of the obtained curve was taken as Tg.

[0106] (3)Shear strain The sheet-like components described later are cut into 10 mm × 10 mm pieces. After peeling off the PET film on one side, they are attached to an aluminum plate with a length of 50 mm × width of 15 mm × thickness of 0.5 mm. Then, the PET film on the other side is peeled off and attached to another aluminum plate in a staggered manner to make a test piece for shear test.

[0107] After heat hardening the test specimens for shear testing at 180°C for 6 hours, tensile tests were performed using a Techno Graph TG-1kN tensile-compression testing machine manufactured by Minebea Mitsumi Co., Ltd., and the displacement at the fracture point was measured. The load cell was set to 1 kN and the tensile speed was 5 mm / min. The displacement at the fracture point was removed and the value obtained by dividing the thickness of the sheet composition was used as the shear strain.

[0108] (4)Heat resistance Regarding the test pieces obtained by the above method for shear testing, which are heat-hardened at 180°C for 6 hours and further heat-hardened at 250°C under vacuum for 1000 hours, tensile tests were conducted using a Techno Graph TG-1kN tensile-compression testing machine manufactured by Minebea Mitsumi Co., Ltd., and the shear strain was calculated. The force gauge was set at 1 kN and the tensile speed was 5 mm / min. The shear strain after heat-hardening at 180°C for 6 hours and the shear strain after heating at 250°C under vacuum for 1000 hours were defined as "good" if the rate of change was less than 30%, and the rate of change was defined as "poor" if it was more than 30%.

[0109] (5) The amide ratio of the synthesized polymer (A) First, the infrared absorption spectrum of polymer (A) was measured to confirm the presence of absorption peaks (around 1780 cm⁻¹ and 1377 cm⁻¹) caused by the amide structure of polyamide. Next, the infrared absorption spectrum of polymer (A) was measured again after heat treatment at 350°C for 1 hour, and the peak intensity around 1377 cm⁻¹ before and after heat treatment was compared. The amide ratio of polymer (A) after heat treatment was set to 100%, and the amide ratio of polymer (A) before heat treatment was calculated.

[0110] (6) Glass transition temperature (Tg) of the synthesized polymer (A) After removing the solvent from the polymer (A), differential scanning calorimetry (DSC) was performed to determine the glass transition temperature (Tg). A differential scanning calorimetry apparatus (DSC6200) manufactured by Seiko Instruments Co., Ltd. was used, with the temperature set to -150℃ to 300℃ and the heating rate set to 10℃ / min. The onset temperature of the obtained DSC curve was taken as the Tg of the polymer (A).

[0111] (7)The weight average molecular weight of the synthesized (A) polymer was determined by dissolving the (A) polymer obtained by the method described in each example and comparative example in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to obtain a polyimide concentration of 0.1% by weight. The determination was performed using a Waters 2690 GPC apparatus (manufactured by Waters) with the structure shown below, and the weight average molecular weight converted from polystyrene was calculated.

[0112] The GPC determination conditions were as follows: the moving layer was set to NMP prepared by dissolving LiCl and phosphoric acid at a concentration of 0.05 mol / L, and the developing speed was set to 0.4 ml / min. Detector: Waters 996; System controller: Waters 2690; Column oven: Waters HTR-B; Thermal controller: Waters TCM; Column: TOSOH guard column (set to prevent column blockage by replenishing coarse particles mixed in with the analyte); Column: TOSOH TSK-GEL α-4000 (exclusion limit molecular weight of 1,000,000); Column: TOSOH TSK-GEL α-2500 (exclusion limit molecular weight of 10,000). The above three columns were connected in series.

[0113] Furthermore, the following details the raw materials represented by abbreviations in each embodiment.

