WO2005123809A1

WO2005123809A1 - Heat-resistant resin, method for production thereof and base plate for dust removal of substrate treating device using the resin

Info

Publication number: WO2005123809A1
Application number: PCT/JP2005/011457
Authority: WO
Inventors: Hirofumi Fujii; Daisuke Uenda; Nobuaki Maruoka; Yoshio Terada; Hitoshi Ishizaka; Makoto Namikawa
Original assignee: Nitto Denko Corporation
Priority date: 2004-06-22
Filing date: 2005-06-22
Publication date: 2005-12-29
Also published as: TW200613370A

Abstract

A heat-resistant resin which is obtained by reacting a tetra-carboxylic acid anhydride, an aliphatic diamine and an elastomer having two or more carboxyl groups; a method for producing the heat-resistant resin; and a base plate for the dust removal of a substrate treating device which uses said heat-resistant resin. The heat-resistant resin can be used, in particular, as a tool for dust removal, even in a situation wherein the contamination of a silicone may cause a serious trouble, such as in HDD use or in a part of semiconductor use.

Description

Heat-resistant resin, method for producing the same, and substrate for dust removal in a substrate processing apparatus using the resin

Technical field

The present invention relates to a heat-resistant dust-removing resin, particularly to a secondary diamine conjugate containing a butadiene-acrylonitrile copolymer structure and a heat-resistant resin capable of obtaining a tetracarboxylic anhydride. Furthermore, the present invention relates to a substrate for dust removal of a substrate processing apparatus such as a semiconductor device obtained by using these resins.

Background art

[0002] Low-elasticity polyimide is used as a low-stress and heat-resistant material for protective films for semiconductors, insulating films for multilayer circuit boards, adhesive films for semiconductors, and coverlays for flexible circuit boards (Patent Document 1). , 2, 3, 4, 5).

However, since these low-modulus polyimides are obtained by copolymerizing diamine or tetracarboxylic anhydride containing silicone, they are seriously affected by silicone contamination such as HDD applications and some semiconductor applications. It could not be used in applications where serious obstacles occur.

[0003] As described above, in HDDs and semiconductor manufacturing equipment, etc., it can be used without causing contamination.

Therefore, a heat-resistant resin having low elasticity has been demanded.

In addition, there is a substrate for dust removal for dust removal in the apparatus, which has a sheet made of a synthetic resin such as acrylic resin on a silicon wafer (see Patent Documents 6 and 7), but heat resistance is particularly required. For a pre-treatment step or the like, the heat resistance is not sufficiently high, and a dust removal substrate excellent in heat resistance has been demanded.

In particular, wafers for dust removal in the first half of semiconductor processing equipment, especially PVD equipment, are often used at high temperatures, and are required to have heat resistance in the temperature range where dust is removed from these equipment and to have stable physical properties. Te ru.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-170901

Patent Document 2: JP-A-6-73178 Patent Document 3: JP-A-6-207024

Patent Document 4: JP-A-6-73178

Patent Document 5: JP-A-2002-50854

Patent Document 6: JP 2001-351960 A

Patent Document 7: JP-A-2002-18377

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention provides a heat-resistant resin that can be used even in a situation where serious contamination may occur due to silicone contamination, such as HDD use and some semiconductor use, and in particular, can be used for dust removal. A method and a substrate for dust removal using the heat-resistant resin are provided.

Means for solving the problem

[0006] The above-mentioned problem has been achieved by the following configurations.

(1) A heat-resistant resin obtained by reacting tetracarboxylic anhydride, aliphatic diamine, and an elastomer having two or more carboxyl groups.

(2) The heat-resistant resin according to the above (1), wherein the elastomer having two or more carboxyl groups is a dicarboxylic acid elastomer.

(3) The heat-resistant resin according to the above (2), wherein the dicarboxylic acid elastomer is a terminal dicarboxylic acid elastomer containing hydrogenated polybutadiene.

(4) Heat resistance obtained by heat-treating the heat-resistant resin described in any of (1) to (3) above on a substrate (for example, by forming it on a substrate by coating or laminating). Sexual fat.

[0007] (5) An elastomer having two or more carboxyl groups and an excess of an aliphatic diamine in a dehydration amount of the elastomer having two or more carboxyl groups are subjected to a dehydration condensation reaction. A method for producing a heat-resistant resin, comprising reacting a product obtained by the above with a tetracarboxylic dianhydride.

[0008] (6) A dust removal substrate of a substrate processing apparatus having a substrate and a cleaning layer containing the heat-resistant resin according to any one of (1) to (4) on at least one surface of the substrate. .

