JP2003286357A - Fluoro rubber molded article and non-adhesive treatment method for fluoro rubber molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluororubber molding having a superior non-adhesive property and to provide a plasma irradiation method which is effective for imparting the fluororubber molding with a superior non-adhesive property. <P>SOLUTION: The molding comprises a fluororubber or a fluororubber composition and on its surface there exist concave portions of 50,000 or more per 1 mm<SP>2</SP>which have a number average diameter of 2.0 μm or smaller. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-adhesive fluororubber molded article, a method for detackifying the fluororubber molded article, and a semiconductor manufacturing apparatus formed from the non-adhesive fluororubber molded article, for wafer transfer. The present invention relates to each sealing material for devices and vacuum containers.

[0002]

2. Description of the Related Art Conventionally, a sealing material made of fluororubber has been widely used in semiconductor manufacturing equipment, wafer transfer equipment, and vacuum containers. However, the fluororubber sealing material often adheres to the mating metal surface to be sealed, which may cause trouble during maintenance. For example, if the sealing material is firmly adhered to the metal surface, the rubber powder may rub off when peeling off when the sealing material is replaced, which may even adversely affect the device later.

Such an adhesion problem is particularly noticeable in a vacuum seal and a seal at a high temperature portion. In addition, even in a portion that is frequently opened and closed, this adhesion problem is important, and it also interferes with normal opening and closing operations. Therefore, in the fluororubber sealing material, in addition to the sealing performance, there is a strong demand for non-adhesion.

As a method for detackifying rubber, 1) compounding oil into rubber, and 2) treating with a surface treatment agent (for example,
JP-A-1-301725), 3) Treatment of impregnating a surface of a rubber material with a cross-linking agent and heating to increase the cross-link density near the surface (for example, JP-B-5-21931), 4) Silicone rubber (For example, Japanese Unexamined Patent Publication No. 5-339456), 5) Coating of rubber material surface with resin or the like (for example, Japanese Unexamined Patent Publication No. 1-141909), 6) Filling of rubber with powder of fluororesin or the like ( For example, Japanese Patent No. 30095676) is known.

However, when applied to fluororubber, the fluororubber has a low compatibility with hydrocarbon oils and silicone oils, so that the method 1) causes problems such as contamination due to oil exudation and reduction in strength of the material itself. Even in the method 2), problems such as a decrease in non-adhesiveness due to the removal of the surface treatment agent and contamination of the sealing surface and fluid cannot be ignored.
According to the method of 3), it is possible to achieve a good detackification to some extent, but a complicated processing operation is required. Further, as shown in Examples described later, the effect is not always satisfactory. The method of 4) also has drawbacks such as insufficient detackification and reduced strength of the fluororubber material. The method 5) has problems such as separation and peeling of the resin layer and deterioration of rubber elasticity due to the presence of the resin layer.
In the simple filling method such as the method of 6), the resin powder that appears in the surface layer is small and sufficient non-adhesiveness is not imparted. If the amount of the filler is increased to improve this point, problems such as deterioration of rubber elasticity and strength and deterioration of crosslinkability occur.

From such a background, it has been practiced to irradiate various kinds of plasma to modify the surface properties of the rubber material to make it non-adhesive. For example, JP-A-59-7
1336 discloses a method of treating the surface of a rubber material with nitrogen gas plasma, and Japanese Patent Publication 1-57131 discloses a method of ashing the surface of nitrile rubber with oxygen plasma.
Japanese Unexamined Patent Publication No. 4-209633 discloses a method of treating silicon rubber with plasma.

[0007]

However, the effectiveness of the above-mentioned detackification treatment method by plasma irradiation for a fluororubber molded article is unknown, and its irradiation condition is unknown. Depending on the type of plasma and the irradiation conditions, tackiness may be imparted as opposed to detackification. For example,
JP-A-5-125202 and JP-A-5-30978
Japanese Patent Publication No. 7 describes that when a fluorine-based member is irradiated with helium gas, adhesiveness occurs.

Further, the degree of non-adhesiveness of the fluororubber molded article, particularly suitable non-adhesiveness in semiconductor manufacturing equipment, wafer transfer equipment, vacuum containers, etc., is unknown, and further non-adhesiveness is exhibited. No knowledge of the surface properties of fluororubber moldings has been obtained.

