JP3827301B2 - Aqueous silicone resin composition - Google Patents

Description

【００７８】
比較例１〜 12
上記調製例で得た（Ａ）成分、(Ｃ)成分および(Ｆ)成分、上記実施例の(Ｂ)成分、（Ｄ）成分、（Ｅ）成分および(Ｇ)成分並びに下記の(Ｆ)成分およびシリコーンゴム微粒子分散液を表２に示した配合量・組成比で混合して表面処理剤組成物としての水性シリコーン樹脂組成物を調製し、これらを用いて実施例と同様にしてEPDM製多孔質体シートの表面処理を行い、評価した。その結果を表２に示す。
【００７９】
・(Ｆ)成分
微粒子分散液F-6：コロイダルシリカスラリー スノーテックスＯ（商品名、日産化学工業(株)製、濃度＝重量20％、粒子径＝10〜20nm）
・シリコーンゴム微粒子分散液
X-52-1539（商品名、信越化学工業(株)製、濃度＝50重量％、平均粒径＝5μm）
【００８０】
【表２】

※ 皮膜がべたつくため、評価せず。
【００８１】
［評価］
比較例１のように(Ａ)成分のオルガノポリシロキサンの複素粘性率が低い場合、表面滑り性、耐摩耗性の乏しいものになり、比較例２のように(Ｂ)成分のオルガノトリアルコキシシランが配合されていない場合には、皮膜の硬化が不十分なものになり、比較例３のように(Ｃ)成分のアミド基およびカルボキシル基含有のオルガノアルコキシシラン並びに(Ｄ)成分のエポキシ基含有のオルガノアルコキシシランが配合されていない場合場合には、表面滑り性、耐摩耗性の乏しいものになり、比較例４のように(Ｃ)成分のアミド基およびカルボキシル基含有のオルガノアルコキシシラン並びに(Ｄ)成分のエポキシ基含有のオルガノアルコキシシランの添加量が多い場合には、耐摩耗性の乏しいものになり、比較例５のように(Ｆ)成分の疎水性微粒子が配合されていない場合には、表面滑り性、耐摩耗性の乏しいものになり、比較例６のように(Ｆ)成分の疎水性微粒子の添加量が多い場合には、耐摩耗性の乏しいものとなることが分かる。
【００８２】
また、比較例７のように(Ｇ)成分の有機樹脂微粒子が配合されていない場合には、表面滑り性、耐摩耗性の乏しいものになり、比較例８のように(Ｇ)成分の有機樹脂微粒子の添加量が多い場合には、耐摩耗性の乏しいものとなり、比較例９、比較例10および比較例11のように(Ｆ)成分がトリメチルシリル基で疎水化されてない微粒子である場合には、表面滑り性、耐摩耗性の乏しいものになることが分かる。
次に、比較例12のように(Ｇ)成分の代わりに、シリコーンゴム微粒子を使用した場合には、表面滑り性の乏しいものになることが分かる。
【００８３】
【発明の効果】
本発明の水性シリコーン樹脂組成物は、ゴム材料または繊維材料からなる基材の表面にコーティングして硬化させ皮膜を形成するものであり、得られた皮膜は基材との密着性に優れ、かつ基材表面に優れた滑り性および耐摩耗性を付与することができる。
【図面の簡単な説明】
【図１】実施例・比較例において、皮膜の表面平滑性を評価するために使用される試験体を示す斜視図である。
【図２】上記試験体を用いて、動摩擦係数を測定する方法を示す図である。
【図３】実施例・比較例において、皮膜の耐摩耗性を測定する方法を示す図である。
【符号の説明】
１，1' EPDM製多孔質体ストリップ
２ 鉄板
３ 穴
４ ひも
５ ガラス板
６ 荷重６
７ 引張り方向
８ ガラスセル
９ EPDM製多孔質体シート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aqueous silicone resin composition useful for surface coating of rubber materials and fiber materials, which provides a film excellent in adhesion to a substrate, abrasion resistance and surface smoothness.
[0002]
[Prior art]
Conventionally, in order to impart smoothness and wear resistance to the surface of various rubbers, a method of coating and curing the surface with a silicone resin composition has been performed.
Examples of the silicone resin composition include a composition comprising an epoxy group-containing organopolysiloxane and an amino group-containing alkoxysilane (Japanese Patent Laid-Open No. 54-43891), a hydroxyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and an epoxy group-containing composition. Composition comprising an organopolysiloxane and an amino group-containing alkoxysilane (JP 54-45361, JP 54-90369, JP 54-90375), a hydroxyl group-containing organopolysiloxane and an organohydrogenpolysiloxane Composition comprising hydrolyzed condensate of alkenyl and amino group-containing dialkoxysilane (JP-A-7-109440, JP-A-7-126417), hydroxyl- or vinyl-group-containing organopolysiloxane, organohydrogenpolysiloxane and dimethylpolysiloxane Composition comprising JP-A-62-215667, containing hydrolyzable groups Composition comprising an organopolysiloxane, an epoxy or amino group and hydrolyzable group-containing organopolysiloxane and an epoxy group or amino group-containing hydrolyzable silane (Japanese Patent Laid-Open No. 7-196984), a hydroxyl and epoxy group-containing polyorgano A composition comprising siloxane, an amino group-containing alkoxysilane and a mercapto group-containing alkoxysilane (Japanese Patent Laid-Open No. 5-5082) has been proposed.
[0003]
However, since the films obtained from these silicone resin compositions are particularly poor in wear resistance and surface smoothness, compositions containing fine powders have been proposed to improve the above properties.
