JP2002363320A - Surface modification method for fluoroelastomer, surface-modified fluoroelastomer, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface modification method wherein an elastomeric sealing material which is used for a liquid crystal/semiconductor production apparatus and is excellent in non-tackiness can be obtained without detriment to the mechanical properties softness, and heat resistance, whereby the work for removing a solvent used in the surface treatment of a substrate elastomer and for removing an unreacted monomer after the surface treatment can be decreased since the solvent and the unreacted monomer does not penetrate into the elastomer, and whereby a clean sealing material of a liquid crystal/ semiconductor production apparatus can be provided. SOLUTION: This surface modification method comprises (1) a step of forming hydroxy-group-reactive points on the surface of a fluoroelastomer by subjecting the surface to a low-temperature plasma treatment, (2) a step of subjecting a water-soluble silicone monomer having a terminal hydroxy group to graft polymerization onto the active points, and (3) a step of washing the substrate surface subjected to the graft polymerization treatment with water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying a surface of a fluorine-containing elastomer, a surface-modified fluorine-containing elastomer, and uses thereof. A method for modifying the surface of a fluorinated elastomer such that an elastomer having excellent non-tackiness and the like can be obtained while maintaining mechanical strength and deformation followability, and a surface-modified fluorinated elastomer obtained from the elastomer. Related to sealing materials.

[0002]

BACKGROUND OF THE INVENTION Generally, elastomer seal materials are
When used as a sealing material, it has a strong surface adhesive force and firmly adheres to the mating surface, hindering the operation of the apparatus and reducing maintenance efficiency. For example, in the case of a sealing material provided at an entrance / exit (gate valve) of a silicon wafer of a semiconductor manufacturing apparatus, if it adheres to a mating surface, the opening / closing of the valve will be hindered, which will significantly hinder product manufacture.
In addition, if the sealing material used in the semiconductor manufacturing apparatus adheres to the mating surface, the maintenance time increases, which causes a reduction in production efficiency. . For this reason, in liquid crystal / semiconductor manufacturing equipment, there is a strong demand for an elastomer material that does not stick to a mating surface and has cleanliness and plasma resistance suitable for a liquid crystal / semiconductor manufacturing environment. Attempts have been made to detackify the surface of the material.

For example, Japanese Patent Application Laid-Open No. H11-255929 discloses a coating method for forming a coating film such as a fluororesin on the surface of an elastomer substrate. A processing solution in which a monomer having a possible functional group is dissolved in a solvent is prepared, and a monomer is present on the surface and inside of the rubber substrate by contacting the rubber substrate, and then the monomer is polymerized by heat treatment. A surface treatment method utilizing a chemical reaction in which the surface of a rubber substrate and its vicinity are modified by a chemical reaction is described.

[0004] However, the above-mentioned publication or the method for making the elastomer sealing material non-adhesive, when used in a liquid crystal / semiconductor manufacturing apparatus, has problems in terms of non-adhesion, low friction, abrasion resistance, plasma resistance and the like. Although it was superior to the conventional product, there was room for further improvement in the following points. When the elastomer sealing material obtained by the coating method described in the above publication is compressed, a crack is generated in the coating layer, which causes peeling, falling off, and gas leak of the coating layer. In addition, the dropped coating layer contains an inorganic filler and the like, and the inorganic filler may be scattered on the wafer surface to cause a problem such as a decrease in yield. The sealing material had room for further improvement.

[0005] The elastomer sealing material obtained by the surface treatment method utilizing the chemical reaction described in the above-mentioned publication is superior to the conventional sealing material as described above, but cracks during compression due to hardening of the surface layer. In addition, there is room for further improvement in terms of gas leakage and gas leakage, and in the production of the elastomer sealing material, the rubber base material is immersed in a solvent to swell the rubber. Removal has become a problem, and there is room for further improvement in terms of contamination of the liquid crystal / semiconductor manufacturing environment.

JP-A-11-172027 discloses that
After contacting the treatment liquid containing the polymerizable double bond-containing monomer, the polymerization initiator and the solvent with the rubber substrate, the resulting contact-treated rubber substrate is heated to polymerize the monomer. A method for producing a surface-modified rubber characterized by modifying the surface of a rubber substrate and its vicinity is described. The production method of the surface-modified rubber described in the publication is for polymerizing monomers, and the treatment liquid contains an organic solvent that permeates the rubber itself. There is still room for improvement in the non-stickiness and cleanliness of the car.

