JP2001288320A - Aqueous composition for fluororubber vulcanization and fluororubber coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous composition for fluororubber vulcanization, capable of forming a film having affinity for a silicone oil. SOLUTION: This aqueous composition for fluororubber vulcanization comprises a substance having affinity for a silicone oil such as a silicone rubber powder suspension, a silicone oil modified with a hydrophilic group, a silica colloid, etc., a fluororubber and a vulcanizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous composition for vulcanization of fluororubber and a coated article, and more particularly to a substance which is capable of forming a silicone oil-philic substance and, if desired, a silicone oil-adsorbing void in a film. The present invention relates to an aqueous composition for vulcanizing a fluororubber, comprising the composition, and an article having a film formed from such a composition.

[0002]

2. Description of the Related Art Silicone rubber is generally used as a roll base material used in office automation (OA) equipment (for example, copying machines, printers, etc.). Silicone oil may be applied to the surface of such a roll for OA equipment in order to impart durability and non-adhesion. For the same purpose, fluororubber and / or
Alternatively, a film may be formed from a fluororesin composition. However, since a film formed from fluororubber or fluororesin is hardly wetted by silicone oil, it has been difficult to further improve durability and non-adhesion by using both of these means in combination.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous composition for vulcanizing a fluororubber which can form a film having a silicone oil-philic property. Another object of the present invention is to provide an article having a film formed from such a composition, especially a roll for OA equipment which has a surface layer formed of fluororubber but is easily wetted by silicone oil. That is.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to provide a fluororubber vulcanizate comprising a fluororubber, a vulcanizing agent, a silicone-lipophilic substance and, if desired, a substance capable of forming a silicone oil-adsorbing void in the film. The problem is solved by an aqueous composition for use and an article having at least a part of its surface coated with a coating layer formed from the composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Each component contained in the composition of the present invention will be specifically described below. (A) Fluororubber Fluororubber is usually supplied as an aqueous dispersion. The fluororubber aqueous dispersion is obtained by dispersing fluororubber in water at a concentration of 10 to 75% by weight in the presence of a surfactant. Fluororubber refers to-
It is a fluorinated copolymer containing a repeating unit represented by CH ₂ —. A typical example is an elastic fluorinated copolymer containing vinylidene fluoride, and more specifically, a copolymer whose main chain contains a repeating unit having the following structure.

## STR1 ## _{-CF 2 -CH 2 -, - CH} 2 -CH 2 -, and -CH ₂ -CH (CH ₃₎ - at least one repeating unit selected from, and,

## STR2 ## _{-CF 2 -CF (CF 3) -} , - CF 2 -CF 2 -,
And -CF ₂ -CF (ORf) - (wherein, Rf is a perfluoroalkyl group having 1 to 6 carbon atoms.) At least one repeating unit selected from.

More specifically, a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and tetrafluoroethylene and hexafluoropropylene, a copolymer of ethylene and hexafluoropropylene, and a copolymer of tetrafluoroethylene And a propylene copolymer. Among them, a vinylidene fluoride copolymer is preferred in view of crosslinkability.

The amount of the fluorine rubber (solid content) contained in the composition of the present invention is 1 to 500 parts by weight, preferably 5 to 300 parts by weight, more preferably 10 to 100 parts by weight of water.
１５０150 parts by weight.

(B) Vulcanizing Agent and Vulcanization Accelerator The vulcanizing agent used in the aqueous composition for vulcanizing a fluororubber of the present invention may be any of known polyamine vulcanizing agents and polyol vulcanizing agents. The polyamine vulcanizing agent has better affinity with silicone oil.