The present invention has been made in view of the above circumstances, and provides a fluororubber molded article having excellent non-adhesiveness and at the same time imparts excellent non-adhesiveness to the fluororubber molded article. An object is to provide an effective plasma irradiation method.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and found that a fluororubber molded article having a specific surface property exhibits excellent non-adhesiveness, It has been found that plasma irradiation can impart excellent non-adhesiveness to a fluororubber molded article.

That is, the present invention is a molded article made of a fluororubber or a fluororubber composition, wherein the surface has 50,000 or more recesses having a number average diameter of 2.0 μm or less per 1 mm ^2. And a fluororubber molded body.

The present invention also provides a non-equilibrium fluororubber molded article, which comprises irradiating a crosslinked or uncrosslinked molded article made of fluororubber or a fluororubber composition with a non-equilibrium plasma of saturated fluorocarbon gas. Detackification of a fluororubber molded article, which comprises subjecting a crosslinked or uncrosslinked molded article made of a tackifying treatment method and a fluororubber or a fluororubber composition to a nonequilibrium oxygen plasma having a high-frequency output of 100 W or more. It is a processing method.

Further, the present invention is a sealing material for a semiconductor manufacturing apparatus, a wafer transfer container and a vacuum container, which is made of the above-mentioned fluororubber molded product.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The fluororubber molded article of the present invention is a fluororubber or fluororubber composition cross-linked and molded into a predetermined shape, and has a number average diameter of 2.0 μm or less on its surface by the plasma treatment described later. 5 recesses per 1 mm ²
There are over 10,000. As a result, excellent non-adhesiveness such as a shear tensile adhesive strength of 1.0 MPa or less after pressure-bonding to an aluminum plate at 200 ° C. for 25 hours at 25% is obtained.

The fluororubber or fluororubber composition includes
There is no limitation and it may be one that has been conventionally used as a sealing material or the like. Specifically, examples of the base fluororubber include hexafluoropropylene / vinylidene fluoride binary copolymer (for example, Viton A manufactured by DuPont Dow Elastomer Co., Ltd., Florel manufactured by Sumitomo 3M Co., Ltd.), and tetra. Fluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer (for example, Viton B manufactured by DuPont Dow Elastomer Co., Ltd., Sumitomo 3M Co., Ltd.)
Manufactured by Asahi Glass Co., Ltd./JSR Co., Ltd.), tetrafluoroethylene / propylene copolymers, tetrafluoroethylene / propylene / vinylidene fluoride copolymers, and polymers with double bonds Afras 200, etc.), pentafluoropropylene / vinylidene fluoride binary copolymer, chlorotrifluoroethylene / vinylidene fluoride binary copolymer (for example, Daiel made by Daikin Co., Ltd.), polymer having a perfluoroalkoxy group. (For example, Daikin Perflo manufactured by Daikin Co., Ltd.), fluorosilicone rubber (for example, Silastic LS manufactured by Dow Corning Co., Ltd.) and the like can be mentioned, but the invention is not limited thereto and any rubber having a fluorine atom in the molecule can be used. Anything can be used. It is also possible to use a plurality of fluororubbers together.

The above-mentioned base fluororubber may be used alone, or if necessary, various known compounds such as carbon black, graphite, silica, reinforcing fibers, processing aids, softening agents and coupling agents may be used. It can also be blended to give a fluororubber composition. Preferably, only carbon black having a small amount of residual hydrocarbons or the like is used. Especially MT, FT,
Carbon black such as SRF, base fluororubber 10
By blending 5 to 50 parts by weight with respect to 0 parts by weight, the strength of the rubber material can be further improved. Further, if desired, a rubber having a high hardness can be used.