[0007] Japanese Patent Publication No. 7-103258 discloses a method in which a polyfunctional unsaturated compound such as triallyl isocyanurate and an organic peroxide are adhered to the surface of a vulcanized fluororubber molded article, and then the molded article is cured. Is described in which the surface of a vulcanized fluoro rubber molded article is heated to a temperature equal to or higher than the decomposition temperature of an organic peroxide. However, according to the method described in this publication, unreacted polyfunctional unsaturated compounds and organic solvents remain inside the vulcanized fluororubber molded article after the treatment, which is required for the sealing material of semiconductor manufacturing equipment. The resulting cleanliness and non-stickiness were not satisfactory.

Japanese Patent Application Laid-Open No. 6-306199 discloses a method for imparting hydrophilicity to the surface of a polymer material.
A surface treatment method for the surface of a polymer material in which the surface of the polymer material is subjected to low-temperature plasma treatment to form two or more hydroxyl groups is described. The purpose of the surface treatment is to impart hydrophilicity to the polymer material. In addition, there is no description or suggestion of a technical idea of modifying the surface of the polymer material to impart non-adhesiveness or the like.

The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and performed low-temperature plasma treatment on the surface of a fluorine-containing elastomer base material to form active sites with hydroxyl groups on the base material surface. Surface-modifying, a step of graft-polymerizing a water-soluble silicone monomer having a hydroxyl group at a terminal to an active point of the plasma-treated substrate surface, and a step of washing the surface of the substrate treated with the silicone monomer with water. When a fluorine-containing elastomer was manufactured, a sealing material having excellent non-adhesion, plasma resistance, and cleanness was obtained by this elastomer.
The inventors have found that the above problems can be solved, and have completed the present invention.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art described above, and to provide a non-adhesive material without impairing the mechanical strength, flexibility and heat resistance of the elastomer sealing material. The purpose of the present invention is to provide a method for modifying the surface of an elastomer base material which is capable of obtaining a sealing material having excellent plasma resistance and cleanliness, and further providing a sealing material for a liquid crystal / semiconductor manufacturing apparatus. I have.

[0011]

SUMMARY OF THE INVENTION The method for modifying the surface of a fluoroelastomer according to the present invention comprises the steps of: (1) subjecting the surface of a fluoroelastomer base material to low-temperature plasma treatment to form active sites with hydroxyl groups on the base material surface. (2) a step of graft-polymerizing a water-soluble silicone monomer having a hydroxyl group at the terminal to the active site; and (3) a step of washing the surface of the substrate subjected to the graft polymerization treatment with water. .

[0012] The low-temperature plasma treatment is performed at an output of 60 W to 5 W.
It is desirable to irradiate the plasma with a 00 W RF wave at a degree of vacuum of 1 to 100 Pa for 1 to 10 minutes.
The surface-modified fluorine-containing elastomer obtained by the above method is used for a sealing material for a liquid crystal / semiconductor manufacturing apparatus.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The method for modifying the surface of a fluorinated elastomer according to the present invention, the surface-modified fluorinated elastomer and its use will be described in detail below. In the present invention, a step (1) of subjecting the surface of a fluoroelastomer base material to low-temperature plasma treatment to form an active site with a hydroxyl group on the base material surface, a water-soluble silicone having a terminal hydroxyl group at the active site The surface modification of the fluorine-containing elastomer is performed by performing a step (2) of graft-polymerizing the monomer and a step (3) of washing the surface of the base material treated with the silicone monomer with water.

Step (1) In the surface modification of the fluoroelastomer of the present invention, the surface of the fluoroelastomer base material is subjected to low-temperature plasma treatment and then reacted with oxygen to form an active site on the base material surface with a hydroxyl group. Is formed. Hereinafter, the fluorine-containing elastomer substrate and the low-temperature plasma treatment will be described.

[Fluorine-Containing Elastomer Substrate] The fluorine-containing elastomer substrate used in the present invention is not particularly limited in terms of material, shape, dimensions and the like, and various conventionally known ones can be used. As the material of such a fluorine-containing elastomer base material, any vulcanization system of the base rubber may be used, and examples thereof include a polyol vulcanization system, a peroxide vulcanization system, a polyamine vulcanization system, and a radiation vulcanization system. Further, as a base rubber composition, a binary fluororubber whose main component is "hexafluoropropylene-vinylidene fluoride", and a main component of which is "hexafluoropropylen-vinylidenefluorite-tetrafluoroethylene" 3 Raw fluororubber, radiation-crosslinked thermoplastic fluororubber which does not require a vulcanizing agent, and the like.

