JP2002012725A - Aqueous composition for vulcanizing fluororubber and fluororubber coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous composition for vulcanizing fluororubber capa ble of producing a coating having heat-resistant, wear-resistant, and flexible. SOLUTION: The aqueous composition for vulcanizing fluororubber comprises fluororubber, a fluorine-containing block copolymer having an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine- containing polymer chain segment, a vulcanizing agent, and water.

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 vulcanizing a fluororubber and an article coated with a fluororubber, and more particularly, to an aqueous composition for vulcanizing a fluororubber containing a specific fluorine-containing multi-segmented polymer and the same. An article having a coating formed from such a composition.

[0002]

2. Description of the Related Art Aqueous compositions for vulcanizing fluororubber utilize the excellent flexibility, heat resistance, weather resistance, oil resistance, solvent resistance and chemical resistance of fluororubber, and are used for fabrics, fibers, metals and the like.
It is widely used as an industrial material by being applied or impregnated on plastic, rubber and other various substrates.

[0003] By taking advantage of these features, aqueous compositions for vulcanizing fluororubber are often used as surface coating materials for rolls used in office automation (OA) equipment (eg, copiers, printers, etc.). . However, in recent years, high-speed or colorization of OA equipment has progressed, and rolls coated with the conventional aqueous composition for vulcanizing fluororubber are not sufficient in terms of heat resistance and abrasion resistance. .

As a roll having excellent durability, a roll coated with a PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer) tube is known, but this roll has a drawback of poor flexibility, and is particularly disadvantageous in color. It was difficult to sufficiently melt and color the toner.

On the other hand, in order to improve the durability of a coating formed from the aqueous composition for vulcanizing a fluororubber and to impart non-stickiness to the surface, a fluororesin or a terminal-modified perfluoropolyether (terminal group having -NH _2, perfluoropolyether compound) be added, etc. has been proposed a functional group capable of reacting with fluorine rubbers such as -CH ₂ OH (e.g., JP-5
7-135871, JP-A-6-264221, etc.). However, since the heat resistance and abrasion resistance of fluororubber itself are higher than that of fluororesin, etc., if a large amount of fluororesin is blended in order to improve the heat resistance and abrasion resistance of the entire composition, flexibility will increase. Is impaired. Further, a composition obtained by blending a terminal modified perfluoropolyether or the like with a fluororubber has good non-adhesive properties, but does not sufficiently improve heat resistance and abrasion resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous composition for vulcanizing a fluororubber in which the resulting film has both heat resistance, abrasion resistance and flexibility. Another object of the present invention is to provide an article having a film formed from a conventional aqueous composition for vulcanizing a fluororubber, and a fluororubber-coated article which has solved the above-mentioned disadvantages of a conventional roll for OA equipment. That is.

[0007]

SUMMARY OF THE INVENTION According to the present invention, there is provided a fluorine-containing rubber, a fluorine-containing multi-segmented polymer having an elastomeric fluorine-containing polymer chain segment A and a non-elastomeric fluorine-containing polymer chain segment B, The problem is solved by a fluororubber vulcanizing aqueous composition comprising a sulfurizing agent and water, and an article having at least a part of its surface coated with a coating layer formed from the fluororubber vulcanizing aqueous composition. In a preferred embodiment, in the fluorinated multi-segmented polymer, the elastomeric fluorinated polymer chain segment A is capable of imparting flexibility to the entire fluorinated multi-segmented polymer, and has at least 90 mol% of its constituent units. Is a perfluoroolefin unit.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Each component contained in the composition of the present invention will be specifically described below. (I) Fluororubber Fluororubber is usually supplied as an aqueous dispersion. Fluororubber aqueous dispersion is a dispersion of fluororubber in water at a concentration of 10 to 75% by weight in the presence of a surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or alkyl sulfonate. It is a thing. The fluorine rubber, -CH ₂ in the main chain - is a fluorine-containing copolymer comprising a repeating unit represented by. 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.

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

Embedded image _{-CF 2 -CF (CF 3) -} , - CF 2 -CF 2 -, and -CF
₂ -CF (OR _f) - (wherein R _f 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 fluororubber 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 150 parts by weight based on 100 parts by weight of water.