The cross-linking form of the fluororubber or fluororubber composition is not particularly limited. As an example, polyol cross-linking,
For example, bisphenol AF, bisphenol A, p,
Cross-linking with polyhydroxy compounds such as p'-biphenol, 4,4'-dihydroxydiphenylmethane, hydroquinone, dihydroxybenzophenone or their alkali metal salts; polyamine cross-links, such as hexamethylenediamine, hexamethylenediamine carbamate,
1,3-diaminocyclohexane carbamate, bis (p-aminocyclohexyl), hexamethylenediamine carbamate (Diak No. 1 from DuPont)
Are commercially available under the tradename of AU), ethylenediamine carbamate (commercially available from DuPont under the trade name of Diak No. 2), N, N'-disinamylidene-6,6-
Hexanediamine (Diak No. 3 from DuPont)
, 4'-bis (aminocyclohexyl) methane carbamate, 4,4'-methylene-bis (2-chloroaniline) (available from DuPont as Mo).
(commercially available under the trademark ca.) and the like, but are not limited thereto. Depending on the type of fluororubber, peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 1,1-di (t-butylperoxy) -3,3,5
-Trimethylcyclohexane, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,1,3-di (t-butylperoxyisopropyl) benzene, 2,5- Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, n-butyl-4,4-di (t-
Butyl peroxy) valerate, α, α'-bis (t-
It can also be crosslinked with butylperoxy-m-isopropyl) benzene, benzoyl peroxide and the like. In the present invention, crosslinking can be achieved by any of the above means. It is also possible to crosslink with radiation such as electron beams and γ rays.

However, in the present invention, the fluororubber molded article is preferably one which has been crosslinked with a polyol, a peroxide or radiation, particularly γ rays. As a result, the detackification effect by plasma irradiation can be made more remarkable.

Upon crosslinking, quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium hydroxide, triethylbenzylammonium bromide, triethylbenzylammonium hydroxide, 8-benzyl-1,8-diazabicyclo [5,5]. 4,0] -7-undecenium hydroxide;
Organic phosphonium compounds such as triphenylethylphosphonium chloride, triphenylethylphosphonium hydroxide, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium hydroxide; bis (phosphino) iminium compounds such as bis (triphenylphosphine) iminium bromide, bis (Triphenylphosphine) iminium chloride, bis (benzylphenylphosphine) iminium chloride,
Bis (benzylphenylphosphine) iminium hydroxide; or basic nitrogen compounds such as n-octylamine, n-butylamine, aniline, 1-amino-2
-Butanol, 1-aminodecane, hexamethylenediamine, di-n-octylamine, di-n-butylamine, N-methylaniline, pyrrole, tri-n-octylamine, 2,2'-dipyridyl, 1,8-diazabicyclo Cross-linking accelerators such as [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, 1,4-diazabicyclo [2,2,2] octane; triallyl A crosslinking aid such as isocyanurate or trimethylolpropane trimethacrylate may be used in combination. Also,
When cross-linking with a polyol or polyamine, magnesium oxide (Mg
O), calcium hydroxide (Ca (OH) ₂ ), calcium oxide (CaO), lead oxide (PbO) and the like are preferably used. Preferably, the base fluororubber 10
About 0 to 10 parts by weight, in particular about 2 to 8 parts by weight of magnesium oxide, or about 1 to 10 parts by weight, especially about 2 to 8 parts by weight of calcium hydroxide, are used per 0 parts by weight. A plurality of these acid acceptors can be used in combination.

The amounts of the cross-linking agent and the cross-linking accelerator (auxiliary agent) are not particularly limited and can be arbitrarily determined by those skilled in the art according to the intended physical properties and the kind of the cross-linking agent. However, it is usually preferred to add about 0.1 to 10 parts by weight of the cross-linking agent and about 0.01 to 1 to 100 parts by weight of the base fluororubber.
0 parts by weight of crosslinking accelerator, more preferably about 0.5 to 7 parts by weight of crosslinking agent and about 0.05 to 7 parts by weight of crosslinking accelerator, particularly preferably about 1 to 5 parts by weight of crosslinking agent. 0.1 to 5 parts by weight of a crosslinking accelerator, about 1 to 10 parts by weight, especially about 2 to 8 parts.
Parts by weight magnesium oxide, or about 1-10 parts by weight,
Especially used with about 2 to 8 parts by weight of calcium hydroxide. When the amount of the polyol and the crosslinking accelerator (auxiliary) is small,
The elasticity of the sealing material becomes poor. On the other hand, if too much, the flexibility may be impaired.

The method of crosslinking and molding each of the above raw materials into a predetermined shape is arbitrary. For example, block-shaped compounded rubber may be put in a mold and heat-molded, or pre-molded by compression molding, extrusion molding or the like and then cross-linked. Injection molding can also be performed. There is no limitation on the shape of the molded product, and the molded product can be molded into various shapes such as an O-ring, a square ring, a U-shape, and a V-shape.