The polyamine vulcanizing agent has the formula:

Embedded image (Wherein, R ¹ is a methyl group or an ethyl group, X is a single bond,
_{-C 2 H 4 NH -, -} CONH-, or -C ₂ H ₄ NH-
C ₂ H ₄ NH—NH—, and y is 2 or 3. )
Or a partial or complete hydrolyzate thereof, or a compound represented by the formula:

Embedded image (Wherein R ² , R ³ and R ⁴ are the same or different, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an amino group, a polyamino group, or at least one hydrogen atom is substituted with an amino group or a polyamino group) Represents an alkyl group having 1 to 6 carbon atoms, provided that at least two of R ² , R ³ and R ⁴ have an amino group or at least one of R ² , R ³ and R ⁴ A polyamino group is present).

The polyol vulcanizing agent includes a compound having at least two hydroxyl groups, particularly a phenolic hydroxyl group in a molecule, and a high molecular compound having vulcanizing performance.

For example,

Embedded image Phenolic compounds, such as

Formula:

Embedded image (Where Y is a hydrogen atom, a halogen atom, R ⁵ , CH ₂ OR
⁵ or OR ⁵ , Z is —CH ₂ — or —CH ₂ OCH
₂ -, R ⁵ is an alkyl group having 1 to 4 carbon atoms, n represents 0 to 100
Represents an integer. )) And a salt of a phenolic resin and a basic compound.

The basic compound includes ammonium salts,
Tertiary amines, phosphonium salts, alkali metals and alkaline earth metals, and the like. Specific examples of ammonium salts include trimethylbenzylammonium, triethylbenzylammonium, dimethyldecylbenzylammonium, triethylbenzylammonium, myristylbenzyldimethylammonium, dodecyltrimethylammonium, dimethyltetradecylbenzylammonium, trimethyltetradecylammonium, coconut trimethylammonium, Examples include stearyltrimethylammonium, distearyldimethylammonium, tetrabutylammonium, 1,4-phenylenedimethylenebistrimethylammonium, 1,4-phenylenedimethylenebistriethylammonium, and ethylenebistriethylammonium.

Specific examples of the tertiary amine include 1,8-diaza-bicyclo [5.4.0] -undecene-7 and 8-methyl-1,8-diaza-bicyclo [5.4.0] -undecene-7. , 8-propyl-1,8-diaza-bicyclo [5.4.0] -undecene-7, 8-dodecyl-1,8-
Diaza-bicyclo [5.4.0] -undecene-7,8-eicosyl-
1,8-diaza-bicyclo [5.4.0] -undecene-7, 8-tetracosyl-1,8-diaza-bicyclo [5.4.0] -undecene-7, 8-
Benzyl-1,8-diaza-bicyclo [5.4.0] -undecene-7,
8-phenethyl-1,8-diaza-bicyclo [5.4.0] -undecene
-7, 8- (3-phenylpropyl) -1,8-diaza-bicyclo [5.
4.0] -undecene-7, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine,
Triisobutylamine, methyldiethylamine, dimethylethylamine, dimethyl-n-propylamine, dimethyl-n-butylamine, dimethylisobutylamine, dimethylisopropylamine, dimethyl-sec-butylamine, dimethyl-tert-butylamine, triallylamine,
Diallylmethylamine, allyldimethylamine, benzyldimethylamine, benzyldiethylamine, N-allylpiperidine, N-ethylpiperidine, N-butylpiperidine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, Nn-butylpyrrolidine, N-ethylpyrrolidine, N-benzylpyrrolidine, 2,4,6-trimethylpyridine and the like can be mentioned.

Specific examples of the phosphonium salt include benzyltriphenylphosphonium, methyltriphenylphosphonium, 2,4-dichlorobenzyltriphenylphosphonium, 4-methylbenzyltriphenylphosphonium,
Chlorobenzyltriphenylphosphonium, m-trifluoromethylbenzyltriphenylphosphonium, 2-cyanobenzyltriphenylphosphonium, α-carbethoxybenzyltriphenylphosphonium, diphenylmethyltriphenylphosphonium, 1-naphthylmethyltriphenylphosphonium, carbethoxymethyl Triphenylphosphonium, methoxymethyltriphenylphosphonium, allyloxymethyltriphenylphosphonium, 1-
Carbethoxyethyltriphenylphosphonium, isobutyltriphenylphosphonium, 4-cyanobutyltriphenylphosphonium, 2-pentyltriphenylphosphonium, allyltriphenylphosphonium, tetraphenylphosphonium, methyltrioctylphosphonium, benzyltrioctylphosphonium, methoxyethoxyethyltri Octylphosphonium, butyltrioctylphosphonium, m-trifluoromethylbenzyltrioctylphosphonium, 2,2,3,3-tetrafluoropropyltrioctylphosphonium, 2,2,3,3,4,4,5,5-octa Fluoropentyltrioctylphosphonium, tetraoctylphosphonium, tetrabutylphosphonium and the like.