[0114] <Resin> ·Selected from polyimide and polyamide (A) polymer <(A) polymer raw materials> X-22-168AS: (manufactured by Shin-Etsu Chemical Co., Ltd.) (Average molecular weight 1000: two-terminal anhydride modified polysiloxane of general formula (2): n=9) (R7~R10 are methyl) X-22-168A: (manufactured by Shin-Etsu Chemical Co., Ltd.) (Average molecular weight 2000: two-terminal anhydride modified polysiloxane of general formula (2): n=19) (R7~R10 are methyl) ODPA: 4,4'-oxyphthalic anhydride (manufactured by Manac Co., Ltd.) BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (manufactured by Mitsubishi Chemical Co., Ltd.) KF8010: Diaminopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) (Average molecular weight 860: Diaminopolysiloxane of general formula (1): m=9) (R1-R4 are methyl, R5 and R6 are trimethylene) X-22-161A: Diaminopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) (Average molecular weight 1600: Diaminopolysiloxane of general formula (1): m=19) (R1-R4 are methyl, R5 and R6 are trimethylene) BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoroisopropylidene (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0115] <(A) Polymer Synthesis> · Polymer A (A) was prepared by setting up a stirrer, thermometer, nitrogen inlet tube, and dropping funnel in a 500 ml four-necked flask. 47.27 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were added under nitrogen atmosphere and stirred at 60°C to dissolve. Then, while stirring at 120°C, 3.66 g of BAHF and 77.40 g of KF8010 were added and stirred 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 (solid content concentration of 80.0% by weight). The weight-average molecular weight of polymer A (A) was determined to be 45,600, and the amide content was determined to be 99%.

[0116] · (A) Polymer B was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 102.24 g of dimethylacetamide, 98.00 g of X-22-168AS, and 7.45 g of ODPA were added under nitrogen atmosphere and stirred at 60°C to dissolve. Subsequently, 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 (A) Polymer B (solid concentration 60.0% by weight). The weight-average molecular weight of (A) Polymer B was determined to be 57,320, and the acetylation rate was determined to be 99%.

[0117] · (A) Polymer C was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 113.92 g of dimethylacetamide, 77.25 g of X-22-168AS, and 23.27 g of ODPA were added under nitrogen atmosphere and stirred at 60°C to dissolve. Subsequently, 5.49 g of BAHF and 112.05 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 (A) polymer C (solid concentration 60.0% by weight). The weight-average molecular weight of (A) polymer C was determined to be 69,750, and the acetylation rate was determined to be 99%.

[0118] · (A) Polymer D was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 92.93 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were added under nitrogen atmosphere and stirred at 60°C to dissolve. Subsequently, 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 (A) Polymer D (solid content concentration 80.0% by weight). The weight-average molecular weight of (A) Polymer D was determined to be 60,350, and the amide content was determined to be 99%.

[0119] · (A) Polymer E was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 132.70 g of triethylene glycol dimethyl ether and 121.00 g of X-22-168A were added under nitrogen atmosphere and stirred at 60°C to dissolve. Subsequently, 2.01 g of BAHF and 76.23 g of X-22-161A 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 (A) Polymer E (solid content concentration 60.0% by weight). The weight-average molecular weight of (A) Polymer E was determined to be 48,020, and the amide content was determined to be 99%.

[0120] · (A) Polymer F was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 39.86 g of triethylene glycol dimethyl ether and 108.00 g of X-22-168AS were added under nitrogen atmosphere and stirred at 60°C to dissolve. Then, while stirring at 120°C, 25.64 g of BAHF and 25.80 g of KF8010 were added and stirred for 1 hour. The temperature was then raised to 200°C and stirred for 3 hours, followed by cooling to room temperature to obtain (A) polymer F (solid content concentration of 80.0% by weight). The weight-average molecular weight of (A) polymer F was determined to be 55,680, and the amide content was determined to be 99%.

[0121] · (A) Polymer G was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. Under 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 stirred at 60 °C to dissolve. Then, while stirring at 120 °C, 3.66 g of BAHF and 77.40 g of KF8010 were added and stirred for 1 hour. The temperature was then raised to 200 °C and stirred for 3 hours, followed by cooling to room temperature to obtain (A) Polymer G (solid content concentration of 80.0% by weight). The weight-average molecular weight of (A) Polymer G was determined to be 59,790, and the amide content was determined to be 99%.

[0122] · (A) Polymer H was prepared in a 300 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 88.39 g of triethylene glycol dimethyl ether and 14.56 g of BPDA were added under nitrogen atmosphere and stirred at 60°C to dissolve. Subsequently, while stirring at 120°C, 1.83 g of BAHF and 72.00 g of X-22-161A were added and stirred for 1 hour. The temperature was then raised to 200°C and stirred for 3 hours, followed by cooling to room temperature to obtain (A) polymer H (solid content concentration of 50.0% by weight). The weight-average molecular weight of (A) polymer H was determined to be 45,300, and the amide content was determined to be 99%.

[0123] · (A) Polymer I was prepared in a 500 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and dropping funnel. 77.13 g of triethylene glycol dimethyl ether and 86.40 g of X-22-168AS were added under nitrogen atmosphere and stirred at 60°C to dissolve. 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 (A) Polymer I (solid content concentration 80.0% by weight). The weight-average molecular weight of (A) Polymer I was determined to be 74,270, and the amide content was determined to be 99%.