The crosslinking conditions are not particularly limited, and those skilled in the art can arbitrarily determine the crosslinking conditions depending on the intended physical properties and the type of the crosslinking (auxiliary) agent. For example, about 100-300
℃, especially about 120-200 ℃ 0.1 minutes ~ 10
The crosslinked product can be obtained by heating for 0 hours, particularly 1 to 30 minutes with a press or the like. Furthermore, in an oven or the like, the temperature is 150 ° C. or higher for 1 to 100 hours, preferably 180
It is also possible to carry out secondary crosslinking at ˜250 ° C. for 2 to 30 hours. Alternatively, the preform may be exposed to radiation, for example 5-300.
It is also possible to crosslink by irradiating with γ-rays of kGy, especially 20 to 150 Gky. The cross-linking method of the fluororubber or the fluororubber composition is a well-known conventional technique, and those skilled in the art can easily select the conditions to obtain a desired molded product.

Plasma irradiation is then performed on the fluororubber molded product made of the above fluororubber or fluororubber composition. For this plasma irradiation, either non-equilibrium plasma of saturated fluorocarbon gas or non-equilibrium oxygen plasma with a high-frequency output of 100 W or more is used.

Plasma is an independent collection of electrons, ions, radicals, excited molecules, etc., and this collection state is maintained for many times the average collision time between particles. Among them, those in which gas temperature and electron temperature have not reached equilibrium and only gas temperature is high are called “non-equilibrium plasma” or “low temperature plasma” (eg Yoshihito Nagata). Edited, published industrial books, "Low-pitched Plasma Material Chemistry"). Unlike non-equilibrium plasma, this non-equilibrium plasma has a low gas temperature, and therefore there is little possibility that the inside of the base fluororubber will be changed and physical properties will be deteriorated. In addition, non-equilibrium plasma is a glow discharge in gas,
It can be easily obtained by corona discharge, arc discharge, dark discharge, high frequency, microwave irradiation, or the like. Above all, glow discharge in a low vacuum state is widely used because it can generate uniform plasma. Also in the present invention, it is preferable to use glow discharge by a high frequency power source. Of course, another plasma plasma generation method may be used, and a commercially available plasma generator can also be used.

Oxygen or saturated fluorocarbon gas is used as the plasma gas. Examples of the saturated fluorocarbon gas include CF ₄ , C ₂ F ₆ , C ₃ F ₈ , C ₂ F ₂ and CH.
Examples thereof include, but are not limited to, fluorinated hydrocarbons such as ₂ F ₂ , CH ₃ F, CHF ₃ , and CF ₃ Br. Further, a plurality of saturated fluorocarbon gases may be mixed and used at an arbitrary ratio.

However, in the present invention, it is preferable to use plasma containing more ions and electrons than radicals. Generally, when a polymer is irradiated with plasma, the surface molecular chains are broken and etched. On the other hand, by using the plasma containing ions and electrons as the main components, it is possible to effectively perform the detackification while suppressing the etching to the minimum. More preferably, a rare gas or a fluorinated methane-based gas, particularly preferably CF ₄ is used. Most of these gases are ionized under glow discharge or high frequency, and radicals or the like are scarcely generated. for that reason,
There is an advantage that etching of the non-adhesive layer of the fluororubber molded body hardly occurs.

A desired plasma can be produced from these gases by glow discharge using a high frequency power source, for example. There is no particular limitation on the frequency during discharge, but 13.56M
A device using a radio wave of Hz is common. The irradiation conditions can be arbitrarily set according to the degree of non-adhesive properties of interest and the type of gas used, but the non-adhesiveness of particular interest in the present invention, that is, 200 ° C. on an aluminum plate.
In order to satisfy the shear tensile adhesive strength of 1.0 MPa or less after pressure bonding at 25% for 22 hours, the high frequency output is 100 W or more, preferably 120 W or more when non-equilibrium oxygen plasma is used, and the irradiation time is preferably Is 20 minutes or more, more preferably 60 minutes or more, and particularly preferably 10 minutes.
0 minutes or more. In addition, when the irradiation time is shortened, there is an advantage that etching is suppressed to a lower level. On the other hand, when non-equilibrium plasma of saturated fluorocarbon is used, 1 to 1
00W, more preferably 5 to 50W, particularly preferably 1
Irradiation may be performed with a power of about 0 to 30 W for 1 to 150 minutes, more preferably 2 to 100 minutes, and particularly preferably 5 to 20 minutes.