Specific examples of the alkali metal include lithium, sodium, potassium and the like. Specific examples of the alkaline earth metal include beryllium, magnesium, calcium, barium and the like. Among them,
Hydroquinone, bisphenol A, bisphenol A
F, a salt of a resol-type phenol resin with an ammonium salt or a tertiary amine is preferred in view of film properties. Hydroquinone, bisphenol A, bisphenol AF, and resol-type phenol resins are particularly preferable because of their excellent vulcanization performance. Also, ammonium salts and tertiary amines are
Unlike alkali metals and alkaline earth metals, it does not leave decomposition residues in the film.

When a polyol vulcanizing agent is used, the following compounds can be blended as a vulcanization accelerator, which is an optional component. Quaternary ammonium salt Formula:

Embedded image NR ⁶ ₄ X or _{^{R 6 3 NR 7 -NR 6 3}} · 2X ( wherein, R ⁶ is identical or different alkyl group having 1 to 20 carbon atoms, a halogenated C20 It represents an alkyl group, an aryl group having 6 to 20 carbon atoms, also more than one R ⁶
May together form a carbocyclic or heterocyclic ring. R ⁷ represents an alkylene group having 2 to 21 carbon atoms or a phenylenedialkylene group having 8 to 12 carbon atoms. X represents an acid group or a hydroxyl group. A quaternary ammonium salt represented by).

Specific examples of the acid group include halide, sulfate, sulfite, bisulfite, thiosulfate, sulfide, polysulfide, hydrogen sulfide, thiocyanate, carbonate, and the like.
Bicarbonate, nitrate, carboxylate, borate, phosphate, biphosphate, phosphite, perchlorate, bifluoride, arsenate,
Ferricyanide, ferrocyanide, molybdate,
Selenate, selenite, uranate, tongue state and the like can be mentioned.

Specific examples of the quaternary ammonium salt include:
The following compounds may be mentioned: trimethylbenzylammonium chloride, triethylbenzylammonium chloride, dimethyldecylbenzylammonium chloride, triethylbenzylammonium chloride, myristylbenzyldimethylammonium chloride, dodecyltrimethylammonium chloride, dimethyltetradecylbenzylammonium chloride, Trimethyltetradecylammonium chloride, coconut trimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, tetrabutylammonium hydroxide, 1,4-phenylenedimethylenebistrimethylammonium dichloride, 1,4-phenylenedimethylenebi Triethylammonium dichloride, alkyl and aralkyl quaternary ammonium salts such as ethylene bis-triethylammonium dibromide;

8-methyl-1,8-diaza-bicyclo [5.4.0] -7-
Undecenium chloride, 8-methyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium iodide, 8-methyl
-1,8-diaza-bicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diaza-bicyclo [5.4.0]-
7-undecenium-methyl sulfate, 8-methyl-1,8-
Diaza-bicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium bromide, 8-dodecyl-1,8-diaza- Bicyclo
[5.4.0] -7-undecenium chloride, 8-dodecyl-1,8
-Diaza-bicyclo [5.4.0] -7-undecenium hydroxide, 8-eicosyl-1,8-diaza-bicyclo [5.4.0]-
7-undecenium chloride, 8-tetracosyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride, 8
-Benzyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride, 8-benzyl-1,8-diaza-bicyclo [5.
4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride, 8- (3-phenylpropyl) -1,8-diaza- Quaternary 1, such as bicyclo [5.4.0] -7-undecenium chloride
8-diaza-bicyclo [5.4.0] -7-undecenium salt and the like.