(II) Vulcanizing Agent and Vulcanization Accelerator The vulcanizing agent used in the aqueous composition for vulcanizing fluororubber of the present invention may be any of conventionally known polyamine vulcanizing agents and polyol vulcanizing agents. However, a polyol-based vulcanizing agent is more preferable for obtaining a film having more excellent flexibility.

The polyamine vulcanizing agents include:

Embedded image (Wherein, R ¹ is a methyl group or an ethyl group, X ¹ 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,

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).

Examples of the polyol vulcanizing agent include compounds having at least two hydroxyl groups, particularly phenolic hydroxyl groups in the molecule, and high molecular compounds having vulcanizing performance. For example,

Embedded image Such as phenolic compounds,

[Formula 8] (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, and potassium.

Specific examples of the alkaline earth metal include beryllium, magnesium, calcium, barium and the like. Among them, hydroquinone, bisphenol A,
Bisphenol AF or a salt of a resole-type phenol resin with an ammonium salt or a tertiary amine is preferred from the viewpoint of film properties. Hydroquinone, bisphenol A, bisphenol AF, and resol-type phenol resins have particularly excellent vulcanization performance, and ammonium salts and tertiary amines do not leave decomposition residues in the film unlike alkali metals and alkaline earth metals.

When a polyol vulcanizing agent is used, the following compounds can be blended as a vulcanization accelerator, which is an optional component. (A) quaternary ammonium salt

Embedded formula: NR ⁶ ₄ X or _{^{R 6 3 NR 7 -NR 6 3}} · 2Y ( wherein, R ⁶ is identical or different alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms halogenated 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. Y 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:
Trimethylbenzylammonium chloride, triethylbenzylammonium chloride, dimethyldecylbenzylammonium chloride, triethylbenzylammonium chloride, myristylbenzyldimethylammonium chloride, dodecyltrimethylammonium chloride, dimethyltetradecylbenzylammonium chloride, trimethyltetradecylammonium chloride, coconut trimethylammonium chloride , Stearyltrimethylammonium chloride,
Alkyl and aralkyl quaternary such as distearyl dimethyl ammonium chloride, tetrabutyl ammonium hydroxide, 1,4-phenylenedimethylenebistrimethylammonium dichloride, 1,4-phenylenedimethylenebistriethylammonium dichloride, ethylenebistriethylammonium dibromide Ammonium salt, 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-undece Hydrogen 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-phenylpropy Le) -1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride
Grade 1,8-diaza-bicyclo [5.4.0] -7-undecenium salt.

(B) quaternary salts of tertiary amines with inorganic or organic acids

Embedded formula: NR ⁶ ₃ or _{^{R 6 2 NR 7 -NR 6 2}} ( wherein, R ⁶ and R ⁷ are the same as defined above.) Tertiary amine represented by. Specific examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triisobutylamine,
Methyl diethylamine, 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, Examples include N-cyclohexylpyrrolidine, Nn-butylpyrrolidine, N-ethylpyrrolidine, N-benzylpyrrolidine, 2,4,6-trimethylpyridine and the like.

Specific examples of the inorganic or organic acid forming the quaternary salt include:

Formula: 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 ⁻ , or (C ₄ H ₉ ) ₃ NH ⁺ R ⁸ COO ⁻ (wherein, R ⁸
Represents an alkyl or alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. ).
Primary or secondary amines are not preferred because reactions other than polyol vulcanization occur.

(C) Quaternary phosphonium salt

Embedded formula: PR ⁶ ₄ X or _{^{R 6 3 PR 7 -PR 6 3}} · 2Y ( wherein, R ^6, R ⁷ and Y are the same as defined above.) Quaternary represented by Phosphonium salts.

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.

(D) 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 not preferred because they may 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, when the composition is applied, dried, and baked, the organic acid is evaporated or thermally decomposed, and the basic compound accelerates the vulcanization reaction.
In the present invention, an organic acid is also included in the “vulcanization accelerator”.