The mechanism for imparting non-adhesiveness to the fluororubber molded article by such specific plasma irradiation is considered to be generation of new crosslinks by plasma irradiation, selective etching removal of uncrosslinked components or low molecular weight components, and the like. To be By the plasma irradiation, only the surface portion of the fluororubber molded article is highly crosslinked, and further, this crosslinked portion is hardly etched, and the low molecular weight component that is the adhesive component is selectively removed to make it non-adhesive. Conceivable. It is also possible that the atomic ratio of fluorine in the surface layer is increased. By irradiating the non-equilibrium plasma of saturated fluorocarbon gas, the fluorine-containing group is introduced into the surface layer of the fluororubber molded article. Further, even when the non-equilibrium oxygen plasma is irradiated, hydrogen atoms are extracted from the surface layer of the fluororubber molded article to form a double bond or a crosslinked portion, thereby relatively increasing the fluorine atom ratio.

The surface of the fluororubber molded article treated by the plasma irradiation is shown in FIG. 1 for the fluororubber molded article according to Example 1, FIG. 2 for the fluororubber molded article according to Example 2, and FIG.
Each electron micrograph of the fluororubber molded article according to Example 10 is shown in Fig. 1, where recesses having a number average diameter of 2.0 µm or less are 1 mm ^2.
There are 50,000 or more, especially 70,000 or more per one, and such minute irregularities cause non-adhesiveness.

It should be noted that fine particles such as decomposition products may adhere to the surface of the fluororubber molded product due to plasma irradiation.
When the fluororubber molded product is used as a sealing material or the like, these may become sources of contamination. Therefore, it is preferable to wash the fluororubber molded product after plasma irradiation.
The washing method is not limited, but a method of immersing the fluororubber molded article in a solvent such as ethanol, propanol, or water, a method of adding stirring or ultrasonic waves to the solvent immersion, or a fluororubber molded article of the solvent. Examples thereof include a method of flowing or spraying on the surface of, and a method of wiping the surface of the fluororubber molded article. Particularly, a cleaning method in which stirring or ultrasonic waves is added to the solvent immersion is a simple and effective cleaning method. Further, for the purpose of keeping the plasma irradiation device clean, it is preferable to perform similar cleaning before plasma irradiation.

Further, it is more preferable to perform ultrapure water cleaning and / or heat treatment at 150 ° C. or higher in an inert gas atmosphere after the cleaning. Thereby, the low molecular weight component (adhesive component) in the fluororubber molded product, the cross-linking agent residue, molding
It is possible to remove the solvent and the like mixed during the washing.

For washing with ultrapure water, water having a specific resistance value of 10 ⁵ Ω · cm or more, particularly 10 ⁶ Ω · cm or more, from which fine particles, metal ions, viable bacteria, organic substances, dissolved oxygen, etc. are highly removed is used. Do it. There is no limitation on the washing method, and any method such as a batch method or a continuous method can be adopted. Preferably 50
It is preferable to adopt a method of immersing in ultrapure water at a temperature of not lower than 80 ° C., particularly not lower than 80 ° C., for 10 seconds or longer, and particularly for 1 minute or longer. Also,
Heating in an inert gas atmosphere is carried out in an atmosphere of nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or the like at 150 ° C. or higher, preferably 180 to 250.
C., especially 200 to 250.degree. C. for 10 minutes to 100 hours,
It is particularly preferable to hold for 1 to 50 hours. By such cleaning with ultrapure water and heat treatment in an inert gas, the amount of gas released from the fluororubber molded article can be reduced to 0.5 ppm or less, particularly 0.1 ppm or less.

Since the fluororubber molded product of the present invention has the above-mentioned characteristics, it is a semiconductor manufacturing apparatus provided with a sealing material for a vacuum container, a sealing material for a wafer transfer container, and a portion that is frequently opened and closed, for example, a highly automated semiconductor. It is most suitable as a sealing material for manufacturing equipment. The present invention also includes a seal material for a semiconductor manufacturing apparatus, a wafer transport container seal material, and a vacuum container seal material, which are formed of the above-mentioned fluororubber molded product.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

(Examples 1 and 2, Comparative Example 1) Aflas 10
OH (tetrafluoroethylene / propylene copolymer manufactured by JSR Corp. and Asahi Glass Co., Ltd., containing a double bond as a cross-linking site) was kneaded at about 100 ° C. with a biaxial roll,
It was dispensed into a sheet having a thickness of 2.2 mm. Place this in a mold at 200 ℃ and heat press at 200 ℃ for 5 minutes for 100kg.
After pressurizing at f / cm ² , cool down to 150 × 150 × 2m
m sheets were molded.

