JP4776401B2 - Rubber coating agent - Google Patents

Description

  The present invention relates to a coating agent for rubber that provides a film excellent in adhesion to rubber and having excellent wear resistance and surface smoothness.

Conventionally, in order to impart smoothness and wear resistance to the surface of various rubbers, there is a method in which a silicone resin composition is applied to a rubber surface and then cured to form a film, and the rubber surface is coated with the film. It's being used.
Examples of the silicone resin composition used in this case include a composition comprising an organopolysiloxane containing an epoxy group and an alkoxysilane containing an amino group (see Patent Document 1), and an organopolysiloxane containing a hydroxyl group. A composition comprising an organohydrogenpolysiloxane, an organopolysiloxane containing an epoxy group and an alkoxysilane containing an amino group (see Patent Documents 2 to 4), an organopolysiloxane containing a hydroxyl group and an organohydrogenpolysiloxane And a hydrolytic condensate of dialkoxysilane containing amino groups (see Patent Documents 5 and 6), organopolysiloxanes containing hydroxyl groups or vinyl groups, organohydrogenpolysiloxanes and dimethylpolysiloxanes Composition Patent Document 7), a composition comprising an organopolysiloxane containing hydrolyzable groups, an organopolysiloxane containing epoxy groups or amino groups and hydrolyzable groups, and a hydrolyzable silane containing epoxy groups or amino groups (See Patent Document 8), a reaction product of a silane or siloxane containing an amino group and a silane or siloxane containing an epoxy group, a polydiorganosiloxane containing a hydroxyl group, and a polyorganohydrogensiloxane (See Patent Document 9), a reaction product of a silane or siloxane containing an amino group and an alkoxy group and a silane or siloxane containing an epoxy group and an alkoxy group, and an alkoxy group or a hydroxyl group and an amino group Composition comprising polyorganosiloxane (Patent text) 10), a polyorganosiloxane containing a hydroxyl group and an epoxy group, a composition comprising an alkoxysilane containing an amino group and an alkoxysilane containing a mercapto group (see Patent Document 11), a polydiorganopolysiloxane containing a hydroxyl group , A polyorganohydrogensiloxane, a polyorganosiloxane containing a water-soluble amino group, an aminosilane compound, an epoxysilane compound, a composition comprising a carboxylic acid and an alkylamine oxide (see Patent Document 12), an acrylic-silicone graft copolymer, A composition comprising a hydrolysis condensate of an amino group-containing dialkoxysilane and an organopolysiloxane containing an epoxy group (see Patent Document 13), a diorganosiloxane containing a hydroxyl group, an epoxy resin, and a silane containing an amino group Consist of Narubutsu (Patent Document 14 reference) have been proposed.

However, since the films obtained from these silicone resin compositions have poor wear resistance and surface smoothness, silicone resin compositions containing fine powders have been proposed to improve the above properties.
As the fine powder, for example, a silicone resin composition containing polymethylsilsesquioxane has been proposed. Specifically, a polyorganosiloxane containing a hydroxyl group, a polyorganosiloxane containing an epoxy group, an amino group Composition comprising alkoxysilane and polymethylsilsesquioxane powder (see Patent Documents 15 and 16), dimethylpolysiloxane containing silanol groups, diorganopolysiloxane containing amino groups, and γ-glycidoxypropyl Examples thereof include a composition composed of trimethoxysilane and polymethylsilsesquioxane fine powder (see Patent Document 17).

  Silicone resin compositions containing silicone rubber fine powders have also been proposed. For example, non-flowable branched organopolysiloxanes, hydrolyzed condensates of dialkoxysilanes containing epoxy groups, and amino groups A composition comprising a hydrolyzed condensate of dialkoxysilane and fine powder of silicone rubber (see Patent Document 18), a non-flowable branched organopolysiloxane, a diorganopolysiloxane containing amino groups, and a digroup containing epoxy groups Hydroxy condensate of alkoxysilane, hydrolyzed condensate of dialkoxysilane containing amino group, trialkoxysilane containing (meth) acryloyl group or amino group and silicone rubber fine powder (see Patent Document 19) ), Organopolysiloxanes, dialkoxysilanes containing epoxy groups Hydrolyzed condensate, dialkoxysilane hydrolyzed condensate containing amino group and silicone rubber fine powder (see Patent Document 20), organopolysiloxane containing hydroxyl group, dialkoxysilane containing epoxy group A composition comprising a hydrolyzed condensate, a water-soluble amino compound and silicone rubber fine powder (see Patent Document 21), an organopolysiloxane containing an alkoxy group or a hydroxyl group, an organotrialkoxysilane, an amide group and a carboxyl group Examples thereof include a composition comprising organoalkoxysilane, an organoalkoxysilane containing an epoxy group, and fine silicone rubber powder (see Patent Document 22).

  Silicone resin compositions containing polycarbonate resin fine powders have also been proposed, for example, compositions comprising organopolysiloxanes having alkenyl groups, organohydrogenpolysiloxanes and polycarbonate resin fine powders (see Patent Document 23). It is done.

  In addition, a silicone resin composition containing a polyethylene resin fine powder has also been proposed, and examples thereof include a curable silicone composition and a composition comprising a polyethylene resin fine powder (see Patent Document 24).

JP 54-43891 A JP 54-45361 A JP 54-90369 A JP 54-90375 A JP-A-7-109441 JP-A-7-126417 JP-A-62-215667 JP-A-7-196984 JP 56-78960 A Japanese Patent Laid-Open No. 11-43647 JP-A-5-5082 JP 2002-188057 A JP-A-7-109440 JP-A-4-318021 JP-A 61-159427 Japanese Patent Laid-Open No. 2-237663 JP 7-251124 A JP 7-233351 A JP-A-7-310051 JP-A-8-245882 JP-A-9-53047 Japanese Patent Laid-Open No. 11-49955 JP-A-9-12891 JP 2002-188056 A

As described in [Prior Art], many silicone resin compositions containing various fine powders have been proposed, but the film obtained from these silicone resin compositions formed on the surface of rubber, The effect of improving wear resistance and surface smoothness is still insufficient, and further improvement is required.
The object of the present invention is to solve the problems of the rubber coating agent comprising the conventional silicone resin composition as described above, and to provide a film having excellent adhesion to rubber, excellent wear resistance and surface smoothness. It is to obtain a rubber coating agent.