[0124] The monomer composition and properties of the synthesized (A) polymer are shown in Tables 1 and 2.

[0125] · Acrylic rubber: Epoxy-containing acrylic rubber with a weight average molecular weight of 850,000, Tg-32℃, monomer copolymerization ratio of ethyl acrylate: butyl acrylate: glycidyl acrylate = 65:35:1, and functional group (epoxy group) content of 0.09 equivalents / kg.

[0126] ·Aromatic Polyimide <Synthesis of Aromatic Polyimide> 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 allowing water and xylene to azeotropically combine. After stirring, the solution was added to 3 L of water to obtain a white precipitate of polymer. The precipitate was filtered and recovered, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours. The infrared absorption spectrum of the obtained polymer solid was measured, and absorption peaks originating from the polyimide structure were detected near 1780 cm⁻¹ and 1377 cm⁻¹. Thus, an aromatic polyimide with functional groups capable of reacting with epoxy groups was obtained.

[0127] · (B) Thermosetting resin jER1032H60: Tris(hydroxyphenyl)methane type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd.) HP4700: Naphthalene type multifunctional epoxy resin (manufactured by DIC Co., Ltd.).

[0128] · (C) Inorganic filler material AA-3: High-purity alumina (average particle size: 3 μm) (manufactured by Sumitomo Chemical Co., Ltd.) AA-04: High-purity alumina (average particle size: 0.4 μm) (manufactured by Sumitomo Chemical Co., Ltd.) SO-E1: High-purity synthetic spherical silicon dioxide (average particle size: 0.3 μm) (manufactured by Admatechs Co., Ltd.).

[0129] ·(D) Hardener or hardening accelerator SEIKACURE-S: 4,4-diaminodiphenyl sulfone (manufactured by Wakayama Seika Kogyo Co., Ltd.) C17Z: 2-heptadecylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

[0130] <Examples 1 to 17, Comparative Examples 1 to 4> Examples 1 to 17 and Comparative Examples 1 to 4 were formulated according to the compositions shown in Tables 3 to 5, and triethylene glycol dimethyl ether was added. The mixture was stirred at 1800 rpm for 10 minutes using a rotary mixer (manufactured by Thinky Corporation) to prepare a composition solution.

[0131] The composition solution was coated with a silicone release agent onto a 38 μm thick polyethylene terephthalate film (RF2·PETcs000 manufactured by Aim Ltd.) using a rod coater to achieve a dry thickness of 50 μm (hereinafter referred to as the composition coating). The film was dried at 120°C for 30 minutes, and a protective film was then laminated at 120°C and 0.4 MPa to produce a sheet composition. Various evaluations were then performed, and the results are shown in Tables 3 to 5.

[0132] [Table 1] [Table 1] project Polymer A Polymer B Polymer C Polymer D Polymer E Tetracarboxylic acid dianhydride (Moll%) X-22-168AS 100 80 50 100 - X-22-168A - - - - 100 ODPA - 20 50 - - BPDA - - - - - diamine (Moll%) KF8010 90 90 90 60 - X-22-161A - - - - 90 BAHF 10 10 10 40 10 characteristic Acrylimide content (%) 99 99 99 99 99 Tg (°C) -95 -75 -36 -65 -120 Weight average molecular weight 45600 57320 69750 60350 48020

[0133] [Table 2] [Table 2] project Polymer F Polymer G Polymer H Polymer I Tetracarboxylic acid dianhydride (Moll%) X-22-168AS 100 30 - 100 X-22-168A - - - - ODPA - 70 - - BPDA - - 100 - diamine (Moll%) KF8010 30 90 - - X-22-161A - - 90 - BAHF 70 10 10 100 characteristic Acrylimide content (%) 99 99 99 99 Tg (°C) -51 -48 -30 -30 Weight average molecular weight 55680 59790 45300 74270