For example, a silicone resin composition containing polymethylsilsesquioxane as a fine powder has been proposed. Hydroxyl group-containing polyorganosiloxane, epoxy group-containing polyorganosiloxane, amino group-containing alkoxysilane, and polymethylsilsesquioxane powder Composition comprising JP-A-61-159427, JP-A-2-33763, silanol group-containing dimethylpolysiloxane, amino group-containing diorganopolysiloxane, γ-glycidoxypropyltrimethoxysilane and polymethylsilsesqui And a composition comprising fine oxane powder (Japanese Patent Laid-Open No. 7-251124).
[0004]
Silicone resin compositions containing fine powders of silicone rubber have also been proposed. For example, non-flowable branched organopolysiloxane, hydrolysis condensate of epoxy group-containing dialkoxysilane, amino group-containing dialkoxysilane Hydrolyzed condensate and silicone rubber fine powder (JP-A-7-233351), non-flowable branched organopolysiloxane, amino group-containing diorganopolysiloxane, epoxy group-containing dialkoxysilane Condensate, hydrolysis condensate of amino group-containing dialkoxysilane, composition comprising (meth) acryloyl group or amino group-containing trialkoxysilane and silicone rubber fine powder (JP-A-7-310051), hydroxyl group-containing organopolysiloxane Hydrolysis condensate of epoxy group-containing dialkoxysilane, water-soluble amino acid The compounds and silicone rubber fine consists powder composition (JP-A-9-53047) and the like.
A silicone resin composition containing a polycarbonate resin fine powder has also been proposed. For example, a composition (JP-A-9-1291) comprising an organopolysiloxane having an alkenyl group, an organohydrogenpolysiloxane, and a polycarbonate resin fine powder.
[0005]
According to the silicone resin composition containing the above fine powder, the effect of improving the wear resistance and surface smoothness is recognized, but the film obtained from the composition containing the fine powder of silicone rubber has a slight surface smoothness. Further, the film obtained from the composition containing the polymethylsilsesquioxane fine powder or the polycarbonate resin fine powder has the disadvantage that it easily damages the surface of other materials that rub against each other. There is a need for improvements.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to obtain an aqueous silicone resin composition that can solve the problems of the conventional silicone resin composition and provides a film excellent in adhesion to a substrate, wear resistance, and surface smoothness. Is.
[0007]
[Means for Solving the Problems]
Therefore, in order to achieve the above object, the present invention provides
Formula (A): [R¹ ₂SiO_2/2] (R¹Is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and the formula: [R²SiO_3/2] (R²Is R¹As the structural unit), and the molar ratio of both units: [R¹ ₂SiO_2/2] / [R²SiO_3/2] = 1 / (0 to 0.01), the complex viscosity at 25 ° C. is 1 × 10^FourmPa · s or more terminal hydroxyl-blocked organopolysiloxane: 100 parts by weight,
(B) Formula: R^ThreeSi (OR^Four)_Three(R^ThreeIs an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms which does not contain any amide bond, carboxyl group or epoxy group, and R^FourIs independently a monovalent hydrocarbon group having 1 to 6 carbon atoms) and / or a partial hydrolysis condensate thereof: 0.01 to 10 parts by weight,
(C) an organoalkoxysilane containing an amide bond and a carboxyl group and not containing an epoxy group and / or a partial hydrolysis condensate thereof: 1 to 20 parts by weight,
(D) an organoalkoxysilane containing an epoxy group and containing neither an amide bond nor a carboxyl group and / or a partial hydrolysis condensate thereof: 1 to 20 parts by weight,
(E) Curing catalyst: effective amount,
(F) (F1) Formula: [SiO_4/2Silica fine particles composed of structural units represented by formula (F2): [SiO_4/2] Units and formula: [R⁶SiO_3/2] (R⁶Is an independently substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and a fine particle having a unit represented by formula (F3): [R⁶SiO_3/2] (R⁶Is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms) at least one selected from the group consisting of polyorganosilsesquioxane fine particles having as a structural unit The surface of the seed microparticles is the formula: [R^Five _ThreeSiO_1/2] (R^FiveIs independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms). Hydrophobic fine particles having an average particle diameter of 5 to 1000 nm and having an average particle size of 5 to 150 Parts by weight, and
(G) Spherical organic resin fine particles having a melting point of 150 ° C. or higher and an average particle size of 0.5 to 50 μm: 5 to 100 parts by weight
An aqueous silicone resin composition is provided.
(Hereinafter, when it is not necessary to distinguish the fine particles (F1), (F2) or (F3) related to the component (F), these fine particles are collectively referred to as “silica / silsesquioxane fine particles”. Sometimes.)
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0009]
[Component (A)]
The component (A) of the aqueous silicone resin composition of the present invention has the formula: [R¹ ₂SiO_2/2] (R¹Is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and the formula: [R²SiO_3/2] (R²Is R¹As the structural unit), and the molar ratio of both units: [R¹ ₂SiO_2/2] / [R²SiO_3/2] = 1 / (0 to 0.01), the complex viscosity at 25 ° C. is 1 × 10^FourIt is a terminal hydroxyl-blocked organopolysiloxane of mPa · s or more. [R¹ ₂SiO_2/2] Units and [R²SiO_3/2The units may be one kind or a combination of two or more kinds.
[0010]
R in the above unit formula¹And R²Specifically, alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group; vinyl group, An alkenyl group such as an allyl group; an aryl group such as a phenyl group and a tolyl group; a cycloalkyl group such as a cyclohexyl group; and a group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, For example, 3,3,3-trifluoropropyl group and the like can be mentioned, and methyl group is particularly preferable.