(7) The method for removing dust from the dust-removing substrate according to (6), by bringing the resin surface of the dust-removing substrate into contact with the surface of the substrate processing apparatus. The invention's effect

[0009] The heat-resistant resin of the present invention is used as a high heat-resistant, low-stress, low-modulus polyimide resin in applications in which serious contamination occurs due to silicone contamination, for example, HDD applications and semiconductor applications. be able to.

The heat-resistant resin of the present invention is particularly useful as a cleaning layer used for a substrate for dust removal in a substrate processing apparatus such as a semiconductor device. O It is now possible to manufacture dust removal wafers that can be used in

Further, the dust removing substrate of the substrate processing apparatus of the present invention is effective for cleaning the inside of a semiconductor device, particularly, a semiconductor device in which a high vacuum is generated, and without reducing the degree of vacuum inside the semiconductor device or more. By quickly recovering the degree of vacuum, cleaning can be performed efficiently and in a short time.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The heat-resistant resin of the present invention is a heat-resistant resin obtained by reacting three components of an elastomer having two or more carboxyl groups, an aliphatic diamine, and a tetracarboxylic anhydride. Here, the heat-resistant resin is intended to include not only an imide resin having an imide bond formed but also a polyamic acid which is a precursor of the imide resin and is imidized.

[0011] More specifically, as the heat-resistant resin of the present invention, a tetracarboxylic anhydride, a stoichiometric excess amount of an aliphatic diamine with respect to the tetracarboxylic anhydride, and a carboxyl group are used. Heat-resistant resin (hereinafter also referred to as heat-resistant resin (A)) obtained by reacting an elastomer having two or more carboxyl groups and an elastomer having two or more carboxyl groups. Heat-resistant resin obtained by reacting a stoichiometric excess amount of an aliphatic diamine with a tetracarboxylic anhydride (hereinafter, also referred to as a heat-resistant resin (B)) Can be mentioned.

[0012] In the heat-resistant resins (A) and (B), the elastomer having two or more carboxyl groups is particularly preferably a dicarboxylic acid elastomer.

As a method for producing the heat-resistant resin (B), a dicarboxylic acid elastomer and an aliphatic diamine in a stoichiometrically excessive amount with respect to the dicarbonic acid elastomer are subjected to a dehydration condensation reaction. The reaction is preferably carried out by reacting the resulting product with tetracarboxylic dianhydride.

Next, each component will be described.

(Elastomer having two or more carboxyl groups)

The elastomer used in the present invention is an elastomer having a plurality of carboxyl groups and two or more carboxyl groups introduced into its skeleton.

The elastomer is not particularly limited, but a polymer having a glass transition point (Tg) of room temperature or lower is preferable. For example, polybutadiene, polybutadiene copolymer represented by polybutadiene-acrylonitrile copolymer, And carboxyl group-modified resins of all of these hydrogenated products, homopolymers or copolymers of atarilic acid or methacrylic acid, and the like. Among them, it is particularly desirable to use hydrogenated polybutadiene having high heat resistance.

An elastomer having two or more carboxyl groups can be synthesized by introducing a carbonyl group into the elastomer by a known method. The carboxyl group can be introduced into the elastomer by, for example, introducing it by copolymerizing a monomer containing a carboxyl group or partially decomposing a double bond obtained by copolymerizing isoprene or butadiene. Can be introduced. In addition, by using a specific catalyst, it can be introduced into both ends of the polymer as a carbonate.

It should be noted that a commercially available elastomer having two or more carboxyl groups may be used.

Elastomers having two or more carboxyl groups preferably have two carboxyl groups.

The weight average molecular weight of the elastomer having two or more carboxyl groups is generally 100 to: L00000, preferably <500 to 2,000.

[Aliphatic diamine]

Examples of the aliphatic diamine include ethylenediamine, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 4,9-dioxa-1,12-diaminododecane, and 1,3. Bis (3-aminopropinole) 1,1,3,3-tetramethynoledisiloxane. The preferred aliphatic diamine is 1,12-diaminododecane is there.

The molecular weight of the aliphatic diamine is usually from 50 to: LOOO, preferably from 100 to 300.

[Aromatic diamine]

In addition, aromatic diamine can be used together with aliphatic diamine.