In the present invention, as the material of the fluorine-containing elastomer base material, a ternary fluorine-containing rubber or a radiation-crosslinked thermoplastic fluorine-containing rubber which does not require a vulcanizing agent is preferably used. Ternary fluorinated rubber is more resistant to various chemicals when vulcanized with organic peroxide than binary, and provides a sealing material suitable for semiconductor manufacturing equipment environments using special chemicals. Therefore, it is preferable. Further, a radiation-crosslinked thermoplastic fluororubber is preferable because a vulcanizing agent is not required in the production process and a sealing material having a high cleanness can be obtained.

The base rubber may be blended with a filler, a vulcanization accelerator, a co-crosslinking agent, and a vulcanizing agent by a conventionally known technique. These compounds are molded and vulcanized by a conventionally known method. By sulfurizing, a fluorine-containing elastomer base material used in the present invention is prepared. Specifically, for example, the vulcanizing agent 1.5 to 100 parts by weight of the fluorine-containing base rubber
3 parts by weight, 4 to 10 parts by weight of co-crosslinking agent, 20 to 60 reinforcing agents
A part by weight is compounded by a conventionally known method using an open roll, and then, the mixture is filled in a mold for a predetermined size of a sealing material, and the mixture is compressed at a temperature of 100 to 200 ° C. by a compression press. Perform compression molding for 30 minutes. Next, after compression molding, secondary vulcanization at a temperature of 100 to 200 ° C. for 1 to 24
After heating for a time, the fluorine-containing elastomer base material used in the present invention is prepared. Examples of the shape of the elastomer base material used in the present invention include, for example, sheet, plate, rod, ring, various complicated block shapes, and any other shapes depending on the application, and are particularly limited. is not.

[Low-Temperature Plasma Processing] In the present invention, low-temperature plasma processing is performed by applying a high-frequency electric field, a microwave electric field, or a direct-current electric field to a low-pressure gas using a conventionally known low-temperature plasma generating apparatus. It can be performed by irradiating the surface of the elastomer substrate with plasma in a plasma atmosphere to generate active species.

The low-temperature plasma treatment is performed under an atmosphere of an inert gas such as argon or nitrogen, an oxygen plasma, or a mixed gas plasma atmosphere.
Using an RF wave of 500 W, preferably 100 to 300 W, and a degree of vacuum of 1 to 100 Pa, preferably 30 to 80 Pa
In this case, it is preferable that the surface of the substrate is irradiated with plasma for 1 to 10 minutes. Performing low-temperature plasma treatment under such conditions is preferable because the surface of the elastomer substrate is uniformly plasma-treated, and deterioration of the elastomer substrate can be minimized by the plasma treatment.

When such a low-temperature plasma treatment is performed under the conditions of an output of 500 W or more and 10 minutes or more, the etching of the surface of the elastomer base material is promoted, and the bonding with the base material surface is weak and the layer easily peels off. Is not preferred. After the low-temperature plasma treatment, the surface of the substrate is reacted with oxygen to form active sites on the surface of the substrate. In order to form an active point by reacting oxygen on the surface of the base material as described above, for example, air may be sent into the plasma generator, and the sample may be taken out after returning to the atmospheric pressure. Alternatively, the reaction may be performed with oxygen used for the plasma gas under the oxygen plasma treatment. As a result, oxygen in the air or oxygen used as the plasma gas reacts with the surface of the rubber substrate subjected to the plasma treatment to form active points on the substrate surface that can react with hydroxyl groups.

Examples of such active sites include functional groups such as a carboxyl group, an ester group and a trace amount of a hydroxyl group, and one or more of these active sites may be formed. In the present invention, it is preferable that a carboxyl group is formed on the surface of the rubber substrate from the viewpoint of reactivity with a hydroxyl group. Further, in the present invention, by performing low-temperature plasma treatment under the above-described conditions, it is desirable that a large amount of carboxyl groups are formed particularly on the surface of the elastomer base material.

Step (2) In the surface modification of the fluorine-containing elastomer of the present invention, after performing the low-temperature plasma treatment step (1),
A step (2) of graft-polymerizing a silicone monomer, that is, a step (2) of graft-polymerizing an active site with a hydroxyl group formed on the surface of the elastomer base material and an aqueous solution-containing silicone monomer having a hydroxyl group at a terminal.