[0011]
The molar ratio of both units is [R¹ ₂SiO_2/2] / [R²SiO_3/2] = 1 / (0 to 0.01), preferably 1 / (0 to 0.005). [R¹ ₂SiO_2/2] [R for one mole of unit²SiO_3/2When the unit content is more than 0.01 mol, the resulting film has low surface smoothness and poor wear resistance.
In addition, [R²SiO_3/2The unit is an arbitrary structural unit and may not be contained in the organopolysiloxane of component (A). In this case, the component (A) is, for example, a linear diorganopolysiloxane having both ends blocked with hydroxyl groups.
[0012]
The complex viscosity of this organopolysiloxane at 25 ° C. is 1 × 10^FourmPa · s or more is required, preferably 1 × 10^FiveMore than mPa · s. The complex viscosity is 1 × 10^FourWhen it is less than mPa · s, the resulting film does not exhibit sufficient adhesion to the substrate and slipperiness. Here, the complex viscosity is easily measured by a commercially available general measuring device. For example, using “Controlled Stress Rheometer CS Model” (manufactured by Borin), “Ares Viscoelasticity Measurement System (for fluid measurement)” (manufactured by Rheometric Scientific), etc., For example, it may be measured at 0.1 rad / s.
[0013]
Such an organopolysiloxane can be prepared by a known method, for example, using an acidic catalyst or an alkaline catalyst: [R¹ ₂SiO]_m(R¹Is as described above, and m is an integer of 3 to 7), and if necessary, the formula: R²Si (OR⁸)_Three(R²Is as above, R⁸Is a monovalent hydrocarbon group having 1 to 6 carbon atoms), and can be synthesized by, for example, equilibrating reaction of trialkoxysilane and water.
[0014]
In the case of the aqueous silicone resin composition of the present invention, it is necessary to blend the organopolysiloxane as the component (A) as an aqueous emulsion, and when the viscosity of the organopolysiloxane is high, Since it is relatively difficult to obtain a stable emulsion, it is preferable to produce an aqueous emulsion by a known emulsion polymerization method.
[0015]
That is, the formula: [R¹ ₂SiO]_m(R¹, M is as described above) and / or the formula: R⁹O [R¹ ₂SiO]_nR⁹(R¹Is as above, R⁹Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 1,000), and if necessary, the formula: R²Si (OR⁸)_Three(R², R⁸Is, for example, trialkoxysilane, dispersed in water using a surfactant, and subjected to a polymerization reaction by an equilibration reaction using an acidic catalyst or an alkaline catalyst. By deactivating the catalyst, an aqueous emulsion of organopolysiloxane as component (A) can be easily obtained. When an acid type surfactant such as alkyl sulfuric acid, alkyl benzene sulfonic acid, polyoxyethylene alkyl ether sulfuric acid or the like is used as the acidic catalyst, the surface active ability and the acid catalytic ability are combined.
[0016]
[Component (B)]
The component (B) of the aqueous silicone resin composition of the present invention functions as a crosslinking agent for the organopolysiloxane that is the component (A).^ThreeSi (OR^Four)_Three(R^ThreeIs an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms which does not contain any amide bond, carboxyl group or epoxy group, and R^FourIs independently a monovalent hydrocarbon group having 1 to 6 carbon atoms) and / or a partial hydrolysis-condensation product thereof.
[0017]
R in the formula^ThreeSpecifically, alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group; vinyl group, Alkenyl groups such as allyl groups; aryl groups such as phenyl groups and tolyl groups; cycloalkyl groups such as cyclohexyl groups; and some or all of the hydrogen atoms bonded to carbon atoms of these groups are halogen atoms, mercapto groups, acryloxy Examples include a group substituted with a hydrocarbon group containing a group, such as 3,3,3-trifluoropropyl group, γ-methacryloxypropyl group, γ-acryloxypropyl group, γ-mercaptopropyl group, and the like. R in the formula^FourSpecific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are particularly preferable.
[0018]
Specific examples of this organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane , Butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, octadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltri Tokishishiran, 3,3,3-trifluoropropyl trimethoxysilane, and their partially hydrolyzed condensates thereof. These can be used singly or in combination of two or more.
[0019]
The amount of component (B) is required to be 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of component (A). When the blending amount is less than 0.01 parts by weight, the resulting film is not sufficiently cured, and when it exceeds 10 parts by weight, the adhesion of the resulting film to the substrate may be inferior.
[0020]
[Component (C)]
Component (C) of the aqueous silicone resin composition of the present invention is a component for improving the adhesion of the resulting film to the base material, and contains an amide bond and a carboxyl group, and an organoalkoxy having no epoxy group Silane and / or its partial hydrolysis condensate. The organoalkoxysilane is obtained by reacting an alkoxysilane containing an amino group with a dicarboxylic acid anhydride.
[0021]
Specific examples of the alkoxysilane containing an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- ( N-β-aminoethyl) aminopropyltrimethoxysilane, γ- (N-β-aminoethyl) aminopropyltriethoxysilane, γ- (N-β-aminoethyl) aminopropylmethyldimethoxysilane, γ- (N- β-aminoethyl) aminopropylmethyldiethoxysilane and the like, and specific examples of the dicarboxylic acid anhydride include phthalic acid anhydride, succinic acid anhydride, methyl succinic acid anhydride, maleic acid anhydride, glutar An acid anhydride, an itaconic acid anhydride, etc. are mentioned.
[0022]
The alkoxysilane containing the amino group according to component (C) can be easily obtained by mixing at room temperature in a parent solvent for both the starting materials, for example, alcohol. In this case, since it is necessary to contain at least one amide bond and a carboxyl group in one molecule of the reaction product, —NH present in one molecule of the alkoxysilane containing an amino group.₂It is necessary to react at least one molecule of dicarboxylic anhydride per group. Component (C) can be used alone or in combination of two or more.