［式中、Ｒ²は非置換又は置換の炭素原子数１〜６の２価炭化水素基、Ｒ³は炭素原子数１〜４の２価炭化水素基、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ水素原子又は非置換もしくは置換の炭素原子数１〜10の１価炭化水素基であり、ｍは０〜６の整数であり、ｍが０ではないとき、前記Ｒ⁴、Ｒ⁵及びＲ⁶のうち少なくとも１つは水素原子であり、またｍが０であるとき、前記Ｒ⁵及びＲ⁶のうち少なくとも１つは水素原子である。］
（Ａ−２）成分：下記式（２）で表されるアルコキシシラン及び／又はその部分加水分解縮合物、

［式中、Ｒ⁷は非置換又は置換の炭素原子数１〜20の１価炭化水素基、Ｒ⁸は独立に炭素原子数１〜６の１価炭化水素基であり、ａは０又は１である。］
（Ａ−３）成分：（Ａ−１）成分と（Ａ−２）成分の合計量100重量部に対して０〜10重量部の縮合触媒、
からなる硬化性シリコーン組成物：100重量部、
（Ｂ）成分：ポリウレタン樹脂：10〜100重量部、
（Ｃ）成分：融点が150℃以上であるか、又は融点を有しない、平均粒径が0.5〜50μmである有機樹脂微粒子：5〜150重量部。 Accordingly, the present invention provides a rubber coating agent comprising an aqueous resin composition containing the following components (A), (B), and (C) in order to achieve the above object. To do.
(A) component:
(A-1) Component: a hydroxyl group and a group selected from the group consisting of groups represented by the formula: R ¹ O— (R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms); An organopolysiloxane in which the group represented by the formula (1) is bonded to the same silicon atom at at least two ends of the polysiloxane chain;

[Wherein R ² is an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ , R ⁵ and R ⁶ are Each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, m is an integer of 0 to 6, and when m is not 0, R ⁴ , R ⁵ and R ⁶ At least one of them is a hydrogen atom, and when m is 0, at least one of the R ⁵ and R ⁶ is a hydrogen atom. ]
(A-2) Component: alkoxysilane represented by the following formula (2) and / or a partial hydrolysis condensate thereof,

[Wherein R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁸ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 0 or 1 It is. ]
(A-3) Component: 0 to 10 parts by weight of a condensation catalyst with respect to 100 parts by weight of the total amount of the components (A-1) and (A-2),
Curable silicone composition comprising: 100 parts by weight,
(B) component: polyurethane resin: 10 to 100 parts by weight,
Component (C): Organic resin fine particles having a melting point of 150 ° C. or higher or having no melting point and an average particle size of 0.5 to 50 μm: 5 to 150 parts by weight.

  The coating agent for rubber of the present invention is applied to the rubber surface and then cured by heating to form a film. The obtained film has excellent adhesion to rubber and excellent rubber surface. Smoothness and wear resistance can be imparted. The coated rubber article is useful as a weather strip material for automobiles, a glass run material, an O-ring, a gasket, various sealing materials such as various packings, and a rubber hose material because of its excellent surface smoothness and wear resistance.

Hereinafter, the present invention will be described in more detail.
As described above, the rubber coating agent of the present invention is an aqueous resin composition containing at least the component (A), the component (B), and the component (C).
(A) component of the coating agent for rubber | gum of this invention is comprised by (A-1) component which is an essential component, (A-2) component, and (A-3) component which is an arbitrary component.
The (A-1) component organopolysiloxane is selected from the group consisting of a hydroxyl group and a group represented by the formula: R ¹ O— (R ¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms). Group (i) and group (ii) represented by the following formula (1) are bonded to the same silicon atom at at least two ends of the polysiloxane chain. The structure of the organopolysiloxane of component (A-1) may be linear, branched, or cyclic having two or more branches, but is preferably linear. In the present invention, the organopolysiloxane of component (A-1) is usually one having an average degree of polymerization of 10 to 2,000.

  In the organopolysiloxane of the component (A-1), the group (i) and the group (ii) described above are bonded to at least one group (i) and one group (ii) on the same silicon atom at the terminal of the polysiloxane chain. ), That is, it is sufficient that two in total are bonded. In particular, the organopolysiloxane of component (A-1) is as described above for each of two or more, preferably 2 to 5, more preferably two silicon atoms at the end of the polysiloxane chain. It is preferable for the reason of stability at the time of storage that the group (i) and the group (ii) are bonded one or two respectively.

In the aforementioned group (i), examples of R ¹ include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, and hexyl groups. Groups are preferred.

In formula (1), R ² is an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms. R ² includes, for example, an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group, an arylene group such as a p-phenylene group; and a hydrogen atom in the hydrocarbon group Examples include a 1-chlorotrimethylene group in which a part or all of is substituted with a fluorine atom, a chlorine atom, or a bromine atom, and a trimethylene group is particularly preferable.

In the formula (1), R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms. Examples of R ³ include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. Among these, an ethylene group is preferable.

In the formula (1), R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ⁴ , R ⁵ and R ⁶ are the same or different, for example, hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group An alkyl group such as a cyclopentyl group and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a 2-phenylethyl group; Alkyl halide such as 3,3,3-trifluoropropyl group, 3-chloropropyl group, etc., in which part or all of hydrogen atoms in the hydrocarbon group are substituted with fluorine atom, chlorine atom or bromine atom A hydrogen atom and a methyl group are preferable.

In the formula (1), m is an integer of 0 to 6, and when m is not 0, at least one of R ⁴ , R ⁵ and R ⁶ is a hydrogen atom, and when m is 0 , At least one of R ⁵ and R ⁶ is a hydrogen atom.

Specific preferred examples of the group represented by the above formula (1) include the following, but are not limited thereto.
_{-C 3 H 6 NH 2, -C} 3 H 6 NHC 2 H 4 NH 2,
_{-C 3 H 6 (NHC 2 H} 4) 2 NH 2,
_{-C 3 H 6 (NHC 2 H} 4) 3 NH 2,
_{-C 3 H 6 NHCH 3, -C} 3 H 6 NHC 2 H 4 NHCH 3

As the organopolysiloxane of the component (A-1), a linear organopolysiloxane represented by the following formula (3) and / or the following formula (4) is particularly preferable.

In said formula (3), R < ⁹ > is a hydrogen atom or a C1-C6 monovalent hydrocarbon group independently. Examples of the monovalent hydrocarbon group for R ⁹ include those similar to R ^1, and alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Among them, a methyl group is preferable.

In the above formula (3), R ¹⁰ and R ¹² are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of R ¹⁰ and R ¹² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group. Alkyl groups such as octadecyl group and icosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; benzyl group and 2-phenylethyl group An aralkyl group such as, and a part or all of the hydrogen atoms in the hydrocarbon group are substituted with a fluorine atom, a chlorine atom or a bromine atom, for example, 3,3,3-trifluoropropyl group, 3-chloropropyl An unsubstituted or substituted monovalent hydrocarbon group having 1 to 20, preferably 1 to 6 carbon atoms, such as a halogenated alkyl group such as a group. It is. In particular, 90 mol% or more of a plurality of R ¹² is preferably a methyl group from the viewpoint of industrial and mold release performance.
In the above formula (3), R ¹¹ is a group represented by the above formula (1).