Examples of the aromatic diamine include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4, 4 'diaminodiphenylpropane, 3, 3'-diaminodiphenylpropane, 4, 4' diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4, 4 'diaminodiphenyl sulfide, 3, 3' —Diaminodiphenyl sulfide, 4,4 'diaminodiphenyl sulfone, 3, 3'-Diaminodiphenyl sulfone, 1,4 bis (4 aminophenoxy) benzene, 1,3 bis (4 aminophenoxy) benzene, 1,3 bis (3 Examples thereof include (aminophenoxy) benzene, 1,3 bis (4aminophenoxy) 2,2 dimethylpropane, and 4,4 ′ diaminobenzophenone.

The amount of the aromatic diamine to be added is generally 0 to 90% by mass, preferably 60 to 80% by mass, based on the aliphatic diamine.

[Tetracarboxylic anhydride]

Examples of the tetracarboxylic anhydride include 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, 2, 2', 3, 3'-biphenyltetracarboxylic dianhydride, 3 , 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride, 2, 2', 3, 3'-benzophenone tetracarboxylic dianhydride, 4, 4'-oxydiphthalic dianhydride, 2,2 bis (2,3 dicarboxyphenyl) hexafluoropropane dianhydride, 2,2 bis (3,4 dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) , Bis (2,3 dicarboxyphenyl) methane dianhydride, bis (3,4 dicarboxyphenyl) methane dianhydride, bis (2,3 dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, pyromellitic dianhydride, ethylene glycol bistrimellitic dianhydride, etc. And these may be used alone or in combination of two or more.

Preferred tetracarboxylic anhydrides are 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2 bis (3,4 dicarboxy Phenol) hexafluoropropane dianhydride (6FDA).

The heat-resistant resin (A) comprises a tetracarboxylic anhydride, a stoichiometrically excess amount of an aliphatic diamine with respect to the tetracarboxylic anhydride, and an elastomer having two or more carboxyl groups. Obtain by reacting.

The amount of the aliphatic diamine to be added is a stoichiometric excess with respect to the tetracarboxylic anhydride, and is generally 1 to 5 times, preferably 2 to 4 times the stoichiometric amount. It is.

The amount of the elastomer having two or more carboxyl groups is generally 0.1 to 10 mol, preferably 0.2 to 0.5 mol, per 1 mol of the tetracarboxylic anhydride.

[0020] Examples of the solvent include N-methyl-2-pyrrolidone, N, N dimethylacetamide, N

, N-dimethylformamide and the like, with N-methyl 2-pyrrolidone being preferred.

[0021] The solute concentration in the reaction solution is generally 5 to 50% by mass, and the reaction temperature is generally room temperature.

(Eg 23 ° C.) to 220 ° C., the reaction time is generally 1 to: L0 hours, preferably 3 to 6 hours.

[0022] The heat-resistant resin (B) is composed of an elastomer having two or more carboxyl groups (particularly, an elastomer of dicarbonate), a stoichiometric excess of an aliphatic diamine, and a tetracarboxylic anhydride. And obtained by reacting

[0023] The amount of the aliphatic diamine added is stoichiometrically excess with respect to the elastomer having two or more carboxyl groups, and is generally 1 to 5 times the stoichiometric amount, preferably 2 to 5 times. 4 times.

The amount of the tetracarboxylic anhydride to be added is generally 0.1 to 10 mol, preferably 2 to 5 mol, per 1 mol of the elastomer having two or more carboxyl groups.

[0024] The reaction conditions and the like are the same as in the case of the heat-resistant resin (A).

[0025] The method for producing the heat-resistant resin (B) includes an elastomer having two or more carboxyl groups and an elastomer having two or more carboxyl groups in a stoichiometric excess. A method of reacting a product obtained by subjecting an amount of an aliphatic diamine to a dehydration condensation reaction with a tetracarboxylic dianhydride is preferred.

[0026] An elastomer having two or more carboxyl groups and a stoichiometric excess of an aliphatic diamine can be subjected to a dehydration reaction in a suitable organic solvent with or without a catalyst. it can. However, in production, an azeotropic dehydration method that does not require isolation of the product is desirable. However, in the azeotropic dehydration method, it is common to use a basic catalyst or the like.However, in the method of the present invention, an excess of an aliphatic diamine having a higher basicity than an aromatic diamine is used. This serves as a catalyst, and the reaction can be easily completed without using any other catalyst.

Here, the solvent used as the organic solvent is a solvent having a high boiling point such as N, N-dimethylacetamide ゃ, N-methyl-2-pyrrolidone, N, N-dimethylformamide and water such as toluene ゃ xylene. Boiling solvents can be used in combination. The reaction temperature is about 150 ° C. to 200 ° C. and can be appropriately determined by adjusting the ratio of the amount of the high boiling solvent to the amount of the azeotropic solvent.