Quaternary salts of tertiary amines with inorganic or organic acids

Tertiary amines represented by the embedded image NR ⁶ ₃ or _{^{R 6 2 NR 7 -NR 6 2}} ( wherein, R ⁶ and R ⁷ are as defined above.).

Specific examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triisobutylamine, methyldiethylamine, dimethylethylamine, and dimethylamine.
-n-propylamine, dimethyl-n-butylamine, dimethylisobutylamine, dimethylisopropylamine, dimethyl-sec-butylamine, dimethyl-tert-butylamine, triallylamine, diallylmethylamine, allyldimethylamine, benzyldimethylamine, benzyldiethylamine, N-allylpiperidine, N-ethylpiperidine, N-butylpiperidine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, Nn-butylpyrrolidine, N-ethylpyrrolidine, N-benzylpyrrolidine, 2,4,6-trimethylpyridine and the like No.

Examples of inorganic or organic acids which form quaternary salts include:

Embedded image HCl, HBr, HF, (C ₂ H ₅ ) ₃ NH ⁺ Cl ⁻ , (C ₂ H ₅ ) ₃ NH ⁺ NO ₃
^- , 2 (C ₂ H ₅ ) ₃ NH ⁺ SO ₄ ²⁻ , 2 (C ₂ H ₅ ) ₃ NH ⁺ CO ₃ ²⁻ , (C ₂ H ₅ ) ₃ NH ⁺ R
_{^{8 O -, (C 2 H}} 5) 3 NH + R 8 COO -, (C 4 H 9) 3 NH + Cl -, (C 4 H 9) 3 NH + NO
^{_{3 -, 2 (C 4 H}} 9) 3 NH + SO 4 2-, 2 (C 4 H 9) 3 NH + CO 3 2-, (C 4 H 9) 3 NH +
R ⁸ O ⁻ , (C ₄ H ₉ ) ₃ NH ⁺ R ⁸ COO ⁻ (wherein, R ⁸ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.) And the like. Primary or secondary amines are not preferred because reactions other than polyol vulcanization occur.

Quaternary phosphonium salt Formula:

Embedded image PR ⁶ ₄ X or _{^{R 6 3 PR 7 -PR 6 3}} · 2X ( wherein, R ^6, R ⁷ and X are as defined above.) Quaternary phosphonium salt represented by .

Specific examples of the quaternary phosphonium salt include:
Benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, methyltriphenylphosphonium methylmethanephosphonate, bis
(Benzyldiphenylphosphine) iminium chloride, 2,4-dichlorobenzyltriphenylphosphonium chloride, 4-methylbenzyltriphenylphosphonium chloride, 4-chlorobenzyltriphenylphosphonium chloride, m-trifluoromethylbenzyltriphenylphosphonium chloride, 2 -Cyanobenzyltriphenylphosphonium bromide, α-carbethoxybenzyltriphenylphosphonium bromide, diphenylmethyltriphenylphosphonium chloride, 1-naphthylmethyltriphenylphosphonium chloride, carbethoxymethyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, Ali Roxymethyltriphenylphosphonium chloride,
1-carbethoxyethyltriphenylphosphonium chloride, isobutyltriphenylphosphonium bromide, 4-cyanobutyltriphenylphosphonium bromide, 2-pentyltriphenylphosphonium bromide,
Allyl triphenyl phosphonium chloride, tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, methyl trioctyl phosphonium chloride, methyl trioctyl phosphonium tetrafluoroborate, methyl trioctyl phosphonium acetate, methyl trioctyl phosphonium dimethyl phosphate, benzyl trioctyl phosphonium chloride, benzyl Trioctylphosphonium bromide, methoxyethoxyethyltrioctylphosphonium chloride, butyltrioctylphosphonium bromide, m-
Trifluoromethylbenzyltrioctylphosphonium chloride, 2,2,3,3-tetrafluoropropyltrioctylphosphonium chloride, 2,2,3,3,4,4,5,5-octafluoropentyltrioctylphosphonium chloride, tetra Octylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and the like can be mentioned.