  In said formula (3), n is an integer of 10-2,000, Preferably 20-1,700. If n is less than 10, the resulting film may be brittle, and if it exceeds 2,000, the organosiloxane becomes too viscous to be finely dispersed in the emulsified dispersion described later, and stored. It may be difficult to obtain an emulsion with good stability.

  The method for producing the organopolysiloxane as the component (A-1) is not particularly limited. For example, α, ω-dihydroxy-dimethylpolysiloxane and a dialkoxysilane compound having an alkylamino group bonded to a silicon atom are removed. Examples include a method of causing an alcohol condensation reaction.

Moreover, in this invention, you may make an organic acid react with the organopolysiloxane of (A-1) component. The organic acid can react with an aminoalkyl group in the organopolysiloxane to form an amine salt (ie, an ion pair), thereby imparting hydrophilicity to the component (A). It can be dispersed more minutely.
The organic acid is not particularly limited as long as it can form the amine salt, and examples thereof include aliphatic carboxylic acids having 1 to 6 carbon atoms such as formic acid, acetic acid, propionic acid, malonic acid, and citric acid; Examples thereof include sulfonic acids having 1 to 6 carbon atoms such as methanesulfonic acid and ethanesulfonic acid, and sulfinic acids having 1 to 6 carbon atoms such as ethanesulfinic acid. Among these, formic acid and acetic acid are particularly preferable. These organic acids can be used singly or in combination of two or more.
The addition amount of the organic acid is preferably 1 molar equivalent or less with respect to the amino group of the aminoalkyl group.

The component (A-2) functions as a crosslinking agent for the component (A-1) and is an alkoxysilane represented by the following formula (2) and / or a partial hydrolysis condensate thereof.

In the formula (2), a is 0 or 1, and R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R ⁷ is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group. Alkyl groups such as icosyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; aralkyl such as benzyl group and 2-phenylethyl group A group; or a group in which some or all of the hydrogen atoms in the hydrocarbon group are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a functional group containing a mercapto group, an acryloyloxy group, an amino group, or the like. For example, halogen such as 3,3,3-trifluoropropyl group, 3-chloropropyl group, etc. Alkyl group; acryloyloxyalkyl group such as γ-methacryloyloxypropyl group and γ-acryloyloxypropyl group; mercaptoalkyl group such as γ-mercaptopropyl group; N-β (aminoethyl) -γ-aminopropyl group, γ- Examples thereof include an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms such as an aminoalkyl group such as an aminopropyl group, preferably 1 to 6, among which a methyl group, a phenyl group, a vinyl group, A γ-acryloyloxypropyl group, a γ-methacryloyloxypropyl group, and a 3,3,3-trifluoropropyl group.

In formula (2), R ⁸ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. Examples of R ⁸ include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Among these, a methyl group, an ethyl group are preferable. It is a group.

Specifically, as the alkoxysilane represented by the above formula (2), when a is 1, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrisilane Methoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyl Trimethoxysilane, octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropi Trimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. In the case of 0, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like, and partial hydrolysis condensates of these alkoxysilanes can be mentioned.
Among these, preferably, methyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, tetramethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane. Ethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, 3,3,3-trifluoropropyltriethoxy Silane and tetraethoxysilane. Further, the component (A-2) can be used alone or in combination of two or more.

The component (A-2) is a crosslinking agent for the component (A-1) and can be cured by a condensation reaction to obtain a silicone elastomer. The condensation reaction is exclusively a condensation reaction of the hydroxyl group and / or R ¹ O— group in the component (A-1) and the R ⁸ O— group in the component (A-2). The condensation reaction of R ⁸ O— groups in the component) is also included.

The amount of the component (A-2) used relative to the component (A-1) is R ^{8 in the} component (A-2) with respect to 1 mol in total of the hydroxyl group and R ¹ O— group in the component (A-1). The amount of the O-group is usually 0.5 to 100 mol, preferably 1.0 to 50 mol.
If the amount of the component (A-2) used is too small, the condensation curing reaction may be insufficient and a silicone elastomer may not be obtained. On the other hand, if the amount is too large, the condensation reaction between the R ⁸ O— groups in the component (A-2) will be excessive, and the hardness of the cured product will be high, resulting in poor elasticity, The amount of certain alcohols may increase.

Component (A-3) is a condensation catalyst for promoting the above condensation reaction, and is a sodium compound, an aluminum compound, a potassium compound, a calcium compound, a vanadium compound, an iron compound, a cobalt compound, a nickel compound, a zinc compound, or a zirconium compound. And one or more metal compounds selected from barium compounds.
Specifically, sodium 2-ethylhexanoate, aluminum 2-ethylhexanoate, potassium 2-ethylhexanoate, calcium 2-ethylhexanoate, vanadium 2-ethylhexanoate, iron 2-ethylhexanoate, 2-ethyl Cobalt hexanoate, nickel 2-ethylhexanoate, zinc 2-ethylhexanoate, zirconium 2-ethylhexanoate, barium 2-ethylhexanoate, sodium neodecanoate, aluminum neodecanoate, potassium neodecanoate, calcium neodecanoate, neodecanoic acid Vanadium, iron neodecanoate, cobalt neodecanoate, nickel neodecanoate, zinc neodecanoate, zirconium neodecanoate, barium neodecanoate, sodium oleate, aluminum oleate, potassium oleate, olein Calcium, vanadium oleate, iron oleate, cobalt oleate, nickel oleate, zinc oleate, zirconium oleate, barium oleate, sodium naphthenate, aluminum naphthenate, potassium naphthenate, calcium naphthenate, vanadium naphthenate, Carboxylic acid metal salts such as iron naphthenate, cobalt naphthenate, nickel naphthenate, zinc naphthenate, zirconium naphthenate, barium naphthenate, aluminum acetylacetonate, calcium acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, Nickel acetylacetonate, zinc acetylacetonate, zirconium acetylacetonate, aluminum ethylacetoacetonate, calcium ethylacetoacetate Organometallic complexes such as tonate, cobalt ethyl acetoacetonate, iron ethyl acetoacetonate, nickel ethyl acetoacetonate, zinc ethyl acetoacetonate, zirconium ethyl acetoacetonate, sodium chloride, aluminum chloride, potassium chloride, calcium chloride, chloride Vanadium, iron chloride, cobalt chloride, nickel chloride, zinc chloride, zirconium chloride, barium chloride, sodium sulfate, aluminum sulfate, potassium sulfate, calcium sulfate, vanadium sulfate, iron sulfate, cobalt sulfate, nickel sulfate, zinc sulfate, zirconium sulfate, Barium sulfate, sodium nitrate, aluminum nitrate, potassium nitrate, calcium nitrate, vanadium nitrate, iron nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, zirconium nitrate, barium nitrate, lithium Sodium phosphate, aluminum phosphate, potassium phosphate, calcium phosphate, vanadium phosphate, iron phosphate, cobalt phosphate, nickel phosphate, zinc phosphate, zirconium phosphate, barium phosphate, sodium carbonate, aluminum carbonate, potassium carbonate , Calcium carbonate, vanadium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, zinc carbonate, zirconium carbonate, barium carbonate and other inorganic metal salts, sodium hydroxide, aluminum hydroxide, potassium hydroxide, calcium hydroxide, vanadium hydroxide, Examples thereof include metal hydroxides such as iron hydroxide, cobalt hydroxide, nickel hydroxide, zinc hydroxide, zirconium hydroxide and barium hydroxide. These can be used singly or in combination of two or more.
Tin compounds can also be used alone or in combination with other compounds, but these are not preferred because their toxicity has recently been regarded as a problem.