[0027] Next, the product obtained by subjecting the above-mentioned elastomer having two or more carboxyl groups to a stoichiometrically excess amount of an aliphatic diamine to undergo a dehydration condensation reaction is combined with a tetracarboxylic dianhydride. Is reacted.

[0028] After the reaction product is recovered, it may be added to a predetermined solvent and added with tetracarboxylic dianhydride, or tetracarboxylic dianhydride may be added directly to the reaction solution containing the reaction product. Give me some calories.

The reaction conditions are the same as in the case of performing the reaction by simultaneously adding the three components in the heat-resistant resins (A) and (B).

[0029] Examples of the solvent used as the reaction solvent include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N-dimethylformamide. For adjustment, a non-polar solvent such as toluene or xylene can be appropriately mixed and used.

[0030] The heat-resistant resin obtained by the above method can be further heat-treated at a high temperature, preferably in an inert atmosphere, to further improve heat resistance. The heat treatment conditions are the same as the heat treatment conditions in the production of the dust removal substrate of the substrate processing apparatus described later.

[Manufacture of Substrate for Dust Removal of Substrate Processing Apparatus]

The dust-removing substrate of the substrate processing apparatus of the present invention can be obtained by applying the above-mentioned heat-resistant resin on the substrate, removing the solvent by drying, preferably heat-treating at a high temperature. The cleaning layer containing the heat-resistant resin of the present invention may contain other resins, additives and the like in addition to the heat-resistant resin of the present invention. It is preferably at most 10 mass%, more preferably at most 10 mass%.

[0032] As a coating method, a spin coating method, a spraying method, or the like is used to directly coat a suitable substrate such as a silicon wafer, a PET film, a polyimide film, a comma coating method, a fountain coating method, or the like. It may be formed by coating using a gravure method, a gravure method, or the like, and transferring and bonding this onto an appropriate substrate such as a silicon wafer.

After drying the solvent, the temperature of the heat treatment at a high temperature is preferably 200 ° C or more, preferably 250 to 350 ° C, and the treatment time is usually 10 minutes to 5 hours, preferably 30 minutes to 2 hours. is there. In order to prevent the resin from deteriorating, it is desirable to perform the heat treatment under an inert atmosphere such as a nitrogen atmosphere or a vacuum. This makes it possible to completely remove the volatile components remaining in the resin.

[0033] The tensile modulus of the cleaning layer (measured in accordance with JIS K7127, measured at a temperature of 23 ° C) is preferably 10 MPa to lGPa. Such a cleaning layer may be prepared by the above method. Monkey

The surface on which the cleaning layer is provided may be provided on at least one surface of the substrate, and may be provided on both surfaces. Further, it may be provided on the entire surface or only a part of the end face (edge portion) or the like. Further, in the present invention, the substrate processing apparatus from which dust is removed is not particularly limited. For example, an exposure apparatus, a resist coating apparatus, a developing apparatus, an asshing apparatus, a dry etching apparatus, an ion implantation apparatus, a PVD apparatus, a CVD apparatus , Visual inspection equipment, wafer prober, etc.

The present invention can also provide the above-described substrate processing apparatus from which dust has been removed by the above method.

Example

[Tensile modulus]

Test ¾ [Measured at 23 ° C by a method according to ISK7127.

[Dust removal properties]

Liner film peeling device for manufacturing cleaning sheets (HR-300C, manufactured by Nitto Seiki) W) was used to evaluate dust removal (apparatus A). First, 20 aluminum pieces cut into lmm x 1 mm were placed on the chuck table of the apparatus. Next, the cleaning layer was dummy-transported to the cleaning transport member on the cleaning transport member A, vacuum-adsorbed (0.5 kgZcm ² ) to the chuck table, and strongly adhered to the cleaning layer and the chuck table contact area. Thereafter, the vacuum suction was released, and the dust removal rate was measured from the number of aluminum pieces on the chuck table when the cleaning conveyance member was removed from the chuck table. The measurement was performed three times, and the average was obtained.

[Conveyability]

In the same manner as above, the wafer was conveyed onto a chuck table, vacuum suction was performed, and after releasing the vacuum, it was evaluated whether the cleaning member could be peeled off with a lift pin by a lift pin. Those that could be peeled off were marked with 〇, those that could not be peeled off were marked with X.