Organic Acid In the present invention, an organic acid can be added to the composition for the purpose of further improving the storage stability. As the organic acid, an organic acid having 1 to 12 carbon atoms, preferably an organic acid having 1 to 4 carbon atoms is used. Organic acids having more than 12 carbon atoms are undesirable because they remain in the film. More preferred organic acids are monocarboxylic acids such as formic acid, acetic acid and propionic acid, and dicarboxylic acids such as oxalic acid, malonic acid and succinic acid.
The organic acid inhibits polyol vulcanization of the fluorinated copolymer contained in the composition during storage. However, applying the composition,
When dried and calcined, the organic acid is evaporated or thermally decomposed, and the basic compound accelerates the vulcanization reaction. Therefore, the organic acid can also be included in the “vulcanization accelerator”.

In the case of the polyamine vulcanization system, the mixing ratio of each component in the composition of the present invention is 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the fluororubber. It is. In the case of a polyol vulcanization system, based on 100 parts by weight of fluororubber, 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, of a basic polyol-based vulcanization agent, 0 to 10 parts by weight of a vulcanization accelerator, preferably 0.01 ~
5 parts by weight. If the amount of the vulcanization accelerator is less than the above lower limit, vulcanization hardly occurs, while if it exceeds the upper limit, vulcanization control may be difficult.

(C) Substance Having a Silicone-Lipophile Substance and a Substance That Can Form Silicone Oil-Adsorbing Voids in a Film According to the present invention, a silicone-lipophilic substance is compounded in an aqueous composition for vulcanization of fluororubber. Therefore, it is possible to form a film that is easily wetted by silicone oil.
Examples of the silicone-lipophilic substance used in the present invention include silicone compounds such as silicone rubber powder suspension, hydrophilic silicone oil and silica colloid.

Conventionally, as a silicone compound to be compounded in an aqueous composition for vulcanizing fluororubber, Japanese Patent Publication No. 58-53
No. 671 and Japanese Patent Publication No. 62-35432 propose silica as a filler. However, silica in these prior arts refers to those usually used in the processing of fluororubber, that is, those usually blended in a fluororubber compound, and has an average particle size of 1 μm or more. Because it is difficult to uniformly disperse silica having such a particle size in the aqueous composition for vulcanizing a fluororubber, such silica is not referred to as a silicone-lipophilic substance in the present invention.

The silicone oil-philic substance used in the present invention includes a silicone rubber powder suspension in which a silicone rubber powder having an average particle diameter of 10 μm or less is dispersed in water, an alcohol-modified silicone oil having a hydrophilic group, and a polyether-modified silicone oil. , Average particle size 50
It refers to a silica colloid in which silica of nm or less is dispersed in water. These substances require that crystals and decomposition residues remain after the calcination of the fluororubber described in (A), and it is considered that these substances have an affinity for silicone oil.

Further, in addition to the silicone oil-philic substance, a substance capable of forming a silicone oil-adsorbing void may be added to the aqueous composition for vulcanizing a fluororubber, or a substance which is easily wetted by the silicone oil may be formed. Is valid. As the substance capable of forming a silicone oil-adsorbing void in the film, a substance having a melting point higher than the melting point of the fluorinated molten resin, and further having an affinity with the fluorinated molten resin, for example, a non-melting fluororesin, preferably Polytetrafluoroethylene (PTFE), modified PTFE, and the like can be used. Such a non-melting fluororesin creates a void inside or on the surface of the film when vulcanizing the fluororubber, and the void on the surface of the film adsorbs the silicone oil, so that the film is easily wetted by the silicone oil. It is considered something. A substance capable of forming a silicone oil-adsorbing void in the film is usually incorporated into the composition as a dispersion.