In the case of a 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 2 parts by weight, of amine compound per 100 parts by weight of fluororubber.
0 parts by weight. In the case of polyol vulcanization, fluoro rubber 1
The amount is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, and 0 to 10 parts by weight, preferably 0.01 to 5 parts by weight of a vulcanization accelerator based on 00 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. In addition, you may use together a polyamine vulcanizing agent and a polyol vulcanizing agent.

(III) Fluorine-Containing Multi-Segmented Polymer The fluorine-containing multi-segmented polymer contained in the composition of the present invention contains an elastomeric fluorine-containing polymer chain segment A (hereinafter simply referred to as “elastomer segment A”) in one molecule. And a non-elastomeric fluorine-containing polymer chain segment B (hereinafter simply referred to as “non-elastomeric segment B”).

A film obtained from the fluororubber vulcanizing aqueous composition containing such a fluorine-containing multi-segmented polymer has heat resistance, abrasion resistance and non-adhesion while maintaining sufficient flexibility. It is a thing. In comparison with this, the film made of the aqueous composition for vulcanization of a fluororubber containing a mere mixture of an elastomeric fluorine-containing polymer and a non-elastomeric fluorine-containing polymer, shows the type of each polymer to be mixed, Although they vary depending on the properties, compatibility, etc., they are generally inferior in mechanical properties, abrasion resistance, flexibility and the like.

The elastomeric segment A refers to a segment having a glass transition point of 25 ° C. or lower, and is generally amorphous. Specific examples of the monomer that is a constituent unit of the elastomeric segment A include tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether (the alkyl group has 1 to 6 carbon atoms),

Formula: CF ₂ = CFO (CF ₂ CFX ⁴ O) _p − (CF ₂ CF ₂ CF ₂ O) _q −
R _f (wherein X ⁴ is a fluorine atom or CF ₃ , and R _f has 1 to 1 carbon atoms.
6, a perfluoroalkyl group, p is an integer of 0 to 5, q is an integer of 0 to 5, provided that p + q ≧ 1. And the like, and combinations and compositions having elastomer properties can be used. In addition, a monomer that provides a curing site for polyamine vulcanization or polyol vulcanization, or a functional group-containing monomer that provides a function such as adhesion to another material may be introduced at 10 mol% or less.

In a preferred embodiment, the elastomeric segment A comprises 50-85 mol% of tetrafluoroethylene and 15-85% of perfluoro (alkyl vinyl ether).
It is an elastic polymer chain consisting of 50 mol%.

The elastomeric segment A can be obtained by a known iodine transfer polymerization method for producing a fluororubber. For example, a method in which emulsion polymerization is carried out in an aqueous medium in the presence of an iodine compound, preferably a diiodine compound and a radical initiator under substantially oxygen-free conditions.

The non-elastomeric segment B preferably has a crystal melting point of 150 ° C. or higher. Among the monomers that can constitute the non-elastomeric segment B, specific examples of the fluorine-containing monomer include tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene,
Perfluoroalkyl vinyl ether,

A compound represented by the formula: CF ₂ CFCF (CF ₂ ) _p X ⁵ (where p is an integer of 1 to 10 and X ⁵ represents a fluorine atom or a chlorine atom) or perfluoro-
Perhaloolefins such as 2-butene; vinylidene fluoride, vinyl fluoride, trifluoroethylene,

Formula: CH ₂ CC (CF ₃ ) ₂ Formula: CH ₂ CCX ^6- (CF ₂ ) _q -X ⁷ (wherein X ⁶ and X ⁷ are each a hydrogen atom or a fluorine atom, q Represents an integer of 1 to 10.) and the like.

Further, monomers copolymerizable with these, for example, ethylene, propylene, vinylidene chloride, vinyl ethers, vinyl carboxylate and acrylics can also be used as copolymer components.