[0134] [Table 3] [Table 3] project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 thermoplastic resin (Conversion of solid components) (g) Polymer A 8.08 8.08 - - - - 8.08 Polymer B - - 8.08 - - - - Polymer C - - - 8.08 - - - Polymer D - - - - 8.08 - - Polymer E - - - - - 8.08 - Polymer F - - - - - - - Polymer G - - - - - - - Polymer H - - - - - - - Polymer I - - - - - - - acrylic rubber - - - - - - - Aromatic polyimide - - - - - - - Thermosetting resins (g) jER1032H60 - - - - - - 0.91 HP4700 0.9 0.9 0.9 0.9 0.9 0.9 - Inorganic filler materials (g) AA-3 - 22.4 22.4 22.4 22.4 22.4 22.4 AA-04 - 2.8 2.8 2.8 2.8 2.8 2.8 SO-E1 - - - - - - - hardener (g) SEIKACURE-S 0.34 0.34 0.34 0.34 0.34 0.34 0.33 C17Z - - - - - - - Evaluation results Elastic modulus (MPa) 3.7 11 14 35 36 6.4 11 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

[0135] [Table 4] [Table 4] project Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 thermoplastic resin (Conversion of solid components) (g) Polymer A 8.08 8.08 8.08 8.08 8.08 8.08 - Polymer B - - - - - - - Polymer C - - - - - - - Polymer D - - - - - - 8.08 Polymer E - - - - - - - Polymer F - - - - - - - Polymer G - - - - - - - Polymer H - - - - - - - Polymer I - - - - - - - acrylic rubber - - - - - - - Aromatic polyimide - - - - - - - thermosetting resins (g) jER1032H60 0.91 0.91 1.24 1.24 1.24 1.24 1.24 HP4700 - - - - - - Inorganic filler materials (g) AA-3 11.9 4.9 22.4 11.9 4.9 - - AA-04 1.49 0.61 2.8 1.49 0.61 - - SO-E1 - - - - - 3.08 3.08 hardener (g) SEIKACURE-S 0.33 0.33 - - - - - C17Z - - 0.062 0.062 0.062 0.036 0.036 Evaluation results Elastic modulus (MPa) 4.3 1.6 43 twenty three 11 6.6 36 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

[0136] [Table 5] [Table 5] project Example 15 Example 16 Example 17 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 thermoplastic resin (Conversion of solid components) (g) Polymer A 8.08 - - - - - - Polymer B - - - - - - - Polymer C - - - - - - - Polymer D - - - - - - - Polymer E - - - - - - - Polymer F - 8.08 - - - - - Polymer G - - 8.08 - - - - Polymer H - - - - - 8.08 - Polymer I - - - - - - 8.08 acrylic rubber - - - 8.08 - - - Aromatic polyimide - - - - 8.08 - - thermosetting resins (g) jER1032H60 1.24 - - - - - - HP4700 - 0.9 0.9 0.9 0.9 0.9 0.9 Inorganic filler materials (g) AA-3 - - - - - - - AA-04 - - - - - - - SO-E1 - - - - - - - hardener (g) SEIKACURE-S - 0.34 0.34 0.34 0.34 0.34 0.34 C17Z 0.036 - - - - - - Evaluation results Elastic modulus (MPa) 0.7 64 72 3.3 4500 110 120 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 bad good good good

[0137] According to Tables 3 to 5, the (A) polymers A to G, which contain polysiloxane backbones in both diamine residues and anhydride residues, used in Examples 1 to 17, all have an elastic modulus of less than 100 MPa and a shear strain of 1.5 or more, thus providing sheets with sufficient flexibility, adhesion to the substrate, and conformability. In addition, they have "good" heat resistance, thus providing sheets that can maintain the bonded state well for a long time. In particular, the (A) polymers A to E, which contain more than 60 mol% of diamine residues (1) in all diamine residues and more than 50 mol% of anhydride residues (2) in all anhydride residues, used in Examples 1 to 15, tend to have lower elastic modulus and higher shear strain. By containing a large amount of siloxane backbone, the flexibility, adhesion to the substrate, and conformability can be further improved.

[0138] On the other hand, according to Table 5, Comparative Example 1, which uses acrylic rubber as a thermoplastic resin, has "poor" heat resistance, and its shear strain decreased significantly after being heated at 250°C for 1000 hours from an initial value of 4.12. Furthermore, Comparative Example 2, which uses aromatic polyimide as a thermoplastic resin, has "good" heat resistance, but its elastic modulus is very high at 4500 MPa, and its shear strain is very small, less than 0.5. Therefore, its flexibility, adhesion to the substrate, and conformability are insufficient. Regarding Comparative Example 3, which uses (A) polymer H containing a polysiloxane structure only in diamine residues as a thermoplastic resin, and Comparative Example 4, which uses (A) polymer I containing a polysiloxane structure only in anhydride residues, compared to Comparative Example 2, their elastic modulus decreased, and their shear strain increased. However, the elastic modulus is still as high as 110 MPa (Comparative Example 3) and 120 MPa (Comparative Example 4), and the shear strain is less than 1.5, indicating insufficient flexibility, adhesion to the bonded body, and followability. [Simplified Explanation of the Diagram]