[0023]
The amount of component (C) is required to be 1 to 20 parts by weight with respect to 100 parts by weight of component (A), preferably 3 to 10 parts by weight, and the amount is less than 1 part by weight. When the amount of the coating film is more than 20 parts by weight, the coating film may not follow the base material and may not be stretched.
[0024]
[Component (D)]
Component (D) of the aqueous silicone resin composition of the present invention is a component for improving adhesion to a substrate, contains an epoxy group, an organoalkoxysilane containing neither an amide bond nor a carboxyl group, and / Or a partial hydrolysis condensate thereof.
[0025]
Specific examples of the component (D) include β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane. , Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxy Silane etc. and these partial hydrolysis-condensation products are mentioned. These can be used singly or in combination of two or more.
[0026]
The blending amount of component (D) is required to be 1 to 20 parts by weight, preferably 3 to 10 parts by weight with respect to 100 parts by weight of component (A), and the blending amount is 1 part by weight. If it is less than the range, the resulting film does not exhibit adhesion to the substrate, and if it exceeds 20 parts by weight, it may be a film that does not follow the substrate and does not stretch.
[0027]
[(E) component]
Component (E) of the aqueous silicone resin composition of the present invention is a curing catalyst for crosslinking and curing the components of the composition of the present invention, specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate , Organotin compounds such as dioctyltin diacetate, tin octylate, zinc compounds such as zinc laurate, zinc acetate, zinc stearate, zinc octylate, tetrapropyl titanate and its partially hydrolyzed condensate, tetrabutyl titanate and The partial hydrolysis-condensation products, organic titanium compounds such as bisdipropoxytitanium, bis (acetylacetonate) titanium oxide, titanium lactate, ammonium titanium lactate and the like can be mentioned. These can be used singly or in combination of two or more.
When this curing catalyst is not water-soluble, it is desirable to preliminarily emulsify and disperse in water using a surfactant to form an aqueous emulsion.
[0028]
The compounding amount of the component (E) may be an effective amount as a catalyst, and is not particularly limited. 2 parts by weight. If the blending amount is too small, the resulting film is not sufficiently cured. Conversely, if the amount is too large, the effect is not changed and it is economically disadvantageous.
[0029]
[(F) component]
The component (F) of the aqueous silicone resin composition of the present invention is a component that improves surface smoothness and wear resistance, and the surface of the silica / silsesquioxane fine particles is represented by the formula: [R^Five _ThreeSiO_1/2] (R^FiveIs independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and is a hydrophobic fine particle having an average particle diameter of 5 to 1000 nm.
[0030]
The silica / silsesquioxane fine particles used are represented by the formula (F1): [SiO_4/2Silica fine particles comprising structural units as units represented by formula (F2): [SiO_4/2] Units and formula: [R⁶SiO_3/2] (R⁶Is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and (F3) formula: [R⁶SiO_3/2] (R⁶Is at least one fine particle selected from the group consisting of polyorganosilsesquioxane fine particles having a unit represented by (1) as a structural unit.
[0031]
Formula (F2): [SiO_4/2] Units and formula: [R⁶SiO_3/2In the case of fine particles having a unit represented by_4/2] Units and [R⁶SiO_3/2] The unit ratio is arbitrary. In addition to this, the formula: [R^Ten ₂SiO_2/2] (R^TenIs independently a unit represented by a substituted or specific substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and / or the formula: [R¹¹ _ThreeSiO_1/2] (R¹¹Is R^TenMay be contained as an arbitrary constituent unit. However, if the content of these units is large, the fine particles become soft and the resulting film has reduced strength and wear resistance. Tend to get worse. Therefore, [SiO_4/2] Units and [R⁶SiO_3/2It is necessary that the total content of the units be 70 mol% or more, preferably 90 mol% or more.
[0032]
R in the structural units in (F2) and (F3) above⁶As, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc. Cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl groups; aralkyl groups such as β-phenylpropyl groups; and these hydrocarbons Halogenation of 3,3,3, -trifluoropropyl group, β- (perfluorobutyl) ethyl group, β- (perfluorooctyl) ethyl group, etc. in which some or all of the hydrogen atoms in the group are substituted with halogen atoms A hydrocarbon group and a part or all of hydrogen atoms of these hydrocarbon groups are amino group, epoxy group, acryloxy group, It is selected from hydrocarbon groups substituted with a functional group such as a methacryloxy group, a mercapto group, or a cyano group. Among these, a methyl group and / or a vinyl group are most preferable. The above R^TenAnd R¹¹Also said R⁶The same group is illustrated.
[0033]
In the present invention, the hydrophobic fine particle of the component (F) is obtained by expressing the surface of the silica / silsesquioxane fine particle with the formula: [R^Five _ThreeSiO_1/2] (R^FiveIs independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms). R^FiveAs the above R⁶The same group is illustrated, and among them, a methyl group is most preferable.
[0034]
The average particle size of the hydrophobic fine particles of the component (F) in the present invention is in the range of 5 nm to 1,000 nm, preferably 10 nm to 500 nm, more preferably 10 nm to 100 nm. When the average particle size is larger than 1,000 nm, the strength of the resulting film is lowered and the wear resistance is deteriorated, and it is difficult to redisperse by sedimentation in the composition during storage. Moreover, it is practically difficult to obtain an average particle size of less than 5 nm.