In one preferred embodiment, the non-elastomeric segment B comprises more than 85 mol% of tetrafluoroethylene up to 100 mol% and of formula (I):

Embedded image CF ₂ ＣＦCF—R _f ¹ (I) wherein R _f ¹ is a trifluoromethyl group or a formula: OR
_f ² (here, R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). ) Is a polymer chain consisting of 0 to less than 15 mol% of the compound represented by

[0034] In another preferred embodiment, the non-elastomeric segment B is tetrafluoroethylene 8
5-99.7 mol%, and the compound of formula (I) 0.
It is a polymer chain composed of 3 to 15 mol%.

Among the above, as the monomer used as the main component, from the viewpoint of heat resistance and abrasion resistance, a fluorine-containing olefin alone, a combination of fluorine-containing olefins, a combination of ethylene and tetrafluoroethylene, and a mixture of ethylene and chloroethylene. Preferred is a combination of trifluoroethylene,
Particularly, a perhaloolefin alone or a combination of perhaloolefins is preferable.

Blocking or grafting of the non-elastomeric segment B can be achieved by emulsion polymerization of the elastomeric segment A followed by polymerization of the above monomer into the non-elastomeric segment B.
The fluorine-containing multi-segmented polymer thus obtained is a polymer molecule (B-A-) in which a non-elastomeric segment B is bonded to both ends of an elastomeric segment A.
B) and a polymer molecule (AB) in which a non-elastomeric segment B is bonded to one end of an elastomeric segment A
Is the main subject. When the number of polymer molecules of only the elastomeric segment A to which the non-elastomeric segment B is not bonded is large, the mechanical properties and abrasion resistance of the obtained film tend to decrease.

The ratio of the elastomeric segment A to the non-elastomeric segment B in the fluorine-containing multi-segmented polymer of the present invention varies depending on the use, required characteristics and the composition of each segment. Segment B (weight ratio) "
Is 5/95 to 98/2, preferably 20/80 to 95 /
5 When the proportion of the elastomeric segment A is small, the flexibility may be insufficient, and when the proportion of the non-elastomeric segment B is small, the heat resistance, abrasion resistance, and mechanical properties may be insufficient. .

The fluorine-containing multi-segmented polymer is preferably used in the form of an aqueous dispersion from the viewpoint of dispersibility.
It is blended at a ratio of 00 parts.

(IV) Fluororesin and Terminal-Modified Perfluoropolyether In order to further improve the heat resistance and abrasion resistance of the resulting film or to adjust various physical properties such as flexibility, the composition of the present invention is used. Fluororesins and / or end-modified perfluoropolyethers can be included.

Specific examples of the fluororesin include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinylether copolymer (EPA), tetrafluoroethylene Fluoroethylene-hexafluoropropylene copolymer (F
EP), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), polytetrafluoroethylene, terminal-modified EPA, terminal-modified FEP, terminal-modified PFA, and the like. One or more of these may be used. it can. Among them, a tetrafluoroethylene-based polymer is preferable in terms of non-adhesiveness. 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 the following structure:

Embedded formula _{:-( CF (CF 3) CF 2} O) -, - (CF 2 O) -, - (CF
₂ CF ₂ O)-and-(CF ₂ CF ₂ CF ₂ O)-at least one type of repeating unit selected from the group consisting of repeating units represented by the formula: It is in the range of 1000.

The functional groups that modify the molecular terminals of the perfluoropolyether include Cl, Br, I, NR ⁹ R ¹⁰ (wherein R ⁹
And R ¹⁰ represents independently a hydrogen atom, an aryl group, an alkyl group of C ₁ -C ₁₀ or cycloalkyl group. ), SH, NC
_{O, NO 2, COOH, PO} 2 H, can be cited SO ₃ H, OH, a glycidyl group or a hydroxyphenyl group. These functional groups may be located at either terminal of the main chain or side chain of the perfluoroalkyl group. These functional groups are directly bonded to the main chain composed of repeating units of the perfluoropolyether represented by the above formula, or

Embedded formula _{:-( CH 2) n -, -} (CF 2) n -, - (CH 2 O)
_n— or — (CF ₂ O) _n — (where 1 ≦ n <100).