The compounding amount of the component (A-3) is usually 0 to 10 parts by weight, preferably 0 to 2 parts by weight, based on 100 parts by weight of the total amount of the components (A-1) and (A-2). Degree. When blended, it is an effective amount, usually 0.1 parts by weight or more. When the reactivity of the component (A-1) and the component (A-2) is high, the component (A-3) is not required or even in a trace amount. Well, if it is too much, the effect will not change so much, but it will also be economically disadvantageous.
In addition, when only (A-3) component has low catalyst activity and sufficient sclerosis | hardenability is not acquired, an amine compound and an alkoxy group containing amino group can also be added as a co-catalyst.

In order to obtain the rubber coating agent of the present invention as an aqueous resin composition, it is necessary to blend the component (A) with the component (B) and the component (C) as an aqueous emulsion. The aqueous emulsion of component (A) is the interface between component (A-1), component (A-2) and component (A-3) or component (A-1) and component (A-2). It can be obtained by emulsifying in water using an activator.
There is no restriction | limiting in particular as surfactant used in that case, A nonionic surfactant, a cationic surfactant, and an amphoteric surfactant are preferable. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Sorbit fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene Alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene-modified organopolysiloxane And polyoxyethylene polyoxypropylene-modified organopolysiloxane, and the cationic surfactants include alkyltrimethylammonium salt, dialkyldimethylammonium salt, polyoxyethylenealkyldimethylammonium salt, dipolyoxyethylenealkylmethylammonium salt Salt, tripolyoxyethylene alkylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridium salt, monoalkylamine salt, monoalkylamidoamine salt and the like, and as the amphoteric surfactant, alkyldimethylamine oxide, Alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, alkylcarboxymethyl Etc. b carboxyethyl imidazolinium betaine. These surfactants can be used singly or in combination of two or more.

In order to obtain an aqueous emulsion of the component (A) from the component (A-1), the component (A-2), and the component (A-3) using a surfactant, (A-1) A mixture of the component organopolysiloxane, the component (A-2) alkoxysilane and / or its partial hydrolysis condensate, and the component (A-3) metal compound is emulsified and dispersed in water using a surfactant. Just do it. In the preparation of the aqueous emulsion of the component (A), when the curing reaction of the component (A-1) proceeds and cannot be emulsified and dispersed before forming a sufficiently uniform aqueous emulsion, A method of emulsifying and dispersing the component (A-1) in water using a surfactant, and then adding and stirring the component (A-2) and the component (A-3). First, the component (A-1) and (A-2) A mixture of components is emulsified and dispersed in water using a surfactant, and then (A-3) component is added and stirred, or first, (A-1) component and (A-3) The component mixture is emulsified and dispersed in water using a surfactant, and then the component (A-2) is added and stirred.
In addition, when the component (A-3) is water-soluble, after the component (A-1) or the component (A-1) and the component (A-2) are emulsified and dispersed in water, the component (A-3) is added. A method of adding or dissolving the component (A-3) in water and emulsifying and dispersing the component (A-1) or the component (A-1) and the component (A-2) in water is preferable.

In order to obtain an aqueous emulsion of the component (A) from the components (A-1) and (A-2) using a surfactant, the organopolysiloxane of the component (A-1) and (A- 2) A mixture of the component alkoxysilane and / or its partially hydrolyzed condensate may be emulsified and dispersed in water using a surfactant. In the preparation of the aqueous emulsion of the component (A), when the curing reaction of the component (A-1) proceeds and cannot be emulsified and dispersed, the component (A-1) is first used with a surfactant. And then emulsifying and dispersing in water, and then adding and stirring the component (A-2).
For emulsification and dispersion, a stirring device such as a propeller blade, a paddle blade, a homomixer, and a disper mixer, or an emulsification device such as a high-pressure homogenizer, a colloid mill, and an ultrasonic emulsifier may be used.

  The total amount of the component (A-1) and the component (A-2) in the aqueous emulsion of the component (A) is usually 5 to 80% by mass, preferably about 10 to 60% by mass. Is good. If the blending amount is too small, it is uneconomical. On the other hand, if the blending amount is too large, the viscosity of the aqueous emulsion becomes too high and handling may be difficult.

The component (B) is a component that improves the adhesion between the film obtained by applying the coating agent for rubber of the present invention to the rubber and the rubber and the wear resistance of the film, and includes a polyol (hydroxyl group (—OH)). It is a polyurethane resin obtained by addition reaction of a compound containing two or more) and a polyisocyanate (a compound containing two or more isocyanate groups (-NCO)).
Examples of the polyol include polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, polythioether polyol, polyacetal polyol, polytetramethylene glycol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, castor oil polyol, and the like. Mixtures of these can also be used.
Of these, polyester polyol and polyether polyol are particularly preferable.
The number average molecular weight of the polyol is preferably in the range of 400 to 5,000.

  Examples of the polyisocyanate include diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene polyisocyanate, xylene diisocyanate, naphthalene diisocyanate and other aromatic polyisocyanates, hexamethylene diisocyanate and other aliphatic polyisocyanates, and dicyclohexylmethane diisocyanate. An alicyclic polyisocyanate such as isophorone diisocyanate or hydrogenated xylylene diisocyanate can be used. In addition, polyisocyanate obtained by modifying the polyisocyanate with carbodiimide, polyisocyanate obtained by modifying the polyisocyanate with isocyanurate, and the like can also be used. These may be used alone or as a mixture. Of these, diphenylmethane diisocyanate, tolylene diisocyanate, and hexamethylene diisocyanate are particularly preferable.