The mixing ratio of the silicone rubber powder is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the fluororubber. The mixing ratio of the silicone oil is 0.1 to 5 parts by weight per 100 parts by weight of the fluoro rubber.
0 parts by weight, preferably 1 to 20 parts by weight. The mixing ratio of the silica colloid is based on 100 parts by weight of the fluoro rubber.
0.1 to 30 parts by weight, preferably 1 to 10 parts by weight. These substances may be used alone or in combination of two or more. When two or more kinds are compounded, the total amount of the silicone-lipophilic substance is 0.1 to 50 parts by weight, based on 100 parts by weight of the fluororubber,
Preferably it is 3 to 20 parts by weight. If the amount is less than the above lower limit, the silicone oil-philicity of the formed film decreases, while if the amount exceeds the upper limit, the surface smoothness of the film may be lost.

The compounding ratio of a substance capable of forming a silicone oil-adsorbing void in the film, for example, PTFE is 0.01 to 500 parts by weight, preferably 0.1 to 200 parts by weight, per 100 parts by weight of the fluororubber. is there.

(D) Fluororesin and terminal-modified perfluoropolyether To improve the heat resistance and abrasion resistance of the resulting film,
The composition of the present invention may be blended with a fluororesin and / or a terminal-modified perfluoropolyether. Specific examples of the fluororesin include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer (EPA), and tetrafluoroethylene- Hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), terminal-modified EPA, terminal-modified FE
P, terminally modified PFA and the like.
More than one species can be used. The fluororesin is preferably used in the form of an aqueous dispersion from the viewpoint of dispersibility.

The terminal-modified perfluoropolyether used in the present invention has a compound represented by the formula:

Embedded image-(CF (CF ₃ ) CF ₂ O)-,-(CF ₂ O)
-,-(CF ₂ CF ₂ O)-, and-(CF ₂ CF ₂ CF
_It comprises at least one type of repeating unit selected from the group consisting of repeating units represented by 2O)-, and the sum of the repeating units is in the range of 1 to 1,000.

Modify the molecular end of perfluoropolyether
The functional groups that can be used include Cl, Br, I, NR⁹R
^Ten(Where R⁹And R^TenIndependently represent a hydrogen atom, an ant
Group, C ₁~ C_TenAlkyl group or cycloalkyl
Represents a group. ), SH, NCO, NO_Two, COOH, PO_Two
H, SO_ThreeH, OH, glycidyl group or hydroxy
And phenyl. These functional groups are
At the terminal of either the main chain or the side chain of the fluoroalkyl group
There may be. These functional groups are
Directly into the main chain consisting of repeating units of fluoropolyether
Combine or the expression:

Embedded image-(CH ₂ ) _n -,-(CF ₂ ) _n -,-(CH ₂ O) _n
— Or — (CF ₂ O) _n — (wherein, 1 ≦ n <100) and the bond is established.

(E) Various additives In addition to the above-mentioned components, the composition of the present invention contains various additives commonly added to a fluororubber composition, such as a filler, a colorant, and an acid acceptor. can do. Examples of the filler include carbon black, calcium carbonate, barium sulfate, and the like, and examples of the colorant include an inorganic pigment and a composite oxide pigment. Examples of the acid acceptor include double salts such as magnesium oxide, lead oxide, zinc oxide, lead carbonate, zinc carbonate, and hydrotalcite, and when a highly active substance such as calcium hydroxide is used, the composition gels. This is not preferred because it is easy to cause Further, the basic compound
Compounds having a pKa lower than the pKa are preferred. If the pKa of the acid acceptor is large, the composition tends to gel. Usually, the acid acceptor can be blended in an amount of 1 to 40 parts by weight based on 100 parts by weight of the fluorine-containing copolymer depending on its activity.