[0020] None

Claims

1. A resin composition for a wafer holder, comprising a polymer (A) selected from polyimide and polyamide having residues of a diamine of general formula (1) (hereinafter referred to as diamine residue (1)) and residues of an anhydride of general formula (2) (hereinafter referred to as anhydride residue (2)), and a thermosetting resin (B), wherein the thermosetting resin (B) is an epoxy resin, and the epoxy resin is 0.1 parts by weight or more and 15 parts by weight or less relative to 100 parts by weight of the polymer (A), and the glass transition temperature (Tg) of the wafer hardened form of the resin composition for a wafer holder is -120°C or more and 0°C or less.

1. In general formula (1), R1 to R4 may be the same or different, representing alkyl, phenyl, or phenoxy groups having 1 to 30 carbon atoms; wherein, Phenyl and phenoxy groups can also be substituted with alkyl groups having 1 to 30 carbon atoms; m R1 and R3 can be the same or different; in general formula (1), R5 and R6 can be the same or different, representing alkyl or aryl groups having 1 to 30 carbon atoms; wherein, aryl groups can also be substituted with alkyl groups having 1 to 30 carbon atoms; in general formula (1), m is an integer selected from 1 to 100; 1. In general formula (2), R7 to R10 may be the same or different, representing alkyl, phenyl or phenoxy with 1 to 30 carbon atoms; wherein phenyl and phenoxy may also be substituted by alkyl with 1 to 30 carbon atoms; n R7 and R9 may be the same or different; in general formula (2), R11 and R12 may be the same or different, representing alkyl or aryl with 1 to 30 carbon atoms; wherein aryl may also be substituted 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 for a wafer holder as described in claim 1, wherein, When the total of all diamine residues and all anhydride residues in the polymer (A) is set to 100 mol%, the total of diamine residues (1) and anhydride residues (2) is more than 55 mol% and less than 100 mol%.

3. The resin composition for a wafer holder as described in claim 1 or claim 2, wherein, When all diamine residues in the polymer (A) are set to 100 mol%, it contains more than 60 mol% and less than 100 mol% of diamine residues (1).

4. The resin composition for a wafer holder as described in claim 1 or claim 2, wherein, When all anhydride residues in the polymer (A) are set to 100 mol%, it contains anhydride residues (2) of more than 50 mol% and less than 100 mol%.

5. The resin composition for a wafer holder as described in claim 1 or claim 2, 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 for a wafer holder as described in claim 1 or claim 2, wherein, The glass transition temperature (Tg) of the polymer (A) is above -150°C and below -30°C.

7. The resin composition for a wafer holder as described in claim 1 or claim 2, wherein, It includes at least one selected from the group consisting of polyimide resins, bismaleimide resins, phenolic resins, carbamate resins, silicone resins, acrylic resins, and polyamide-imide resins.

8. The resin composition for a wafer holder as described in claim 1 or claim 2, wherein, The epoxy resin is selected from at least one group consisting of epoxy resins containing an aromatic backbone, epoxy resins containing acyclic carbon compounds, epoxy resins containing a silicate backbone, and crystalline epoxy resins.

9. The wafer holder resin composition as described in claim 1 or claim 2, comprising (C) an inorganic filler material.

10. The wafer holder resin composition as described in claim 1 or claim 2, comprising (D) a hardener or a hardening accelerator.

11. A sheet-like composition formed by sheeting a wafer holder as described in any one of claims 1 to 10 using a resin composition.

12. A sheet-cured material, formed by curing a wafer holder resin composition as described in any one of claims 1 to 10 or a sheet composition as described in claim 11.

13. A laminate is formed by further laminating resin sheets onto a wafer holder resin composition as described in any one of claims 1 to 10, a sheet composition as described in claim 11, or a sheet hardener as described in claim 12.

14. A laminated member having, in sequence, a member A, a sheet hardener as described in claim 12, and a member B, wherein the coefficients of linear expansion of member A and member B differ by more than 1.

15. A wafer holder comprising the stacking member as described in claim 14.

16. A semiconductor manufacturing apparatus comprising a wafer holder as described in claim 15.