In order to obtain the rubber coating agent of the present invention as an aqueous resin composition, it is necessary to blend component (B) with component (A) and component (C) as an aqueous emulsion or aqueous solution. . The aqueous emulsion or aqueous solution of component (B) comprises a polyol and excess polyisocyanate in a molar ratio of polyol: polyisocyanate of 1:
Addition reaction of 1.1 to 10, preferably 1: 1.3 to 5 to synthesize a urethane prepolymer having an isocyanate group at the molecular end, and then emulsifying the urethane prepolymer in water using a surfactant It can be obtained by dispersing or solubilizing. If the molar ratio of polyol: polyisocyanate is less than 1: 1.1, sequential addition polymerization is likely to occur, and a high molecular weight product is formed. If it is greater than 1:10, the residual amount of free isocyanate increases, and stability during storage. May decrease.
There is no restriction | limiting in particular as said surfactant, The nonionic surfactant mentioned above, a cationic surfactant, and an amphoteric surfactant are preferable. The emulsification dispersion or solubilization may be performed using the above-described emulsification apparatus.

When preparing an aqueous emulsion or aqueous solution of component (B), in addition to the polyol and polyisocyanate, a compound having an active hydrogen atom that reacts with an isocyanate group and a salt-forming group is used to form a urethane prepolymer. The urethane prepolymer synthesized and obtained may be emulsified or solubilized in water using a salt-forming agent.
Examples of the compound having an active hydrogen atom that reacts with an isocyanate group and a salt-forming group include hydroxy acids, aminocarboxylic acids, aminosulfonic acids, hydroxysulfonic acids, and the like, and the salt-forming agents therefor are metal hydroxides. Ammonia, a tertiary amine compound, and the like.
In addition, examples of the compound having an active hydrogen atom and a salt-forming group that react with other isocyanate groups different from the above include amino alcohols, amines, and the like, and salt-forming agents for them include organic acids, inorganic acids, Examples thereof include compounds having a reactive halogen atom.
Furthermore, examples of the compound having an active hydrogen atom and a salt-forming group that react with another isocyanate group different from the above include alcohols having a halogen atom, and as a salt-forming agent therefor, a tertiary amine, sulfides, A phosphine etc. are mentioned. In this method, the aforementioned surfactant may be used in combination. The salt forming agent is usually added in an equivalent amount.

  Also, when preparing an aqueous emulsion or aqueous solution of component (B), use the above polyol and polyisocyanate, and further polyoxyethylene monoalkyl ether and / or polyoxyethylene polyoxypropylene monoalkyl ether. A urethane prepolymer may be synthesized and the obtained urethane prepolymer may be emulsified or solubilized in water. In this method, the aforementioned surfactant may be used in combination.

The urethane prepolymer in the aqueous emulsion or solubilizing solution is made to have a high molecular weight by reaction with water, or a polyvalent amine compound is added to the obtained aqueous emulsion or solubilizing solution to add a polyvalent amine. By making it high molecular weight by reaction with an amine compound, it can be set as the aqueous emulsion or solubilization liquid of the polyurethane resin of (B) component.
The polyurethane resin as component (B) thus obtained preferably has a number average molecular weight in the range of 4,000 to 100,000.

  (B) The compounding quantity of component is 10-100 weight part with respect to 100 weight part of (A) component, Preferably it is 15-80 weight part, Most preferably, it is 20-60 weight part. When the blending amount is less than 10 parts by weight, the film obtained from the composition has poor adhesion to rubber, and the film strength is reduced, resulting in poor wear resistance, exceeding 100 parts by weight. In addition, the film obtained from the present composition has reduced surface smoothness and wear resistance, and becomes inflexible and sometimes cannot follow the deformation of the rubber.

(C) component of this composition is a component which improves surface smoothness, and is organic resin microparticles | fine-particles.
The melting point of the organic resin fine particles is 150 ° C. or higher, preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher. When the melting point of the organic resin fine particles is lower than 150 ° C., the shape of the organic resin fine particles is deformed and the surface smoothness of the resulting film is lowered.
In addition, if the hardness of the organic resin fine particles is high, there is a risk of damaging the surface of the mating material with which the film obtained from the composition rubs, so a relatively soft resin is desirable as the organic resin constituting the organic resin fine particles. Also, a resin with rubber elasticity is desirable.

  Further, the shape of the organic resin fine particles is preferably spherical, and the average particle size thereof is 0.5 to 50 μm, preferably 1 to 20 μm, particularly preferably 2 to 15 μm. When the average particle size is less than 0.5 μm, the surface smoothness is deteriorated, and when it exceeds 50 μm, the film strength is lowered and the wear resistance may be deteriorated.

  The material is not particularly limited as long as it is an organic resin that satisfies the above conditions, but a polyamide resin such as nylon 6 and nylon 66, a crosslinked polyurethane resin such as a polymer of a polyol, a polyisocyanate, and a trivalent or higher amine compound, Crosslinked acrylic resins such as polymers of alkyl (meth) acrylates and polyfunctional functional copolymerizable compounds, acrylic polyols polymerized using 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. as monomers An acrylic urethane resin that is a polymer with isocyanate, or a fluororesin such as polytetrafluoroethylene, polychlorotrifluoroethylene, and tetrafluoroethylene-hexafluoropropylene copolymer is preferred.

  In order to produce organic resin fine particles of component (C), for example, a method of mechanically pulverizing a solid organic resin, an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a spray drying method, a liquid curing method Solvent evaporation method, dissolution dispersion cooling method, etc. may be used.

  The amount of component (C) is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of component (A). When the blending amount of the component (C) is less than 5 parts by weight, the film obtained from the rubber coating agent of the present invention has poor surface smoothness and wear resistance, and when it exceeds 150 parts by weight, the film strength decreases. However, the wear resistance may deteriorate.

  In the rubber coating agent of the present invention, as long as it does not impair the effects of the present invention, as necessary, in addition to the component (A), component (B), and component (C), Silicone resin powder, carbon black, paraffin wax, polyethylene wax, silicone oil, various organic pigments or inorganic pigments, wetting agents, thickeners, antifoaming agents, preservatives, and the like can be blended.

  The rubber coating agent of the present invention is obtained by dispersing and mixing the components (A), (B), and (C) in water. Although the component (C) may be blended as it is, as described above, the component (A) and the component (B) need to be blended as an aqueous emulsion previously emulsified and dispersed in water. The component (C) may also be blended after previously emulsifying and dispersing in water using a dispersant such as a surfactant.