Hereinafter, the aqueous silicone monomer and the graft polymerization will be described. [Aqueous Solution Silicone Monomer] The aqueous solution silicone monomer used in the present invention is an aqueous solution silicone monomer containing a hydroxyl group at a terminal. Examples of such aqueous silicone monomers include an aqueous silicone monomer having a main skeleton (main chain) of dimethylpolysiloxane having hydroxyl groups at both ends, a silicone monomer having a hydroxyl group at one end, and a silicone monomer having a hydroxyl group at one end. It is desirable to use an aqueous solution of silicone monomers containing one or two hydroxyl groups in the side chain, or a combination thereof, and preferably containing hydroxyl groups at both ends.

Furthermore, the aqueous silicone monomer used in the present invention has a viscosity (25 ° C.) of 40 to 4
It is desirable to use one having a pressure of 00 mPa · s, preferably 96 to 320 mPa · s. By using a water-soluble silicone monomer having the above structure and viscosity, a sealing material having excellent non-adhesiveness can be obtained. The aqueous silicone monomer containing a total of two hydroxyl groups at both ends of the main chain and the like forms an ester bond with an active site such as a carboxyl group on the substrate surface generated by a low-temperature plasma treatment and the like. Dehydration condensation,
It is thought that graft polymerization is caused by an ether bond. Further, when using an aqueous solution silicone monomer having a hydroxyl group at one end, it is considered that the active site on the substrate surface, for example, an ester bond with a carboxyl group, etc., which also causes the monomer on the substrate surface It is believed that a non-sticky siloxane bond is formed.

As the aqueous silicone monomer used in the present invention, specifically, an alcohol-modified silicone oil comprising the aqueous silicone monomer having the above structure is used, and an alcohol-modified silicone oil having reactivity with a carboxyl group is used. Although not particularly limited for, in the present invention, taking into account the washing step after the reforming treatment,
It is desirable to use a water-soluble silicone oil.

As such a water-soluble silicone oil, for example, a water-soluble silicone oil as shown in Table 1 below, which is a compound whose both ends are alcohol-modified, is exemplified.
It is desirable to use a water-soluble silicone oil having a viscosity within the above numerical range. Specifically, SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.), KF-6
001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are preferable. These water-soluble silicone oils can be used alone or in combination of two or more.

By causing such a low-polarity silicone monomer to undergo a fixing reaction on the surface of the elastomer base material,
Non-stick properties can be imparted to the elastomer surface.

[0028]

[Table 1]

[Graft Polymerization] The graft polymerization performed in the above step (2) contains a hydroxyl group at the above-mentioned terminal starting from an active site formed on the surface of the elastomer base material by the low-temperature plasma treatment in the step (1). It is carried out by graft-polymerizing a water-soluble silicone monomer (alcohol-modified silicone oil). Such graft polymerization is usually performed by bringing the above-mentioned substrate into contact with a water-soluble silicone monomer in the presence of a catalyst. At this time, a solvent (solvent) or the like may be used.

In order to carry out such graft polymerization, first, the above-mentioned alcohol-modified silicone oil and catalyst are mixed to prepare a treatment liquid used for graft polymerization. Examples of such a catalyst include concentrated sulfuric acid and p-toluenesulfonic acid, and concentrated sulfuric acid is preferably used. In addition, the solvent (solvent) can reduce the viscosity of the treatment liquid. Examples of such a solvent, such as toluene and xylene, which hardly swell the elastomer base material under low-temperature conditions Organic solvents and the like can be mentioned. Since these organic solvents cause swelling of the elastomer base material when used under high-temperature conditions, they are preferably used under low-temperature conditions.

The above-mentioned treatment liquid for graft polymerization may not contain an organic solvent, but a solvent used if necessary is preferably selected so as to hardly damage the elastomer itself. Therefore, the unreacted monomer or solvent hardly penetrates or impregnates into the elastomer, and there is no need to perform these extraction and removal operations in the present invention. Furthermore, since an organic solvent or the like does not permeate into the elastomer, the amount of gas released from the obtained elastomer is extremely small, and a clean elastomer product can be provided.