[Vacuum arrival time]

The degree of vacuum reached is 1 x 10 " ⁹ when the cleaning transport member lcm ² is charged into a thermal desorption mass spectrometer (EMD-WA1000S, manufactured by Denshi Kagaku) at 50 ° C. The time to return to Torr (1.33 X 10 " ⁷ Pa) was measured. Here the measurement conditions, maintaining the temperature in the chamber foremost 50 ° C, the sample size is lcm ^2, and the initial vacuum degree ^{3 X 10- 1Q Torr (4. 0} X 10 "8Pa), after sample loading, The time when the degree of vacuum returned to 1 X 10 " ⁹ Torr (l. 33 X 10" ⁷ Pa) was calculated as the time to reach vacuum.

It is preferable that the vacuum arrival time is short, since the influence on the actual production under vacuum is small.

[Example 1]

36.6 g of hydrogenated polybutadiene-terminated carboxylic acid conjugate (CI 1000 manufactured by Nippon Soda, acid value: 52 (KOH mg / g), mass average molecular weight: 2000, carboxyl group: 2), and 1,12 diamino 22.8 g of dodecane was heated and dissolved in a mixed solvent of 119 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) and 59 g of xylene. The temperature was increased to 195 ° C. while removing xylene under a nitrogen stream, and azeotropic dehydration and condensation were carried out until no more water was distilled off. After cooling, 119 g of NMP and 119 g of xylene were dried and heated again to 80 ° C., and 30.0 g of 4,4′-oxydiphthalic dianhydride (hereinafter abbreviated as ODPA) shown below was added and reacted. The resin solution obtained by cooling was applied on a mirror surface of an 8-inch silicon wafer and a shine surface of a rolled copper foil by a spin coater, and dried at 90 ° C. for 20 minutes. In a nitrogen atmosphere And heat-treated at 280 ° C for 2 hours to form a heat-resistant resin film having a thickness of 20 m.

[0041] [Formula 1]

Example 2

23.0 g of hydrogenated polybutadiene carboxylic acid conjugated product (Nippon Soda CI 1000, acid value: 52 (KOH mg / g), mass average molecular weight: 2000, carboxyl group: 2), 23.0 g, and 1,12 diamino 21.5 g of dodecane was heated and dissolved in a mixed solvent of 89 g of NMP and 45 g of xylene. The temperature was increased to 195 ° C while removing xylene under a nitrogen stream, and azeotropic dehydration and condensation were carried out until water distilling stopped. After cooling, 105 g of NMP and 105 g of xylene were added and heated again to 80 ° C., and 30.0 g of ODPA was added and reacted. After cooling, the obtained resin solution was applied on a mirror surface of an 8-inch silicon wafer and a shine surface of a rolled copper foil by a spin coater, and dried at 90 ° C. for 20 minutes. This was heat-treated at 280 ° C. for 2 hours in a nitrogen atmosphere to form a heat-resistant resin film having a thickness of 20 m.

Example 3

51.8 g and 1,12-diaminododecane hydrogenated polybutadiene bi-terminal carboxylic acid compound (CI 1000 manufactured by Nippon Soda, acid value: 52 (KOH mg / g), mass average molecular weight: 2000, carboxyl group: 2) 12.1 g was heated and dissolved in a mixed solvent of 126 g of NMP and 63 g of xylene under a nitrogen stream, and azeotropically dehydrated and condensed at 195 ° C. until water did not evaporate. After cooling, 175 g of NMP and 175 g of xylene were added, heated to 80 ° C again, and 24.8 g of 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) shown below and And 30.0 g of ODPA were added and reacted. After cooling, the obtained resin solution was applied on a mirror surface of an 8-inch silicon wafer and a shine surface of a rolled copper foil with a spin coater, and dried at 90 ° C. for 20 minutes. This is heat-treated at 280 ° C for 2 hours in a nitrogen atmosphere, A thermal resin film was formed.

[0044] [Formula 2]

Example 4

Hydrogenated polybutadiene bi-terminal carboxylic acid compound (CI 1000 manufactured by Nippon Soda, acid value: 52 (KOH mg / g), mass average molecular weight: 2000, carboxyl group: 2) 38.5 g and 1,12-diaminododecane 24.0 g was heated and dissolved in a mixed solvent of 138 g of NMP and 69 g of xylene under a nitrogen stream, and was subjected to azeotropic dehydration and condensation at 195 ° C. until water did not evaporate. After cooling, 116 g of NMP and 116 g of xylene are dried, heated to 80 ° C again, and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BDPA) shown below. 30. Og was added and reacted. After cooling, the obtained resin solution was applied on a mirror surface of an 8-inch silicon wafer and a shine surface of a rolled copper foil by a spin coater, and dried at 90 ° C. for 20 minutes. This was heat-treated at 280 ° C. for 2 hours in a nitrogen atmosphere to form a heat-resistant resin film having a thickness of 20 m.