A silicone rubber is generally used for a roll base material used in office automation (OA) equipment, and a silicone oil is applied to the surface thereof for the purpose of imparting durability and non-adhesiveness. Alternatively, a film made of a fluororubber and / or a fluororesin composition is formed. However, since a film formed from fluororubber or fluororesin is hardly wetted by silicone oil, it has been difficult to further improve durability and non-adhesion by using both of these means in combination. However, since the film formed from the composition of the present invention is easily wetted by silicone oil, it is possible to greatly improve the durability and non-adhesiveness of the film by using it in combination with silicone oil.

The composition of the present invention can be applied and vulcanized by the same method as the conventional composition for vulcanizing a fluorine-containing copolymer. That is, brush coating, spray coating, dip coating, flow coating,
Apply to the substrate by dispenser coating, screen coating, etc.
Bake at 0-300 ° C for 10-120 minutes. It is preferable that the surface of the article substrate (substrate) is sufficiently degreased and washed before applying the composition. In order to improve the adhesiveness between the article substrate and the composition, it is desirable to form a primer layer on the surface of the article to be coated with a silane-based primer, a silicone-based primer, or the like.

Examples of the article substrate coated with the composition of the present invention include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates and glass fiber woven and non-woven fabrics; Molded products and coatings of general-purpose and heat-resistant resins such as oxymethylene, polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone; SB
Molded articles and coatings of general-purpose rubbers such as R, butyl rubber, NBR and EPDM, and heat-resistant rubbers such as silicone rubber and fluorine rubber; woven and non-woven fabrics of natural and synthetic fibers;

The coating formed from the composition of the present invention can be used in fields requiring heat resistance, solvent resistance, lubricity, and non-adhesion. Specific applications include copying machines, printers, and facsimile machines. Rolls for OA equipment such as (for example,
Fixing belts, pressure rolls) and conveyor belts; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, engine gaskets, and the like.

[0042]

The present invention will be described below in detail with reference to examples. Example 1 Preparation of aqueous composition for vulcanizing fluororubber Aqueous composition for vulcanizing fluororubber (GL manufactured by Daikin Industries, Ltd.)
-252A solution) 100 parts by weight, silica colloid (Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.) 7 parts by weight, polyamine vulcanizing agent (GL-252B solution manufactured by Daikin Industries, Ltd.)
5 parts by weight were mixed and dispersed to prepare an aqueous composition for vulcanizing a fluororubber.

Formation of film: The prepared aqueous composition for vulcanization of fluororubber was spray-coated on an aluminum plate (A-1050), dried at 80 to 100 ° C. for 15 minutes, and dried.
Calcination was performed at 30 ° C. for 30 minutes to obtain a film having a thickness of about 20 μm.

Evaluation of silicone oil-philicity of the film: One drop of silicone oil (SH200-100, manufactured by Toray Dow Corning Silicone Co., Ltd.) was dropped on the surface of the obtained film, and a goniometer (manufactured by Kyowa Interface Science Co., Ltd.) was used. Was used to measure the contact angle.

Example 2 In the preparation of the aqueous composition for vulcanization of fluororubber, the procedure of Example 1 was repeated except that 4 parts by weight of silicone oil (SH3746 manufactured by Dow Corning Toray Silicone Co., Ltd.) was used instead of silica colloid. The procedure was repeated.

Example 3 A silicone rubber powder suspension (DY33-42 manufactured by Toray Dow Corning Silicone Co., Ltd.) was used instead of silica colloid in the preparation of the aqueous composition for vulcanizing fluororubber.
0M) The procedure of Example 1 was repeated except that 7 parts by weight were blended.

Example 4 A silicone rubber powder suspension (DY33-42 manufactured by Toray Dow Corning Silicone Co., Ltd.) was used instead of silica colloid in the preparation of the aqueous composition for vulcanizing fluororubber.
0M), and 5 parts by weight of a polyol vulcanizing agent (a 10% by weight aqueous solution of bisphenol AF ammonium salt) and a vulcanization accelerator (U-CAT manufactured by San Apro Co., Ltd.) in place of the polyamine vulcanizing agent. (SA610-50) 0.5
The procedure of Example 1 was repeated except that parts by weight were used.