[0035]
The component (F) of the present invention has a formula: R as a hydrophobizing agent for surface treatment in an aqueous dispersion of silica / silsesquioxane fine particles containing an anionic surfactant and an acidic catalyst.^Five _ThreeSiOR¹²(R^FiveIs as above, R¹²Is a monovalent hydrocarbon group having 1 to 6 carbon atoms) or a formula: R^Five _ThreeSiOH (R^FiveIs added as described above) to cause a condensation reaction, or similarly to an aqueous dispersion of silica / silsesquioxane fine particles containing a cationic surfactant and an alkaline catalyst, The aqueous silicone resin composition of the present invention is preferably blended as an aqueous dispersion obtained by adding the hydrophobizing agent for surface treatment and causing a condensation reaction.
[0036]
The acidic catalyst used together with the anionic surfactant is not particularly limited as long as it is an acidic substance, but a strong acid having a low pH value in a small amount is preferable. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, alkyl sulfuric acid, alkylbenzene sulfonic acid And polyoxyethylene alkyl ether sulfuric acid. These can be used singly or in combination of two or more. When alkyl sulfuric acid, alkyl benzene sulfonic acid, or polyoxyethylene alkyl ether sulfuric acid is used, both surface activity ability and acid catalytic ability are combined. The amount of the acidic catalyst to be added is preferably such that the pH of the aqueous dispersion is in the range of 1.0 to 4.0, more preferably 1.5 to 3.0. When the pH of the aqueous dispersion is higher than 4.0, the reaction rate of the surface treating hydrophobizing agent is deteriorated, and even if the pH is less than 1.0, improvement of the reaction rate cannot be expected.
[0037]
The sex catalyst used together with the cationic surfactant is not particularly limited as long as it is an alkaline substance. For example, alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide; calcium hydroxide, hydroxide Alkaline earth metal hydroxides such as barium; alkali metal carbonates such as potassium carbonate and sodium carbonate; ammonia, tetramethylammonium hydroxide or monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentamine, dimethylamine Further, amines such as diethylamine, trimethylamine, triethanolamine, and ethylenediamine can be used. These can be used singly or in combination of two or more. The amount of the alkaline catalyst to be added is preferably such that the pH of the aqueous dispersion is in the range of 9.0 to 13.0, more preferably 10.0 to 12.0. When the pH of the aqueous dispersion is less than 9.0,
The reaction rate of the hydrophobizing agent for surface treatment is deteriorated, and even if the pH is higher than 13.0, improvement of the reaction rate cannot be expected.
[0038]
The anionic surfactant may be a known one, for example, alkyl sulfate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, N-acyl taurate, alkyl benzene. Sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, α-orphine sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether disulfonates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ethers Sulfosuccinate, fatty acid salt, polyoxyethylene alkyl ether acetate, N-acyl amino acid salt, alkenyl succinate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, and And the like of the acid. These can be used alone or in combination of two or more.
[0039]
Any known cationic surfactant may be used, for example, alkyltrimethylammonium salt, dialkyldimethylammonium salt, polyoxyethylenealkyldimethylammonium salt, dipolyoxyethylenealkylmethylammonium salt, tripolyoxyethylene. Examples include alkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridium salts, monoalkylamine salts, and monoalkylamidoamine salts. These can be used alone or in combination of two or more.
[0040]
Here, the formula of (F1): [SiO_4/2In the case of using an aqueous dispersion of silica fine particles composed of units represented by the following formula, there is no particular limitation. For example, water glass is used as a starting material, alkali is extracted by ion exchange, and the core of the particles becomes silica sol. A so-called colloidal silica slurry obtained by growing to a maximum can be used. When this colloidal silica slurry is used, since it does not contain a surfactant, it is preferable to incorporate an anionic surfactant or a cationic surfactant. Furthermore, 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, polyoxyethylene Nonionic field surfactants such as reoxypropylene-modified organopolysiloxane and / or alkyldimethylamine oxide, alkyldimethylcarboxybetaine, alkylamidopropyldimethylcarboxybetaine, alkylhydroxysulfobetaine, alkylcarboxymethylhydroxyethylimidazolinium betaine A small amount of amphoteric surfactants such as these may be used together.
[0041]
Further, the above formula (F2): [SiO_4/2] Units and formula: [R⁶SiO_3/2In the case where an aqueous dispersion of fine particles having a unit represented by the following formula is used, an anionic surfactant or a cationic surfactant is added to the colloidal silica slurry, and an acidic or alkaline condition is used. An aqueous dispersion obtained by adding organotrialkoxysilane and hydrolytic condensation can be used. An anionic surfactant or a cationic surfactant is added as necessary. Furthermore, a small amount of the nonionic surfactant and / or amphoteric surfactant may be used in combination.
[0042]
Next, the formula (F3): [R⁶SiO_3/2In the case of using an aqueous dispersion of polyorganosilsesquioxane fine particles having a unit represented by the following formula, as described in Japanese Patent Publication No. 52-12219, an aqueous dispersion of silsesquioxane fine particles is used. Add the organotrialkoxysilane or the partially hydrolyzed condensate thereof to the liquid, that is, water containing an anionic surfactant and an acidic catalyst, or water containing a cationic surfactant and an alkaline catalyst. An aqueous dispersion obtained by a method of decomposing and condensing can be used. An anionic surfactant or a cationic surfactant is added as necessary. Furthermore, a small amount of the nonionic surfactant and / or amphoteric surfactant may be used in combination.
[0043]
As a hydrophobizing agent for surface treatment, the formula: R^Five _ThreeSiOR¹²(R^FiveIs as above, R¹²Is a monovalent hydrocarbon group having 1 to 6 carbon atoms) or a formula: R^Five _ThreeSiOH (R^FiveIs as described above). R in the silane compound that is the hydrophobizing agent for surface treatment¹²Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group and an ethyl group are particularly preferable.