When such a treatment liquid comprises an alcohol-modified silicone oil and a catalyst, the treatment liquid contains
The amount of the catalyst is 1 to 80 to 100 parts by weight, preferably 90 to 95 parts by weight, of the alcohol-modified silicone oil.
It is desirable that it be contained in an amount of up to 20 parts by weight, preferably 5 to 10 parts by weight. When the treatment liquid is composed of an alcohol-modified silicone oil, a catalyst and an organic solvent, the catalyst is used in an amount of 40 to 100 parts by weight, preferably 60 to 80 parts by weight of the alcohol-modified silicone oil in the treatment liquid. It is desirable that the organic solvent is contained in an amount of 1 to 20 parts by weight, preferably 5 to 10 parts by weight, and the organic solvent is contained in an amount of 10 to 40 parts by weight, preferably 20 to 30 parts by weight.

In the graft polymerization in the step 2, specifically, an elastomer substrate is put into the treatment liquid obtained as described above, and the treatment liquid is heated at 30 to 100 ° C., preferably at 4 to 100 ° C.
While keeping the temperature in the range of 0 to 80 ° C., the mixture may be stirred in the container for 30 minutes to 16 hours, preferably 1 to 3 hours. As a result, the hydroxyl group of the silicone monomer and the carboxyl group on the surface of the elastomer base material undergo an esterification reaction, and the silicone monomers can be graft-polymerized on the surface of the elastomer base material.

By performing the graft polymerization under such conditions, it becomes possible to produce a surface-modified fluorine-containing elastomer capable of forming a sealing material having non-adhesion, plasma resistance and cleanliness. Step (3) In the surface modification of the fluoroelastomer substrate of the present invention, the surface of the treated elastomer substrate obtained in the above step (2) is then washed with water to be present on the surface of the substrate. Unreacted silicone monomer is removed to obtain the surface-modified fluorine-containing elastomer of the present invention.

In the present invention, an organic solvent is not used for the treatment liquid, and a solvent which does not attack the elastomer base material even if used is used, so that the solvent and unreacted monomer permeate and diffuse into the elastomer. Instead, they are substantially only present on the substrate surface. Further, a water-soluble silicone monomer is preferably used, but when such a water-soluble silicone monomer is used, unreacted silicone monomer can be easily removed only by washing the surface of the base material with water. In addition, it is possible to reduce the burden of removing unreacted silicone monomer and the like as compared with the case of washing with an organic solvent, and it is possible to further reduce the influence on the human body and environmental pollution.

According to the surface-modified fluorine-containing elastomer produced in this manner, a small amount of gas is released from the elastomer, and a clean sealing material can be provided. Sealing material The sealing material of the present invention can be used for various applications,
Although it is not limited to a specific use, it is preferably used as a sealing material for a liquid crystal / semiconductor manufacturing device, and more preferably as a sealing material for a semiconductor manufacturing device.

Specific examples of such a sealing material for a liquid crystal manufacturing device include a sealing material for a sputtering device;
Sealing material for VD equipment (plasma CVD, laser CVD, etc.); sealing material for etching equipment (dry etching equipment, wet etching equipment, etc.); sealing material for peeling equipment; sealing material for oxidation / diffusion / ion implantation equipment Sealing materials for vapor deposition devices (vacuum vapor deposition devices, vapor deposition polymerization devices, etc.); sealing materials for cleaning devices (dry cleaning type, wet cleaning type); various inspection devices (mask inspection device, pattern inspection device, etc.) ); Sealing material for an exposure device (proximity type, stepper type); sealing material for an annealing device (lamp annealing device, excimer laser annealing device, etc.); Sealing materials for devices;

Examples of the sealing material for semiconductor manufacturing equipment include coaters and developers, etching equipment (plasma etching equipment, etc.), plasma ashing equipment, resist stripping equipment, cleaning / drying equipment, etc. Sealing material; Furnace sealing material for oxidation / diffusion furnace, lamp annealing device, etc .; Metal CVD device, plasma CVD
Equipment, CVD equipment such as LP-CVD equipment, etc., and sealing materials such as sputtering equipment; various types of transfer devices (such as O-rings or transfer belts for transfer of wafer transfer devices); various types of resist transfer devices (register transfer containers) Cap sealing material, etc.); various inspection apparatus groups; and the like.