Example 5 In the preparation of an aqueous composition for vulcanizing a fluororubber, a silicone rubber powder suspension (DY33-4 manufactured by Toray Dow Corning Silicone Co., Ltd.) was used instead of silica colloid.
20M) and the procedure of Example 1 was repeated except that 7 parts by weight of PTFE dispersion (molecular weight about 5 million) was mixed.

Comparative Example 1 The procedure of Example 1 was repeated except that no silica colloid was added in the preparation of the aqueous composition for vulcanizing fluororubber. Comparative Example 2 In the preparation of the aqueous composition for vulcanization of fluororubber, no silica colloid was blended, and instead of a polyamine vulcanizing agent, a polyol vulcanizing agent (bisphenol AF ammonium salt 1) was used.
The procedure of Example 1 was repeated except that 5 parts by weight of a 0% by weight aqueous solution) and 0.5 parts by weight of a vulcanization accelerator (U-CAT SA610-50 manufactured by San Apro Co., Ltd.) were used.

Table 1 shows the above results.

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08J 7/04 CEZ C08J 7/04 CEZ 4J035 C08K 3/36 C08K 3/36 4J038 5/17 5/17 C08L 71/00 C08L 71/00 Z 83/04 83/04 C09D 127/12 C09D 127/12 171/00 171/00 Z 183/04 183/04 F16C 13/00 F16C 13/00 A // G03G 15/20 103 G03G 15/20 103 (72) Inventor Seitaro Terasaka 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Seisakusho (72) Inventor Yasutoshi Nakaya 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industrial Co., Ltd. F term in the Yodogawa Plant (reference) 2H033 BB01 BB05 BB06 BB08 BB28 3J103 AA02 FA12 GA02 GA57 GA58 GA60 GA66 HA03 HA43 HA53 4F006 AA02 AA04 AA12 AA14 AA18 AA31 AA32. AA09 BA00 BC00 BD04 BD05 BD06 BD07 4J035 BA02 CA01K CA01U CA04M CA06M CA07M FB01 LA08 LB01 4J038 CB031 CB091 CD111 CD112 CD121 CD122 CD131 CD132 CE052 DA062 DA082 DB292 DF012 DL032 DL052 DL082 GA02 GA03 GA09 MA08 MA10 MA14 NA02 PA19 PB09

Claims (10)

[Claims] 1. An aqueous composition for vulcanization of a fluororubber comprising a fluororubber, a vulcanizing agent and a silicone-philic substance. 2. The fluororubber vulcanizing aqueous composition according to claim 1, wherein the silicone oil-philic substance is a silicone rubber powder suspension in which a silicone rubber powder having an average particle size of 10 μm or less is dispersed. 3. The aqueous composition for vulcanizing fluororubber according to claim 1, wherein the silicone oil-philic substance is a silicone oil modified with a hydrophilic group. 4. The substance having an average particle size of 5 having a silicone oil-philic substance.
2. The fluororubber vulcanizing aqueous composition according to claim 1, which is a silica colloid in which silica having a diameter of 0 nm or less is dispersed. 5. The fluororubber vulcanizing aqueous composition according to claim 1, further comprising a substance capable of forming a silicone oil-adsorbing void in the film. 6. The material capable of forming a silicone oil-adsorbing void in a film is a non-melting fluororesin.
The aqueous composition for vulcanization of a fluororubber according to the above. 7. The aqueous composition for vulcanizing a fluororubber according to claim 1, wherein the vulcanizing agent is a polyamine vulcanizing agent. 8. The aqueous composition for vulcanizing a fluororubber according to claim 1, further comprising a fluororesin and / or a terminal-modified perfluoropolyether. 9. An article, the surface of which is at least partially covered with a coating layer formed from the composition according to claim 1. Description: 10. The article according to claim 9, which is a roll for office automation equipment.