(V) Various additives In addition to the above-mentioned components, the composition of the present invention further comprises a conductivity-imparting agent and various additives commonly added to the fluororubber composition, for example, a filler, a colorant, and an acid acceptor. Agents and the like can be blended.
Examples of the conductivity-imparting agent include carbon blacks (Ketjen, acetylene, etc.); carbons such as PAN-based carbon fibers, pitch-based carbon fibers, and pulverized expanded graphite; and fluorocarbons obtained by completely or partially fluorinating these carbons. Metals (powder, flake, fiber, etc.) such as Ag, Ni, Cu, brass, silver-plated copper, Zn, Al, and stainless steel; SnO ₂ (Sb-doped), In ₂ O ₃ ( Sn dope), Z
Fine particle metal oxides such as nO (Al-doped); ferrites; and high dielectric substances such as barium titanate. The addition amount of the conductivity-imparting agent is appropriately selected depending on the kind or the intended surface resistance value or volume resistance value, but the proportion of 0 to 40 parts by weight is relative to 100 parts by weight of the aqueous composition for vulcanizing the fluororubber. Mix in.

Examples of the filler include calcium carbonate, barium sulfate, and fibrous fillers such as glass fiber, carbon fiber, asbestos fiber, and potassium titanate fiber. Examples of the coloring agent include inorganic pigments and composite oxide pigments. Examples of the acid acceptor include double salts such as magnesium oxide, lead oxide, zinc oxide, lead carbonate, zinc carbonate, and hydrotalcite, but those having high activity such as calcium hydroxide are likely to cause gelation and are not preferred. . Further, a compound having a pKa smaller than that of the basic compound is preferable. If the pKa of the acid acceptor is large, the composition tends to gel. Usually, the acid acceptor is added to 100 parts by weight of the fluorinated copolymer in accordance with its activity.
Up to 40 parts by weight can be blended.

The composition of the present invention can be applied and vulcanized by the same method as the conventional vulcanizing composition for a fluorine-containing copolymer. That is, brush coating according to the properties of the composition,
The composition is applied to a substrate by spray coating, dip coating, flow coating, dispenser coating, screen coating, or the like, dried sufficiently, and then baked at 150 to 300 ° C. for 10 to 120 minutes.

The fluororubber vulcanizing aqueous composition of the present invention comprises:
The resulting film can have both heat resistance, abrasion resistance and flexibility. A surface layer may be further formed on the coating layer formed from the composition of the present invention. The surface layer can be formed by a conventional method from at least one of the above-mentioned fluorine-containing multi-segmented polymer, fluororesin, and terminal-modified perfluoropolyether.

It is preferable that the surface of the article substrate (object to be coated) be sufficiently degreased and washed before the composition is applied. Further, 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; SBR,
Molded products and coatings of general-purpose rubbers such as butyl rubber, NBR and EPDM, and heat-resistant rubbers such as silicone rubber and fluororubber; woven and non-woven fabrics of natural and synthetic fibers;
Etc. can be used.

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 and belts (such as fuser rolls, pressure rolls, fuser belts) and transport belts for OA equipment such as; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants , An engine gasket and the like.

[0050]

The present invention will be described below in detail with reference to examples. Example 1 Preparation of fluoro rubber dispersion A: vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer (monomer composition: 65 by emulsion polymerization)
/ 18/17 (molar ratio)), and the obtained aqueous dispersion is treated with a surfactant (a 20% by weight aqueous solution of EAD-13 manufactured by NOF Corporation and a 20% by weight aqueous solution of EAD-15 manufactured by the company): both the main component is concentrated by _{C 13 H 27 -O (CH 2} CH 2 O) n H), and a solid concentration of 60 wt%. This is called "fluoro rubber dispersion A".

Preparation of Fluorine-Containing Multi-Segmented Polymer Dispersion A: Example 3 of WO 99/33891
The translucent aqueous dispersion obtained by the procedure described in the above was used as a surfactant (20% by weight aqueous solution of EAD-13 and 20% by weight of EAD-15).
% Aqueous solution), and the solid content concentration becomes 45% by weight.
And This is referred to as "fluorine-containing multi-segmented polymer dispersion A". The composition of the non-elastomeric fluorine-containing polymer chain segment in the fluorine-containing multi-segmented polymer contained in the aqueous dispersion is TF
E / PFVE = 99.0 / 1.0 (molar ratio), and the composition of the elastomeric fluoropolymer chain segment is:
TFE / PMVE = 60/40 (molar ratio).