[0046]

Example 5

23.4 g of hydrogenated polybutadiene carboxylic acid bi-terminal carboxylic acid compound (CI 1000 manufactured by Nippon Soda; acid value; 52 (KOH mg / g), mass average molecular weight: 2000, carboxyl group: 2) and 23.4 g shown below as m —6.0 g of xylene diamine was dissolved by heating in 30 g of xylene. Nitrogen The temperature was increased to 220 ° C while removing xylene while flowing down, and azeotropic dehydration and condensation were performed until no water distilled. After cooling, 16.6 g of BAPP and 300 g of NMP were added and dissolved.Then, the mixture was heated again to 80 ° C, and 30.0 g of bistrimellitic ester dianhydride of ethylene glycol shown below as B was removed and reacted. Was.

After cooling, the obtained resin solution was applied on a mirror surface of an 8-inch silicon wafer and a shine surface of a rolled copper foil with a spin coater, and dried at 90 ° C. for 20 minutes. This was heat-treated at 280 ° C. for 2 hours in a nitrogen atmosphere to form a heat-resistant resin film having a thickness of 20 m.

Example 6

Carboxylated polybutadiene (BN-1015, manufactured by Nippon Soda: acid value; 134 (KOH mg / g), mass average molecular weight: 1260, carboxyl group: average 3) 26.2 g and 3.7 g of 5-aminovaleric acid in 30 g of xylene A solution of the reacted polybutadiene polycarboxylic acid compound was obtained. To this was added 7.4 g of m-xylenediamine. Then, the temperature was increased to 220 ° C while removing xylene under a nitrogen stream, and azeotropic dehydration and condensation were carried out until no more water was distilled. After cooling, 20.6 g of BAPP and 300 g of NMP were dissolved in kamen ぇ and heated again to 80 ° C, and 30.Og of bistrimellitate dianhydride of ethylene glycol shown below as B Well, let it react.

[0049] For the 8-inch silicon wafer on which the heat-resistant resin film formed in Examples 1 to 6 was formed, the heat-resistant resin film was used as the dust-removing surface, and the dust-removing property, transportability, and arrival time in vacuum were determined by the above method. Was evaluated. For the heat-resistant resin film formed on the copper foil, after the copper foil was removed by etching with a ferric chloride solution, the tensile modulus was measured according to the method described above.

[0050] [Formula 4]

[Comparative Example 1]

^The resin was not coated on the ^8- inch silicon wafer, and the mirror surface was used as an adhesive surface to evaluate dust removal, transportability and vacuum arrival time.

[Table 1] Table 1

The dust-removing substrate having a heat-resistant cleaning layer derived from the imide resin of the present invention exhibits excellent dust-removing properties, and the vacuum arrival time is not so long compared to a normal wafer, and the transportability is also improved. I understand that there is no problem.

Claims

The scope of the claims

[1] A heat-resistant resin obtained by reacting a tetracarboxylic anhydride, an aliphatic diamine, and an elastomer having two or more carboxyl groups.

[2] The heat-resistant resin according to claim 1, wherein the elastomer having two or more carboxyl groups is a dicarboxylic acid elastomer.

[3] The heat-resistant resin according to claim 2, wherein the dicarboxylic acid elastomer is a terminal dicarboxylic acid elastomer containing hydrogenated polybutadiene.

[4] A heat-resistant resin obtained by heat-treating the heat-resistant resin according to any one of claims 1 to 3 at 200 ° C or higher.

[5] An elastomer obtained by subjecting an elastomer having two or more carboxyl groups to a dehydration-condensation reaction with an elastomer having two or more carboxyl groups and an excess amount of an aliphatic diamine with respect to the elastomer having two or more carboxyl groups. A method for producing a heat-resistant resin, comprising reacting the product obtained with tetracarboxylic dianhydride.

[6] A dust removal substrate for a substrate processing apparatus, comprising: a substrate; and a cleaning layer containing the heat-resistant resin according to any one of claims 1 to 4 on at least one surface of the substrate.

[7] A method for removing dust by bringing the resin surface of the dust removal substrate according to claim 6 into contact with the surface of the substrate processing apparatus.