Of these, a plasma etching apparatus,
It is particularly preferably used for devices requiring plasma resistance, such as a plasma ashing device, a plasma CVD device, and a wafer transfer device as an auxiliary device of these devices (these devices are collectively referred to as a “plasma processing device”). The sealing material of the present invention can impart a non-adhesive property to the surface of the elastomer substrate because the silicone monomer having a low polarity reacts and is fixed (fixed) on the surface of the sealing material. And the silicone monomer are chemically bonded by graft polymerization, so that the surface-modified layer of the substrate is stable. When such a sealing material is used as a sealing material for a liquid crystal / semiconductor manufacturing device, the sealing material exhibits non-adhesiveness to these devices, and is extremely difficult to adhere to these devices. Maintenance becomes easy, and the production efficiency of liquid crystals, semiconductors, and the like can be improved.

[0040]

According to the present invention, the mechanical strength, flexibility and heat resistance of the elastomer sealing material are not impaired.
A surface treatment method as a sealing material for a liquid crystal / semiconductor manufacturing apparatus having excellent non-adhesiveness can be provided. Further, according to the surface treatment method of the present invention, since the solvent used in the surface treatment of the base elastomer and further the unreacted monomer do not penetrate into the elastomer, the work of removing them after the surface treatment can be reduced. It is possible to provide a clean sealing material for a liquid crystal / semiconductor manufacturing apparatus.

[0041]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The surface-modified fluoroelastomer and the like obtained in Examples, Reference Examples and Comparative Examples were measured according to the following methods. (1) Weight increase rate Fluorine-containing elastomer obtained by press molding is 100
After the substrate was sufficiently dried in an electric furnace at ℃ to prepare a substrate, the weight of the substrate before treatment was measured using a precision balance. afterwards,
The obtained fluorine-containing elastomer substrate is subjected to plasma surface treatment, immersion treatment in a silicone oil solution, and further washed with pure water (toluene is used for hydrophobic silicone oil), under the same conditions as before the treatment. Dry underneath. The weight of the fluorine-containing elastomer after the grafting was measured using a precision balance, and the weight increase (%) was determined from the weight before and after the grafting. The amount of silicone monomer grafted on the surface of the elastomer substrate was determined from the weight increase rate. (2) Change in adhesion force A sample (50 × 50 × 2 tmm sheet) is sandwiched between aluminum (2017 plates), compressed at 200 ° C. for 72 hours, and then peeled off the aluminum plate (Ra = 1.2). Was measured with an Instron (tensile tester) to determine the adhesive force. In order to maintain the cleanliness of the sample surface, the sample surface was washed with methanol at the end of the test and used for the next test. This test was repeated ten times, and the first and tenth adhesions were compared. By comparing the change in the fixing force as described above, the non-adhesion specific evaluation of the surface treatment layer and the durability evaluation were performed.

[0042]

Example 1 A fluorine-containing elastomer substrate was prepared as follows. Fluororubber (Daiel G902 (hexafluoropropylene-vinylidenefluoride-tetrafluoroethylene copolymer: manufactured by Daikin Industries, Ltd.)) 1
A mixture consisting of 00 parts by weight, 1.5 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 4 parts by weight of triallyl isocyanurate, and 20 parts by weight of MT carbon was treated with an open roll. 17 in a known manner using
After press molding at 0 ° C. × 10 minutes, secondary vulcanization is performed at 180 ° C. × 4 hours, and 150 mm × 190 mm × 2 m (thickness)
Into a sheet.

The above-mentioned sheet-like molded product was put in a low-temperature plasma generator (manufactured by Hirano Kotone Co., Ltd.), and an RF wave having a degree of vacuum of 60 Pa and an output of 100 W was used in an argon gas atmosphere.
Plasma irradiation was performed for 3 minutes. After the low-temperature plasma treatment, air was sent into the plasma generator, and the pressure was returned to the atmospheric pressure. Then, the sheet was taken out and placed in the following treatment solution for graft polymerization. The treating solution was a silicone oil modified with alcohol at both ends (hydrophilic, SF-8427 (manufactured by Dow Corning Toray Silicone Co., Ltd.)) having a viscosity of 320 mPa ·
s) was prepared by adding 10 parts by weight of 90% by weight concentrated sulfuric acid to 90 parts by weight. In the present embodiment, the sheet-like material was put in this treatment liquid and the temperature was 50 ° C. for 1 hour.
Graft polymerization was carried out while stirring for an hour. After the graft polymerization treatment, the sheet-shaped molded product was taken out, washed with water, and dried to produce a surface-modified fluorine-containing elastomer.