[0044]
  The above formula: R used as a hydrophobizing agent for surface treatment^Five _ThreeSiOR¹²As the silane compound represented by, trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, trihexylmethoxysilane, triphenylmethoxysilane, tribenzylmethoxysilane, diethylvinylmethoxysilane, dimethylpropylmethoxysilane, Trimethyl such as dimethylphenylmethoxysilane, dimethyloctylmethoxysilane, dimethyloctadecylmethoxysilane, diphenylmethylmethoxysilaneHydrocarbylMethoxysilane; trimethylethoxysilane, triethylethoxysilane, tripropylethoxysilane, tributylethoxysilane, trihexylethoxysilane, triphenylethoxysilane, tribenzylethoxysilane, dimethylvinylethoxysilane, dimethylpropylethoxysilane, dimethylphenylethoxysilane, Dimethyloctylethoxysilane, dimethyloctadecylethoxysilane, diphenylMethylTris such as ethoxysilaneHydrocarbylEthoxysilane; trimethylpropoxysilane, triethylpropoxysilane, tripropylpropoxysilane, tributylpropoxysilane, trihexylpropoxysilane, tribenzylpropoxysilane, dimethylvinylpropoxysilane, dimethylpropylpropoxysilane, dimethylphenylpropoxysilane, dimethyloctylpropoxysilane, Trimethyl dimethyloctadecylpropoxysilane, diphenylmethylpropoxysilane, etc.HydrocarbylPropoxysilane; trimethylbutoxysilane, triethylbutoxysilane, tripropylbutoxysilane, tributylbutoxysilane, triphenylbutoxysilane, tribenzylbutoxysilane, dimethylvinylbutoxysilane, dimethylpropylbutoxysilane, dimethylphenylbutoxysilane, dimethyloctylbutoxysilane, Trimethyl dimethyloctadecylbutoxysilane, diphenylmethylbutoxysilane, etc.HydrocarbylButoxysilane;
[0045]
Trimethylpentyloxysilane, triethylpentyloxysilane, tripropylpentyloxysilane, tributylpentyloxysilane, trihexylpentyloxysilane, triphenylpentyloxysilane, tribenzylpentyloxysilane, dimethylvinylpentyloxysilane, dimethylpropylpentyloxysilane Dimethylphenylpentyloxysilane, dimethyloctylpentyloxysilane, dimethyloctadecylpentyloxysilane, diphenylmethylpentyloxysilane,HydrocarbylPentyloxysilane; trimethylhexyloxysilane, triethylhexyloxysilane, tripropylhexyloxysilane, tributylhexyloxysilane, trihexylhexyloxysilane, triphenylhexyloxysilane, tribenzylhexyloxysilane, dimethylvinylhexyloxysilane, dimethyl Tripropylene such as propylhexyloxysilane, dimethylphenylhexyloxysilane, dimethyloctylhexyloxysilane, dimethyloctadecylhexyloxysilane, and diphenylmethylhexyloxysilane.HydrocarbylHexyloxysilane; dimethyl-γ-glycidoxypropylmethoxysilane, dimethyl-γ-methacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane, and the like. Among them, trimethylmethoxysilane or trimethylethoxysilane is particularly preferable in terms of reactivity. preferable.
[0046]
In addition, the above formula: R used as a hydrophobizing agent for surface treatment^Five _ThreeExamples of silanol compounds represented by SiOH include trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, trihexylsilanol, triphenylsilanol, tribenzylsilanol, dimethylvinylsilanol, dimethylpropylsilanol, dimethylphenylsilanol, dimethyloctylsilanol, Examples thereof include dimethyloctadecylsilanol and diphenylmethylsilanol, and among them, trimethylsilanol is preferable.
[0047]
As described above, the hydrophobic fine particles as the component (F) of the present invention are a hydrophobizing agent for surface treatment with stirring in an aqueous dispersion of silica / silsesquioxane fine particles containing a surfactant and a catalyst. It is preferable to be blended as an aqueous emulsion produced by adding The amount of the hydrophobizing agent for surface treatment to be added is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the silica / silsesquioxane fine particles. When the addition amount is less than 0.1 parts by weight, the hydrophobization by the surface treatment is insufficient, and even when the addition amount exceeds 20 parts by weight, the surface treatment amount does not increase.
[0048]
The temperature at which the hydrophobizing agent for surface treatment is added to the aqueous suspension of silica / silsesquioxane fine particles may be between the freezing point and the boiling point of the aqueous dispersion. In order to complete the reaction, stirring is preferably continued for a while after the addition. Thereafter, neutralization is performed by adding an acidic substance or an alkaline substance as necessary.
[0049]
The blending amount of the component (F) is required to be 5 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the component (A) as surface-treated fine particles. When the amount is less than 5 parts by weight, the strength of the resulting film is low and the wear resistance is deteriorated, and when it exceeds 150 parts by weight, a film that does not follow the substrate and does not stretch may be formed.
[0050]
[(G) component]
Component (G) in the aqueous silicone resin composition of the present invention is a component that improves surface smoothness, and is spherical organic resin fine particles.
The aqueous silicone resin composition of the present invention is applied to a substrate and then cured by heating to form a coating film. If the melting point of the spherical organic resin fine particles is low, the particle shape is deformed and the surface becomes smooth. Therefore, the melting point is required to be 150 ° C. or higher, preferably 200 ° C. or higher, and may not have a melting point. In addition, if the hardness of the organic resin is high, there is a risk of damaging the surface of the mating material with which the resulting coating rubs, so a relatively soft resin is desirable.
[0051]
The average particle diameter of the spherical organic resin fine particles is required to be 0.5 to 50 μm, and preferably 1 to 20 μm. When the average particle size is less than 0.5 μm, the surface smoothness is deteriorated.