Four 32 × 10 × 2 mm test pieces were punched from each of the obtained sheets and irradiated with plasma under the conditions shown in Table 1 (however, in Comparative Example 1, no plasma irradiation). As a plasma irradiation device, "Compact Etcher FA-" manufactured by Samco International Laboratories, Inc.
1 ”was used and the gas flow rate was 20 ml / min. Table 1 also shows the amount of reduction in weight per exposed area after plasma irradiation (average value of 4 bodies).

Further, in order to evaluate the tackiness, a tensile shearing test according to JIS K6854 was performed using three test pieces after plasma irradiation. That is, each of the three pairs of test pieces is sandwiched between two 2.5 mm-thick aluminum plates, and the whole is S
It is sandwiched between US plates and compressed by 25%, and it is held at 200 ° C for 22 hours. After decompressing and allowing to cool, the upper and lower aluminum plates are 100 ml.
Adhesive strength (MPa) by pulling in opposite directions at a speed of / min and dividing the load required for peeling by the adhesive area (320 mm ² ).
Was calculated. The test results (median value of 3 bodies) are also shown in Table 1.

An electron micrograph was taken of the remaining one body. FIG. 1 is an electron micrograph (500 times) of the test piece of Example 1, and FIG. 2 is an electron micrograph (500 times) of the test piece of Example 2, showing that a large number of fine irregularities are formed on the entire surface. I understand. On the other hand, FIG. 3 shows an electron micrograph (500 times) of the test piece of Comparative Example 1, but the surface is not formed with fine irregularities like the test pieces of Example 1 and Example 2. Then, image analysis was performed on these electron micrographs to measure the diameter distribution of the dark portion (recess). Here, the diameter is 2 × (dark area / π) ^1/2 , and the average diameter is calculated by number average. As analysis software, "Image-ProPLUS" manufactured by Planetron Co., Ltd.
It was used. The results are shown in Table 1 together with the median value of 3 points. The test piece of Comparative Example 1 did not show fine irregularities, and the diameter of this dark portion could not be measured.

(Examples 3 to 4, Comparative Examples 2 to 3) Example 1
The 150 × 150 × 2 mm sheet obtained by the same operation as in (1) was irradiated with γ-rays of 120 kGy in a nitrogen gas atmosphere to crosslink. Next, from this crosslinked sheet, 32 × 10 ×
Four 2 mm test pieces were punched out and irradiated with plasma under the conditions shown in Table 1 (however, in Comparative Example 3, no plasma irradiation). Then, the same physical property measurements as in Example 1 were performed. The results are also shown in Table 1. For Comparative Examples 2 and 3, the diameter of the dark part could not be measured.

[0041]

[Table 1]

As shown in Table 1, in accordance with the present invention, a non-equilibrium plasma of saturated fluorocarbon gas or high frequency power 100
It is clear that irradiation with a nonequilibrium oxygen plasma of W or higher imparts excellent nontackiness. In particular,
When irradiated with a non-equilibrium saturated fluorocarbon gas (CF ₄ ), excellent non-adhesiveness (peeling immediately after decompression) is imparted without much weight reduction due to etching, and among them, gamma rays Cross-linked test piece (Example 4)
The effect is remarkable in.

(Examples 5-6, Comparative Example 4) Aflas 10
100 parts by weight of OH, 2 parts by weight of 2,2-dimethyl-2,5-bis (t-butylperoxy) hexane, and 2 parts by weight of triallyl cyanurate (peroxide crosslinking aid) are twin-rolled. I kneaded it. This kneaded product is placed in a mold at 170 ° C, and 200 kg for 15 minutes at 170 ° C hot press.
After pressurizing at f / cm ² , cool down to 150 × 150 × 2m
m sheets were molded. Then, this sheet was subjected to secondary crosslinking in an oven at 150 ° C. for 4 hours. Four 32 × 10 × 2 mm test pieces were punched out from the obtained sheet and irradiated with plasma under the conditions shown in Table 2 (however, in Comparative Example 4, no plasma irradiation), and the same physical properties as in Example 1 were obtained. The measurement was performed. The results are also shown in Table 2. In Comparative Example 4, the diameter of the dark area could not be measured.