With respect to the surface-modified fluorine-containing elastomer, the rate of increase in weight and the change in fixing force were evaluated according to the above-mentioned measuring methods. Table 2 shows the results.

[0045]

Reference Example 1 In Example 1, the silicone oil modified at both ends was replaced with an epoxy polyether-modified silicone oil having a skeleton represented by the following formula [I] (SF-8421 (Dow Corning Toray Toray) Co., Ltd.): A surface-modified fluorine-containing elastomer was produced in the same manner as in Example 1, except that the viscosity was changed to 3500 mPa · s) 90 parts by weight.

With respect to the surface-modified fluorine-containing elastomer, the rate of weight increase and the change in fixing force were evaluated according to the above-mentioned measuring methods. Table 2 shows the results.

[0047]

Embedded image

[In the formula [I], x, y, and z represent the number of repeating units, R ¹ and R ² each represent a divalent linking group.
A represents a polyoxyalkylene group. ].

[0049]

Reference Example 2 In Example 1, the silicone oil modified at both ends was modified with an amino-modified silicone oil having a skeleton represented by the following formula [II] (SF-8417).
(Manufactured by Dow Corning Silicone Toray Co., Ltd .: viscosity: 1200 mPa · s), and a surface-modified fluorine-containing elastomer was produced in the same manner as in Example 1 except that the water washing was changed to toluene washing.

With respect to this surface-modified fluorine-containing elastomer, the rate of weight increase and the change in fixing force were evaluated according to the above-mentioned measuring methods. Table 2 shows the results.

[0051]

Embedded image

[In the formula [II], x and y represent the number of repeating units, and R represents a divalent linking group. ] Is represented.

[0053]

COMPARATIVE EXAMPLE 1 In Example 1, a sheet-shaped fluoroelastomer substrate was used without low-temperature plasma treatment, and the change in adhesion was evaluated according to the above-described measurement method. Table 2 shows the results.

[0054]

Comparative Example 2 In Example 1, the fluoroelastomer base material molded into a sheet was treated under the same conditions as in Example 1 by using the same treatment liquid as in Example 1 without performing low-temperature plasma treatment. A surface-treated fluorine-containing elastomer was produced. With respect to this surface-treated fluorine-containing elastomer, the weight increase rate and the change in the fixing force were evaluated according to the above-mentioned measuring methods.

Table 2 shows the results.

[0056]

Comparative Example 3 A fluorine-containing elastomer base material formed into a sheet in Example 1 was prepared by the method described in Japanese Patent Application Laid-Open No. 5-27144.
By treating in the same manner as in the method described in JP-A No. 8-No. 8, a surface-coated fluorine-containing elastomer was produced. That is, the phenolic resin (Mirex XL-210 (Mitsui Toatsu Chemicals)
The sample base material was immersed in a solution prepared by dissolving 1 gram of methyl ethyl ketone in 100 ml for 10 seconds, air-dried for 1 hour, and then dried in an oven.
After heating at 0 ° C. for 24 hours, the surface of the elastomer substrate was coated with a phenol resin. After the above treatment, the sheet-shaped molded product was taken out of the oven, washed with toluene, and the surface-coated fluorine-containing elastomer produced was evaluated for the change in the fixing force according to the above-described measurement method.

Table 2 shows the results.

[0058]

[Table 2]

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Claims (4)

[Claims] (1) a step of subjecting the surface of a fluorine-containing elastomer base material to low-temperature plasma treatment to form an active site with a hydroxyl group on the base material surface; (2) the active site containing a hydroxyl group at a terminal A method for modifying the surface of a fluorine-containing elastomer, comprising a step of graft-polymerizing a water-soluble silicone monomer and a step of (3) washing the surface of the substrate subjected to the graft polymerization treatment with water. 2. The method according to claim 1, wherein the low-temperature plasma processing has an output of 60 W to 5 W.
2. The method for modifying the surface of a fluorine-containing elastomer according to claim 1, wherein the method is performed by irradiating a plasma at a degree of vacuum of 1 to 100 Pa for 1 to 10 minutes using an RF wave of 00 W. 3. A surface-modified fluoroelastomer obtained by the method according to claim 1. 4. The surface-modified fluorine-containing elastomer according to claim 3, wherein the surface-modified fluorine-containing elastomer is used for a sealing material for a liquid crystal / semiconductor manufacturing apparatus.