  The mixing of the above components may be performed by a conventionally known mixing stirrer equipped with a paddle type, saddle type or the like. Then, if necessary, water may be added for dilution.

  The rubber to which the rubber coating agent of the present invention can be applied is not particularly limited. For example, natural rubber, EPDM, SBR, NBR, butadiene rubber, butyl rubber, chloroprene rubber, isoprene-isobutylene rubber, nitrile rubber, silicone Various synthetic rubbers such as rubber, urethane rubber, fluororubber and the like can be mentioned. The form of the rubber may be a porous body, a hard body or the like, and is not limited at all.

  Examples of the method for applying the rubber coating agent of the present invention to the rubber surface include brush coating, spray coating, roll coating, flow coating, dip coating, knife coating and the like. When the rubber coating agent of the present invention is used, the coating agent may be applied to the rubber surface by these methods, and then heated and dried to be cured to form a film. The film thickness of the resulting film is preferably in the range of 0.1 to 20 μm, particularly preferably in the range of 0.5 to 10 μm.

  Hereinafter, although a measuring method, a preparation example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the viscosity in the following examples is a value at 25 ° C. measured with an Ostwald viscometer.

<Measurement method>
1. Surface smoothness As shown in FIG. 1, two EPDM rubber sheets 1 and 1 ′ (10 mm × 50 mm, thickness 2 mm) are coated by brushing with an aqueous resin composition to be described later. Adhere double-sided tape to the other side that has not been coated, and then test the rubber 1 and 1 ', respectively, along the opposite sides of the nearly square iron plate 2 (50 mm x 50 mm, thickness 0.3 mm) A piece was made. A hole 3 (radius 1 mm) is opened near one of the other two sides of the iron plate 2, and a string 4 (length 50 mm) is passed through the hole 3 so that the specimen can be pulled. ing.
Next, as shown in FIG. 2, the test piece is placed on a glass plate 5 (60 mm × 190 mm, thickness 3 mm) so that the surface to which the rubber sheets 1 and 1 ′ are attached is on the lower side. Further, a load 6 (weight 1 kg) was applied. Thereafter, the string 4 was pulled horizontally in the direction of the tensile direction 7 (arrow) so that the tensile speed was 100 mm / min on the glass plate 5, and the test piece was moved. At this time, the dynamic friction coefficient between the coated surface of the rubber sheets 1 and 1 ′ and the glass plate was measured.
2. Adhesiveness The surface of a rubber sheet (15 mm x 150 mm, thickness 2 mm) is coated by brushing with an aqueous resin composition to be described later to form a film, and this film is rubbed twice with the thumb and peeled off. Observed whether or not.
3. Abrasion resistance As shown in FIG. 3, a glass cell 8 (line contact, line width: 5 mm) whose surface was polished with a paper file (AA80) was used for the rubber sheet in which the film was not peeled in the adhesion evaluation. The glass cell 8 was subjected to a thrust load of 350 g. In this state, the glass cell 8 is rubbed back and forth on the coating surface under the conditions of a friction speed of 60 reciprocations / minute and a friction stroke of 70 mm, and observed every 50 reciprocations. The number of reciprocating frictions until scraping was measured.