Preparation of Pig Paste A: 3 parts by weight of a filler (Talox R-516L manufactured by Titanium Industry Co., Ltd.) and 5 parts by weight of an acid acceptor (DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.) were added to a surfactant. (20% by weight aqueous solution of EAD-13) Pure water 4 with 2 parts by weight
The paste was dispersed in 6 parts by weight to prepare a paste. This is called "Pi
g paste A ".

Preparation of Paint A: 38 parts by weight of a fluororubber dispersion A, 52 parts by weight of a fluorine-containing multi-segmented polymer dispersion A, and 12 parts by weight of Pig paste A were mixed and sufficiently dispersed. This aqueous dispersion 100
Polyamine-based vulcanizing agent (GLS-Daikin Industries, Ltd.)
223 B solution) was added to prepare a paint. This is called "Paint A".

Preparation of Film and Measurement of Tensile Properties: Paint A
Spray coated on aluminum foil, 80-100
C. and dried at 330.degree. C. for 15 minutes. The aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 500 mm / min.

Example 2 In preparing a paint, a polyol-based vulcanizing agent (bisphenol AF ammonium salt) was used in place of the polyamine-based vulcanizing agent.
The procedure of Example 1 was repeated except that 7 parts by weight of a 0% by weight aqueous solution and 0.8 parts by weight of a vulcanization accelerator (SA610-50 manufactured by San Apro Co., Ltd.) were used.

Example 3 Preparation of Fluororesin Dispersion A: An aqueous dispersion obtained by preparing a tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (monomer composition: 95/5 (weight ratio)) by emulsion polymerization The surfactant (EA
(A 20% by weight aqueous solution of D-13 and a 20% by weight aqueous solution of EAD-15) to give a solid concentration of 48% by weight.
This is called "fluororesin dispersion A".

Preparation of paint B: 38 parts by weight of fluororubber dispersion A, 26 parts by weight of fluorine-containing multi-segmented polymer dispersion A, 26 parts by weight of fluororesin dispersion A, and 12 parts by weight of Pig paste A were mixed sufficiently. Dispersed. To 100 parts by weight of this aqueous dispersion, 5 parts by weight of a polyamine vulcanizing agent (GLS-223B solution) was added to prepare a coating. This is called "paint B".

Preparation of Film and Measurement of Tensile Properties: Paint B
Spray coated on aluminum foil, 80-100
C. and dried at 330.degree. C. for 15 minutes. The aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 500 mm / min.

Example 4 In the preparation of paint, 7 parts of a polyol vulcanizing agent (10% by weight aqueous solution of bisphenol AF ammonium salt) and a vulcanization accelerator (SA610-5) were used in place of the polyamine vulcanizing agent.
0) Example 3 was repeated except that 0.8 parts by weight were used.

Comparative Example 1 Preparation of Coating C: 38 double parts of fluororubber dispersion A, 52 double parts of fluororesin dispersion A, and 12 double parts of Pig paste A were mixed and sufficiently dispersed. 100 parts by weight of this aqueous dispersion was mixed with a polyamine vulcanizing agent (GLS-22).
3B solution) was added in an amount of 5 parts by weight to prepare a paint. This is called "Paint C".

Preparation of film and measurement of tensile properties: Paint C
Spray coated on aluminum foil, 80-100
C. and dried at 330.degree. C. for 15 minutes. The aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 500 mm / min.

Comparative Example 2 In the preparation of the paint, 7 parts of a polyol vulcanizing agent (a 10% by weight aqueous solution of bisphenol AF ammonium salt) and a vulcanization accelerator (SA610-5) were used instead of the polyamine vulcanizing agent.
0) Comparative Example 1 was repeated except that 0.8 parts by weight was used.