[0052]
The material is not particularly limited as long as the organic resin satisfies the above conditions, but polyamide resin such as nylon 6 and nylon 66, acrylic urethane resin, or polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene A fluororesin such as a copolymer is preferred.
[0053]
The amount of component (G) is required to be 5 to 100 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of component (A), and the amount is 5% by weight. If it is less than part, the resulting film has poor surface smoothness and poor wear resistance, and if it exceeds 100 parts by weight, the film strength may decrease and the wear resistance may deteriorate.
[0054]
[Preparation of aqueous silicone resin composition]
The aqueous silicone resin composition of the present invention can be obtained by dispersing and mixing the components (A) to (G) in water using a surfactant. However, the components (B), (C), (D) and (G) may be blended as they are, but as described above, the components (A) and (F) are preliminarily added to water using a surfactant. It is necessary to formulate as an emulsified and dispersed aqueous emulsion. In addition, when the component (E) is not water-soluble, it is desirable to preliminarily emulsify and disperse in water using a surfactant and blend it as an aqueous emulsion. The component (G) may be preliminarily emulsified and dispersed in water using a surfactant.
The above-mentioned components may be mixed using a conventionally known mixing stirrer equipped with a paddle type, saddle type or the like. And what is necessary is just to add water and dilute as needed.
[0055]
In the range of the aqueous silicone resin composition of the present invention, the silicone resin powder, carbon black, paraffin wax, polyethylene wax, It is optional to add silicone oil, various organic or inorganic pigments, thickeners, antifoaming agents, preservatives and the like.
[0056]
[Coating substrate, coating method]
Examples of the rubber material that is a base material whose surface is coated with the aqueous silicone resin composition of the present invention include natural rubber, EPDM, SBR, chloroprene rubber, isoprene-isobutylene rubber, nitrile rubber, and the like. The form of the rubber article made of the rubber material is a porous body, a hard body, etc., and is not limited at all. Similarly, examples of the fiber material include synthetic fibers such as nylon, polyester, acrylic, vinylon, and acetate, and natural fibers such as cotton, silk, and wool.
[0057]
Examples of the method for coating the surface of the substrate with the aqueous silicone resin composition of the present invention include brush coating, spray coating, roll coating, flow coating, dip coating, knife coating and the like. After applying the aqueous silicone resin composition to the surface of the substrate by these methods, the film may be formed by heating, drying and curing. The film thickness of the obtained film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm.
[0058]
The film obtained from the aqueous silicone resin composition of the present invention is excellent in adhesion to a substrate, abrasion resistance and surface smoothness. In particular, the rubber article coated as described above has excellent wear resistance and surface smoothness on its surface, so that weatherstrip materials for automobiles, glass run materials, O-rings, gaskets, various packings, etc. It is particularly useful as a sealing material, rubber hose material, and the like.
[0059]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
[0060]
[Evaluation methods]
1. Complex viscosity measurement method
Using a controlled stress rheometer CS type (manufactured by Bolin), using a 20mmφ cone plate as a fixture, measure the complex viscosity of the organopolysiloxane component at a fixed frequency of 0.1 rad / sec at 25 ° C. did.
2. Surface smoothness
As shown in Fig. 1, two EPDM porous material strips 1 and 1 '(10mm x 50mm, thickness 2mm, hardness (JIS K 6301 A) 36, specific gravity 0.63) coated on one side with silicone resin An adhesive was applied to the surface that was not subjected to the above-mentioned treatment, and a test specimen was prepared by applying the adhesive to opposite sides of a substantially square iron plate 2 (50 mm × 50 mm). A hole 3 is opened at a position close to one of the remaining sides of the iron plate 2, and a string 4 is passed through the hole 3 so that the test piece can be pulled.
As shown in FIG. 2, this test specimen is placed on the glass plate 5 with the strips 1 and 1 'face down, and a load of 6 (1 kg) is applied, and the pulling speed is 100 mm / min. Then, the glass plate 5 was pulled horizontally by the string 4 in the direction of the arrow 7. At this time, the dynamic friction coefficient between the coated surface of the strips 1 and 1 ′ and the glass plate was measured.
[0061]
3. Abrasion resistance
EPDM porous sheet coated with silicone resin (15mm x 150mm, thickness 2mm, hardness (JIS K 6301 A) 36, specific gravity 0.63) is rubbed twice with your thumb twice, and the coating film falls off Whether or not and the degree of omission were evaluated by visual observation. Next, 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 made of the above-mentioned EPDM with respect to the case where the coating film did not fall off and did not fall off. Place on the coated surface of the porous sheet 9, and apply a reciprocating friction with the coated surface under the conditions of a friction speed of 60 reciprocations / minute and a friction stroke of 70 mm while applying a thrust load of 350 g to the glass cell 8. The number of reciprocating frictions until the surface film was scraped was measured.
[0062]
[Preparation Example]
[Preparation Example 1 of Component (A)]
350 g of octamethylcyclotetrasiloxane and 7 g of 10% by weight aqueous dodecylbenzenesulfonic acid solution are charged into a 1 liter glass beaker, and phase inversion from W / O type to O / W type occurs at 6000 rpm using a homomixer, increasing the viscosity. And stirring was continued for another 10 minutes. Next, while stirring at 2000 rpm, 343 g of water was added, and then passed twice through a high-pressure homogenizer at a pressure of 30 MPa to obtain a stable emulsion.