<Preparation example>
-(A) component-
(Preparation Example 1)
In a 1,000 mL glass beaker, 350 g of an organopolysiloxane having a viscosity of 65 mm ² / s represented by the following formula (5) and 50 g of vinyltrimethoxysilane were charged and stirred with a homomixer for 5 minutes. Next, 20 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 15 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), and 265 g of water were added, and the mixture was stirred with a homomixer for 15 minutes. A silicone aqueous emulsion (curable silicone aqueous emulsion A-1) was obtained by passing twice through a high-pressure homogenizer set at 30 MPa.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 2)
A 1,000 mL glass beaker was charged with 350 g of an organopolysiloxane having a viscosity of 65 mm ² / s represented by the above formula (5) and 35 g of vinyltrimethoxysilane, and stirred for 5 minutes with a homomixer. Next, 20 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 15 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), and 280 g of water were added, and the mixture was stirred with a homomixer for 15 minutes. A silicone aqueous emulsion (curable silicone aqueous emulsion A-2) was obtained by passing twice through a high-pressure homogenizer set at 30 MPa.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 3)
A 1,000 mL glass beaker was charged with 350 g of an organopolysiloxane having a viscosity of 65 mm ² / s represented by the above formula (5) and 50 g of phenyltrimethoxysilane, and stirred for 5 minutes with a homomixer. Next, 20 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 15 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), and 265 g of water were added, and the mixture was stirred with a homomixer for 15 minutes. By passing twice through a high-pressure homogenizer set at 30 MPa, a silicone aqueous emulsion (curable silicone aqueous emulsion A-3) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 4)
A 1,000 mL glass beaker was charged with 350 g of an organopolysiloxane having a viscosity of 65 mm ² / s represented by the above formula (5) and 35 g of tetramethoxysilane, and stirred for 5 minutes with a homomixer. Next, 20 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 15 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), and 280 g of water were added, and the mixture was stirred with a homomixer for 15 minutes. A silicone aqueous emulsion (curable silicone aqueous emulsion A-4) was obtained by passing twice through a high-pressure homogenizer set at 30 MPa.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 5)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 770 mm ² / s represented by the following formula (6) and 11 g of vinyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 12 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), 3 g of 10% potassium carbonate aqueous solution, and 378 g of water were added. The mixture was stirred for 15 minutes and then passed twice through a high-pressure homogenizer set at a pressure of 100 MPa to obtain a silicone aqueous emulsion (curable silicone aqueous emulsion A-5).
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 6)
A 1,000 mL glass beaker was charged with 280 g of an organopolysiloxane having a viscosity of 11,400 mm ² / s represented by the following formula (7) and 11 g of vinyltrimethoxysilane, and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 12 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40) and 25 g of water were added and stirred with a homomixer. Admitted. Add 3 g of 10% potassium carbonate aqueous solution, knead and mix with a disper mixer for 10 minutes, and add 353 g of water to this to dilute the silicone aqueous emulsion (curable silicone aqueous emulsion A-6). Obtained.
24 hours after the preparation of the aqueous silicone emulsion, several g was taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 7)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the following formula (8) and 11 g of vinyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Further, add 3 g of 10% potassium carbonate aqueous solution, knead and stir with a disper mixer for 10 minutes, and add 357 g of water to this and dilute to form an aqueous silicone emulsion (curable silicone aqueous emulsion A-7). Got.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 8)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of γ-acryloyloxypropyltrimethoxysilane were charged and stirred with a homomixer for 5 minutes. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Further, add 3 g of 10% potassium carbonate aqueous solution, knead and stir for 10 minutes with a disper mixer, add 357 g of water to this, and dilute to form an aqueous silicone emulsion (curable silicone aqueous emulsion A-8). Got.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 9)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of 3,3,3-trifluoropropyltrimethoxysilane were charged and stirred with a homomixer for 5 minutes. . Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, 3 g of 10% potassium carbonate aqueous solution was added, kneaded with a disper mixer for 10 minutes, stirred, and 357 g of water was added thereto to dilute the silicone aqueous emulsion (curable silicone aqueous emulsion A-9). Got.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 10)
A 1,000 mL glass beaker is charged with 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 5 g of a mineral spirit solution of iron 2-ethylhexanoate (metal Fe content = 8%). The mixture was stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring with a disper mixer for 10 minutes, 355 g of water was added thereto for dilution, 11 g of methyltrimethoxysilane was added, and the mixture was stirred for 1 hour with a vertical stirring blade, whereby an aqueous silicone emulsion ( A curable silicone aqueous emulsion A-10) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 11)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring for 10 minutes with a disper mixer, 354 g of water was added and diluted, and 6 g of a mineral spirit solution of zirconium 2-ethylhexanoate (metal Zr content = 12%) was added. By stirring with a stirring blade for 1 hour, a silicone aqueous emulsion (curable silicone aqueous emulsion A-11) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 12)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring with a disper mixer for 10 minutes, 342 g of water was added to dilute this, 18 g of toluene solution of vanadium naphthenate (metal V content = 2%) was added, and 1 hour with a vertical stirring blade By stirring, a silicone aqueous emulsion (curable silicone aqueous emulsion A-12) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 13)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring with a disper mixer for 10 minutes, 353 g of water was added to dilute this, 7 g of toluene solution of nickel 2-ethylhexanoate (metal Ni content = 6%) was added, and a vertical stirring blade Was stirred for 1 hour to obtain a silicone aqueous emulsion (curable silicone aqueous emulsion A-13).
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 14)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Further, after kneading and stirring for 10 minutes with a disper mixer, 348 g of water was added to dilute the mixture, and 12 g of a toluene solution of barium 2-ethylhexanoate (metal Ba content = 8%) was added thereto. Was stirred for 1 hour to obtain a silicone aqueous emulsion (curable silicone aqueous emulsion A-14).
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 15)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring with a disper mixer for 10 minutes, 356 g of water was added and diluted, and 4 g of a mineral spirit solution of cobalt 2-ethylhexanoate (metal Co content = 12%) was added, followed by vertical stirring. By stirring with a wing for 1 hour, a silicone aqueous emulsion (curable silicone aqueous emulsion A-15) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 16)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 232,000 mm ² / s represented by the following formula (9) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Further, 1 g of calcium chloride dihydrate was added, kneaded with a disper mixer for 10 minutes, stirred and added with 359 g of water to dilute the silicone aqueous emulsion (curable silicone aqueous emulsion A-16). )
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 17)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 232,000 mm ² / s represented by the above formula (9) and 2 g of aluminum dibutoxyacetylacetonate were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, after kneading and stirring for 10 minutes with a disper mixer, 358 g of water was added and diluted, 11 g of methyltrimethoxysilane was added, and the mixture was stirred for 1 hour with a vertical stirring blade to obtain an aqueous silicone emulsion (cured). Aqueous silicone emulsion A-17) was obtained.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 18)
In a 1,000 mL glass beaker, 280 g of an organopolysiloxane having a viscosity of 232,000 mm ² / s represented by the above formula (9) and 11 g of methyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Furthermore, 3 g of 10% aqueous sodium carbonate solution was added, kneaded with a disper mixer for 10 minutes, stirred and added with 357 g of water to dilute the silicone aqueous emulsion (curable silicone aqueous emulsion A-18). Got.
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

(Preparation Example 21)
A 1,000 mL glass beaker was charged with 280 g of an organopolysiloxane having a viscosity of 112,000 mm ² / s represented by the above formula (8) and 14 g of vinyltriethoxysilane, and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 21 g of water were added and stirred with a homomixer. Admitted. Further, knead and stir for 10 minutes with a disper mixer, and add and dilute 347 g of water, 5 g of mineral spirit solution of zinc 2-ethylhexanoate (metal Zr content = 8%) and polyoxyethylene decyl ether (ethylene Mole oxide addition number = 8) 5 g of a mixture was added and stirred with a vertical stirring blade for 1 hour to obtain a silicone aqueous emulsion (curable silicone aqueous emulsion A-21).
24 hours after preparation of the aqueous silicone emulsion, a few grams were taken in a petri dish, and water was volatilized at room temperature for 24 hours to obtain a solid. This was confirmed to be elastic with no tackiness by finger touch.

-(B) component-
-Polyurethane resin aqueous emulsion B:
Superflex 600 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyether-based, nonvolatile content = 25% by weight)

-(C) component-
・ Organic resin fine particles C-1:
Acrylic urethane fine particles BC-79 (trade name, manufactured by Gifu Shellac Co., Ltd., shape: spherical, average particle size: 8 μm, no melting point)
・ Organic resin fine particles C-2:
Nylon fine particles SP-500 (trade name, manufactured by Toray Industries, Inc., shape: spherical, average particle size: 5 μm, melting point 165 ° C.)
・ Organic resin fine particles C-3:
Cross-linked acrylic fine particle art pearl J-7P (trade name, manufactured by Negami Kogyo Co., Ltd., shape: spherical, average particle size: 6 μm, no melting point)
・ Organic resin fine particles C-4:
Cross-linked urethane fine particle dimic beads UCN-5070D (trade name, manufactured by Dainichi Seika Kogyo Co., Ltd., shape: spherical, average particle size: 7μm, no melting point)

<Examples 1 to 26>
Ingredients (A), (B), and (C) shown in the above preparation examples were blended in the blending amounts (g) shown in Tables 1 and 2, and these were uniformly mixed with a vertical stirring blade. When mixed, (A) component, (B) component, and (C) component (in the table, active ingredients) are in the weight ratios shown in Tables 1 and 2 (the numbers in the table represent parts by weight). An aqueous resin composition as a rubber coating agent was prepared.
And this is applied to the surface of the EPDM rubber sheet (2 mm) by brush, and left in a hot air circulating thermostat set at 150 ° C. for 5 minutes to form a film. Surface smoothness, adhesion, and abrasion resistance were measured and evaluated. The results are shown in Tables 1 and 2.