(Examples 7-9, Comparative Example 5) Florel F
100 parts by weight of LS-2650 (vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer manufactured by Sumitomo 3M Ltd.) and 5 parts by weight of magnesium oxide,
3 parts by weight of α, α′-bis (t-butylperoxy) diisopropylbenzene and 2 parts by weight of triallyl isocyanurate were kneaded with a biaxial roll. 16 of this kneaded material
Place in a mold at 0 ℃, heat press at 160 ℃ for 10 minutes,
After pressurizing at 200 kgf / cm ² , cool down to 150 x 1
A 50 x 2 mm sheet was molded. Then, this sheet was subjected to secondary crosslinking in an oven at 200 ° C. for 4 hours.
Four 32 × 10 × 2 mm test pieces were punched from each of the obtained sheets and irradiated with plasma under the conditions shown in Table 2 (however, in Comparative Example 5, no plasma irradiation), and the same physical properties as in Example 1 were obtained. The measurement was performed. The results are also shown in Table 2. In Comparative Example 5, the diameter of the dark part could not be measured.

[0045]

[Table 2]

As shown in Table 2, the crosslinked test piece was irradiated with a non-equilibrium plasma of a saturated fluorocarbon gas or a non-equilibrium oxygen plasma having a high frequency output of 100 W or more according to the present invention. It is clear that tackiness is imparted. In addition, saturated fluorocarbon gas (C
When irradiated with F ₄ ) non-equilibrium plasma, excellent non-tackiness is imparted without much weight reduction due to etching.

(Examples 10 to 14 and Comparative Example 6) 100 parts by weight of Florel FC-2145 (vinylidene fluoride / hexafluoropropylene copolymer manufactured by Sumitomo 3M Ltd.), 5 parts by weight of magnesium oxide, and carbon 30 parts by weight of black (MT), 2 parts by weight of a polyol-based crosslinking aid (curative 20, main component: triphenylbenzylphosphonium salt), and 4 parts by weight of a polyol-based crosslinking material (curative 30, main component: bisphenol AF) Was kneaded with a biaxial roll. This kneaded material is placed in a mold at 200 ° C., and hot pressed at 200 ° C. for 15 minutes to obtain 200 kgf.
After pressurizing at / cm ² , cool down to 150 × 150 × 2mm
Sheet was molded. Then, this sheet was subjected to secondary crosslinking in an oven at 200 ° C. for 20 hours. Four 32 × 10 × 2 mm test pieces were punched from each of the obtained sheets and irradiated with plasma under the conditions shown in Table 3 (however, in Comparative Example 6, no plasma irradiation), and the same physical properties as in Example 1 were obtained. The measurement was performed. The results are also shown in Table 3. Also, FIG.
The electron micrograph (500 times) of the test piece of Example 10 is shown in FIG. 7, but it can be seen that, like the test pieces of Example 1 and Example 2, fine irregularities are formed on the entire surface. In Comparative Example 6, the diameter of the dark part could not be measured.

Separately from the sheet after the secondary crosslinking, JI
A No. S6 dumbbell was punched out, irradiated with the same plasma, and then subjected to a tensile test according to JIS K6251. The results are also shown in Table 3.

Separately from the sheet after the secondary cross-linking, 32
After punching out a test piece of × 10 × 2 mm and performing the same plasma irradiation, pure water of 90 to 95 ° C. (specific resistance value of about 18 M
Ω · cm) was immersed in 500 ml for 10 minutes. During this immersion, the same pure water as above was continuously added at a rate of 100 ml / min. Then, the test piece was taken out, and nitrogen (purity 9
200% in an oven replaced with
Hold at 12 ° C for 12 hours. During this period, the same nitrogen gas as above was continuously supplied to the oven at a rate of 5 liters / minute.
With respect to the test piece thus treated, the amount of released gas was measured by purge & trap-gas chromatograph mass spectrometry. The heating condition at the time of measurement is 100 ° C. for 30 minutes,
Helium was used as the purge gas. In addition, n-decane was used as a standard substance at the time of quantification. The measurement results are also shown in Table 3.