Comparative Example 3 Preparation of Paint D: 50 parts by weight of a fluorine-containing multi-segmented polymer dispersion A, 5 parts by weight of ethylene glycol, and 1 part by weight of diethanolamine were mixed and sufficiently dispersed. This is called "Paint D".

Preparation of Film and Measurement of Tensile Properties: Paint D
Spray coated on aluminum foil, 80-100
C. and dried at 330.degree. C. for 15 minutes. The aluminum foil was dissolved with hydrochloric acid, and the obtained film was punched into a JIS No. 4 dumbbell shape, and a tensile test was performed at a tensile speed of 500 mm / min. Tables 1 and 2 show the above results.

[0065]

[Table 1]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 53/00 C08L 53/00 61/14 61/14 71/00 71/00 Z C09D 127/12 C09D 127 / 12 127/18 127/18 127/20 127/20 127/22 127/22 129/10 129/10 151/04 151/04 153/00 153/00 F16C 13/00 F16C 13/00 A (72) Inventor Seitaro Terasaka 1-1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Nakatani Yasutori 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works F-term (reference) 3J103 AA02 AA21 FA01 FA02 FA07 FA12 FA14 FA18 GA02 GA57 GA58 HA03 HA04 HA05 HA12 HA31 HA41 HA43 HA53 4F100 AH02H AK17A AK17J AK17K AK18A AL02A AL09A AT00B BA02 CA03A CC00A GB51 GB71 JJ03 JK09 JK14 YBJBJBJBJB10B14 BD15W BD15Z BD16W BD16Z BE04Z BN03X BP03X CC07Y CH05Z EJ016 EJ036 EJ056 EX076 FD14Y FD146 HA08 4J038 CD091 CD092 CD111 CD112 CD121 CD122 CD131 CD132 CD141 CD142 CD151 CD152 CP021 CP022 CQ001 JQ12 DA0311 JA0811

Claims (9)

[Claims] 1. An aqueous composition for vulcanizing a fluororubber, comprising a fluororubber, a fluorinated multi-segmented polymer having an elastomeric fluoropolymer chain segment and a non-elastomeric fluoropolymer chain segment, a vulcanizing agent, and water. object. 2. The elastomeric fluorine-containing polymer chain segment is capable of imparting flexibility to the entire fluorine-containing multi-segmented polymer, and at least 90 mol% of its constituent units are perfluoroolefin units. The aqueous composition for vulcanization of a fluororubber according to the above. 3. The elastomeric fluorine-containing polymer chain segment contains 50 to 85 mol% of tetrafluoroethylene.
And perfluoro (alkyl vinyl ether) 15-5
The aqueous composition for vulcanizing a fluororubber according to claim 1 or 2, which is an elastic polymer chain comprising 0 mol%. 4. The non-elastomeric fluoropolymer chain segment comprises more than 85 mol% of tetrafluoroethylene and up to 100 mol% and of formula (I): CF ₂ ＣＦCF—R _f ¹ (I) Wherein R _f ¹ is a trifluoromethyl group or a formula: OR
_f ² (here, R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). 2. The aqueous composition for vulcanizing a fluororubber according to claim 1, which is a polymer chain comprising 0 to less than 15 mol% of the compound represented by the formula 5. The non-elastomeric fluorine-containing polymer chain segment comprises tetrafluoroethylene 85 to 99.7.
Mol%, and formula (I): CF ₂ ＣＦCF—R _f ¹ (I) wherein R _f ¹ is a trifluoromethyl group or a formula: OR
_f ² (here, R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). 2. The aqueous composition for vulcanizing a fluororubber according to claim 1, which is a polymer chain comprising 0.3 to 15 mol% of the compound represented by the formula (1). 6. The fluororubber vulcanizing aqueous composition according to claim 1, further comprising a fluororesin and / or a terminal-modified perfluoropolyether. 7. The aqueous composition for vulcanizing a fluororubber according to claim 1, wherein the vulcanizing agent is a polyol vulcanizing agent. 8. An article, the surface of which is at least partially covered with a coating layer formed from the aqueous composition for vulcanizing a fluororubber according to claim 1. Description: 9. The article according to claim 8, which is a roll or belt for office automation equipment.