<Comparative Examples 1-6> In addition to the (A) component, (B) component, and (C) component obtained in the above preparation examples, the following A-19 component, A An aqueous resin composition as a rubber coating agent was prepared in the same manner as in Examples 1 to 26 except that the -20 component was also used.
And the said (A) component, (B) component, and (C) component which were prepared are mix | blended with the compounding quantity (g) shown in Table 3, (A) component, (B) component by said operation. And (C) component (in the table, active ingredient) manufactured by EPDM in the same manner as in the Examples, using an aqueous resin composition having the weight ratio shown in Table 3 (the values in the table represent parts by weight). The sheet was subjected to surface treatment, and surface smoothness, adhesion, and abrasion resistance were measured and evaluated according to the above-described measurement methods 1 to 3. The results are shown in Table 3.

(Preparation Example 19)
In a 1,000 mL glass beaker, 350 g of an organopolysiloxane having a viscosity of 62 mm ² / s represented by the following formula (10) and 50 g of vinyltrimethoxysilane were charged and stirred for 5 minutes with a homomixer. Next, 20 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 4), 15 g of polyoxyethylene decyl ether (number of moles of ethylene oxide added = 40), 3 g of 10% potassium carbonate aqueous solution, and 262 g of water were added. The mixture was stirred for 15 minutes and passed through a high-pressure homogenizer set at a pressure of 30 MPa twice to obtain a silicone emulsion. This was diluted by adding 359 g of water to obtain a silicone aqueous emulsion (curable silicone aqueous emulsion A-19).
24 hours after preparation of the silicone emulsion, a few grams were taken in a petri dish and water was volatilized for 24 hours at room temperature. However, the residue was liquid and the silicone was not cured.

(Preparation Example 20)
A 1,000 mL glass beaker was charged with 280 g of an organopolysiloxane having a viscosity of 750 mm ² / s represented by the following formula (11) and 15 g of vinyltrimethoxysilane, and stirred for 5 minutes with a homomixer. Next, 16 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 4), 12 g of polyoxyethylene decyl ether (number of moles of added ethylene oxide = 40), and 371 g of water were added, and the mixture was stirred for 15 minutes with a homomixer. Two passes through the high-pressure homogenizer set at 100 MPa. Thereto was added 6 g of a mineral spirit solution of zirconium 2-ethylhexanoate (metal Zr content = 12%), and the mixture was stirred with a vertical stirring blade for 1 hour, whereby an aqueous silicone emulsion (curable silicone aqueous milk). A suspension A-20) was obtained.
24 hours after the preparation of the aqueous silicone emulsion, several g was taken in a petri dish, and water was volatilized for 24 hours at room temperature. However, the residue was liquid and the silicone was not cured.

(Evaluation)
As can be seen from the above results, in Examples 1 to 26 according to the present invention, good results were obtained in any of surface smoothness, adhesion, and wear resistance.
On the other hand, as in Comparative Example 1, when the component (A-1) is an organopolysiloxane that does not contain the group represented by the formula (1), the curability of the component (A) is insufficient. As a result, the resulting film has poor surface smoothness and adhesion.
Further, as in Comparative Example 2, when the component (A-1) is an organopolysiloxane containing a group represented by the formula (1) in the side chain instead of the molecular chain end, (A) Insufficient curability of the components results in poor surface smoothness and adhesion of the resulting film.
Moreover, when the polyurethane resin of (B) component is not mix | blended like the comparative example 3, the adhesiveness of the membrane | film | coat obtained becomes a poor thing.
Moreover, when the addition amount of the polyurethane resin of (B) component is large like the comparative example 4, it turns out that the surface smoothness and abrasion resistance of the membrane | film | coat obtained are scarce.
Moreover, when the organic resin fine particle of (C) component is not mix | blended like the comparative example 5, the surface smoothness and abrasion resistance of the membrane | film | coat obtained become poor.
In addition, as in Comparative Example 6, when the amount of the organic resin fine particles as the component (C) is large, the obtained film has poor wear resistance.

It is a perspective view which shows the test body used in order to evaluate the surface smoothness of a film | membrane. It is a figure which shows the method of measuring a dynamic friction coefficient using said test body. It is a figure which shows the method of measuring the abrasion resistance of a film | membrane.

Explanation of symbols

1 EPDM rubber sheet 1 'EPDM rubber sheet 2 Iron plate 3 Hole 4 String 5 Glass plate 6 Load 7 Tensile direction 8 Glass cell 9 EPDM rubber sheet

Claims (5)

A rubber coating agent comprising an aqueous resin composition comprising the following component (A), component (B), and component (C).
(A) component:
(A-1) Component: Organopolysiloxane represented by the following formula (3) and / or (4) ,

[Monovalent hydrocarbon group wherein, R ⁹ is independently a monovalent hydrocarbon group hydrogen atom or 1 to 6 carbon atoms, R ¹⁰ is 1 to 20 carbon atoms independently, R ¹¹ is formula (1 ), R ¹² is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is 10 to 2,000. ]

[Wherein R ² is an unsubstituted or substituted divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ , R ⁵ and R ⁶ are Each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, m is an integer of 0 to 6, and when m is not 0, R ⁴ , R ⁵ and R ⁶ At least one of them is a hydrogen atom, and when m is 0, at least one of the R ⁵ and R ⁶ is a hydrogen atom. ]
(A-2) Component: alkoxysilane represented by the following formula (2) and / or a partial hydrolysis condensate thereof,

[Wherein R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁸ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is 0 or 1 It is. ]
(A-3) Component: 0 to 10 parts by weight of a condensation catalyst with respect to 100 parts by weight of the total amount of the components (A-1) and (A-2),
Curable silicone composition comprising: 100 parts by weight,
(B) component: polyurethane resin: 10 to 100 parts by weight,
Component (C): or a melting point is 0.99 ° C. or higher, or having no melting point, the average particle diameter of Ri 0.5~50μm der, polyamide resin, the organic resin fine particles comprising a crosslinked acrylic resin or fluorine resin: 5 to 150 wt Department. The amount of the component (A-2) used relative to the component (A-1) is R in the component (A-2) with respect to a total of 1 mol of the hydroxyl group and R ¹ O-group in the component (A-1). The rubber coating agent according to claim 1, wherein the amount of ⁸ O-group is 0.5 to 100 mol. The alkoxysilane as the component (A-2) is methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, or γ-acryloyloxypropyltrimethoxysilane. Γ-acryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl The rubber coating agent according to claim 1 or 2, which is triethoxysilane, tetramethoxysilane, or tetraethoxysilane. The condensation catalyst of the component (A-3) is one or more selected from sodium compounds, aluminum compounds, potassium compounds, calcium compounds, vanadium compounds, iron compounds, cobalt compounds, nickel compounds, zinc compounds, zirconium compounds, and barium compounds. The rubber coating agent according to any one of claims 1 to 3, wherein the metal coating compound is a metal compound. An article formed by applying the rubber coating agent according to any one of claims 1 to 4.

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