Comparative Example 7 Four sheets of 32 × 10 × 2 mm test pieces were punched out from the sheet before secondary cross-linking produced by the same operation as in Example 10, and a surface treatment agent (Shinko Giken Co., Ltd.) was punched on the surface. "SAT-500F" (main component: isocyanate silane) was applied, air-dried, and then heat-treated at 70 ° C for 30 minutes. Physical properties similar to those in Example 10 were measured for the treated test pieces. The results are also shown in Table 3.

(Comparative Example 8) "ST-1" made by Dupont Dow Elastomer (containing a crosslinking agent for fluorine rubber and an accelerator)
Was diluted to 2 volumes with an acetone / methanol (1: 1) mixed solvent to prepare a surface treatment solution. 32 × 10 × 2 m from the sheet before secondary cross-linking produced by the same operation as in Example 10
Four test pieces of m were punched out, and 3 pieces were put in this surface treatment solution.
Soak for 0 minutes. After the immersion, it was air-dried for 16 hours, further heated and dried in an oven at 120 ° C. for 2 hours, and then heat-treated at 200 ° C. for 20 hours. Physical properties similar to those in Example 10 were measured for the treated test pieces. The results are also shown in Table 3.

[0052]

[Table 3]

As shown in Table 3, the crosslinked test piece was irradiated with non-equilibrium plasma of saturated fluorocarbon gas or non-equilibrium oxygen plasma having a high frequency output of 100 W or more in accordance with the present invention. It is clear that tackiness is imparted. In addition, saturated fluorocarbon gas (C
When irradiated with F ₄ ) non-equilibrium plasma, excellent non-tackiness is imparted without much weight reduction due to etching. It is also understood that the plasma irradiation has little influence on the tensile strength and the like.

Furthermore, in addition to being superior in non-tackiness as compared with the case of using a commercially available surface treatment agent, the amount of released gas is also small.

[0055]

As described above, by irradiating the fluororubber molded article with a specific plasma according to the present invention, excellent non-adhesiveness can be imparted without lowering the mechanical strength. Provided is a fluororubber molded article suitable as a sealing material for a semiconductor manufacturing apparatus, a wafer transfer apparatus, and a vacuum container.

[Brief description of drawings]

FIG. 1 is an electron micrograph (500 times) of the surface of a test piece of Example 1.

2 is an electron micrograph (500 times) of the surface of the test piece of Example 2. FIG.

FIG. 3 is an electron micrograph (500 times) of the surface of the test piece of Comparative Example 1.

4 is an electron micrograph (500 times) of the surface of the test piece of Example 10. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29L 31:26 C08L 27:12 C08L 27:12 B65D 85/38 RF term (reference) 3E096 BA16 BB03 DA30 EA07Y FA03 GA07 4F073 AA05 BA15 BB02 CA01 4F209 AA16 AB03 AE10 AG05 AH33 AK03 PA14 PB01 PC03 PC05 PH02

Claims (9)

[Claims] 1. A molded product made of a fluororubber or a fluororubber composition, wherein the surface has 50,000 or more recesses having a number average diameter of 2.0 μm or less per 1 mm ^2. Molded body. 2. An aluminum plate at 200 ° C. for 22 hours,
Shear tensile adhesive strength after compression by 25% is 1.0 MPa
The fluororubber molded article according to claim 1, wherein: 3. The fluororubber molded article according to claim 1, wherein the fluororubber or fluororubber composition molded article is a cross-linked product. 4. A detackifying treatment for a fluororubber molded article, which comprises irradiating a crosslinked or uncrosslinked molded article made of fluororubber or a fluororubber composition with non-equilibrium plasma of saturated fluorocarbon gas. Law. 5. A high-frequency output 10 is applied to a crosslinked or uncrosslinked molded article made of fluororubber or a fluororubber composition.
A method for detackifying a fluororubber molded article, which comprises irradiating a nonequilibrium oxygen plasma of 0 W or more. 6. A fluororubber molded article, which has been surface-treated by the detackifying treatment method according to claim 4 or 5. 7. A sealing material for semiconductor manufacturing equipment, comprising the fluororubber molded article according to claim 3 or 6. 8. A sealing material for a wafer transfer container, comprising the fluororubber molded article according to claim 3 or 6. 9. A sealant for a vacuum container, comprising the fluororubber molded article according to claim 3 or 6.