[0063]
The emulsion is then transferred to a 1 liter glass flask equipped with a stirrer, thermometer and reflux condenser, reacted at 70 ° C. for 6 hours, aged at 15 ° C. for 12 hours, and then 10% by weight aqueous sodium carbonate solution. 13 g was added and neutralized to pH = 6.6 to obtain a uniform white turbid aqueous emulsion (aqueous emulsion A-1).
[0064]
Several grams of this aqueous emulsion was weighed and dried in a hot air circulating thermostat set at 105 ° C for 3 hours, and the amount of dry residue was measured. As a result, the content of organopolysiloxane in this aqueous emulsion was Was 46.0% by weight. Isopropyl alcohol was added to this aqueous emulsion to break the emulsion, and then the organopolysiloxane-containing phase was separated and dried at 105 ° C. for 24 hours. As a result of measuring the complex viscosity of the resulting organopolysiloxane, 2.3 × 10⁶mPa · s.
[0065]
[Preparation Example 2 of Component (A)]
Uniform in the same manner as in Preparation Example 1 except that 350 g of octamethylcyclotetrasiloxane and 1.3 g of phenyltriethoxysilane were used instead of 350 g of octamethylcyclotetrasiloxane, and neutralization to pH = 6.4. A white turbid aqueous emulsion (aqueous emulsion A-2) was obtained.
As a result of measuring in the same manner as in Preparation Example 1, the content of organopolysiloxane in this aqueous emulsion was 46.2% by weight, and the complex viscosity of the resulting organopolysiloxane was 2.8 × 10 6.⁷mPa · s.
[0066]
[Preparation Example 3 of Component (A)] (For comparison)
Using 350 g of octamethylcyclotetrasiloxane, a stable emulsion was obtained in the same manner as in Preparation Example 1 above.
Next, this emulsion was transferred to a glass flask having a capacity of 1 liter equipped with a stirrer, a thermometer and a reflux condenser, reacted at 85 ° C. for 16 hours, and then added with 13 g of 10% by weight aqueous sodium carbonate solution, pH = The mixture was neutralized to 6.4 to obtain a uniform white turbid aqueous emulsion (aqueous emulsion A-3).
As a result of measurement in the same manner as in Preparation Example 1, the content of organopolysiloxane in this aqueous emulsion was 46.2% by weight, and the complex viscosity of the resulting organopolysiloxane was 7.4 × 10 6.^ThreemPa · s.
[0067]
[Preparation Example of Component (C)]
A glass flask having a capacity of 1 liter equipped with a stirrer, a thermometer and a reflux condenser was charged with 108 g of maleic anhydride and 350 g of ethanol, dissolved uniformly, and then 242 g of γ-aminopropyltriethoxysilane was added at room temperature. It was added dropwise over time. After completion of the dropwise addition, the reaction was continued for further 1 hour to obtain a pale yellow transparent solution (solution C).
Several grams of this solution was weighed and dried in a hot air circulating thermostat set at 105 ° C. for 3 hours, and then the amount of dry residue was measured. As a result, the content of the reaction product in this solution was 49.5% by weight. there were. When the dried residue was subjected to instrumental analysis using GPC, IR, NMR, etc., it was found that this reaction product was mainly composed of the compound represented by the following formula (1).
[0068]
[Chemical 1]
HOOCCH = CHCONHC_ThreeH₆Si (OC₂H_Five)_Three
[0069]
[Preparation Example 1 of Component (F)]
Colloidal silica slurry Snowtex O (trade name, manufactured by Nissan Chemical Industries, Ltd., concentration = 20 wt%, particle size = 10 to 20 nm) and 1 g of dodecylbenzenesulfonic acid are charged into a 1 liter glass flask and mixed and dissolved. When the temperature of the aqueous dispersion was 20 ° C., the pH was 2.0. While stirring, 10 g of trimethylsilanol was added and stirred for 1 hour while maintaining the liquid temperature at 15 to 25 ° C. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then neutralized by adding 1.9 g of triethanolamine, and an aqueous dispersion of fine particles of silica fine particles whose surface was trimethylsilylated (fine particle dispersion F- 1) got.
[0070]
Several grams of this hydrophobic fine particle dispersion was weighed and dried in a hot air circulating thermostat set at 105 ° C. for 3 hours, and the amount of dry residue was measured. As a result, the treated silylated silica fine particles in this aqueous dispersion were measured. The content of was 21.1% by weight. The average particle size of the silica fine particles to be treated was 22 nm as measured using a particle size measuring device N4Plus (manufactured by Beckman Coulter, Inc.).
[0071]
[Preparation Example 2 of Component (F)]
A 1 liter glass flask was charged with 974 g of colloidal silica slurry Snowtex O and 2 g of dodecylbenzenesulfonic acid, mixed and dissolved, and the temperature of the aqueous solution was adjusted to 20 ° C., resulting in a pH of 2.0. While stirring at a liquid temperature of 15 to 25 ° C., 20 g of vinyltrimethoxysilane was added dropwise over 20 minutes, and then 2 g of trimethylsilanol was added and stirred for 1 hour. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then neutralized by adding 1.9 g of triethanolamine, and an aqueous dispersion of fine particles of silica-polyvinylsilsesquioxane fine particles whose surface was trimethylsilylated (fine particles) Dispersion F-2) was obtained.
As a result of measurement in the same manner as in Preparation Example 1 of the component (F), the content of the silica-polyvinylsilsesquioxane fine particles to be treated in this aqueous dispersion was 21.62% by weight, and silica-polyvinyl to be treated. The average particle diameter of the silsesquioxane fine particles was 21 nm.
[0072]
[Preparation Example 3 of Component (F)]
A 1-liter glass flask was charged with 847 g of ion-exchanged water and 2 g of dodecylbenzenesulfonic acid, mixed and dissolved, and when the temperature of the aqueous solution was 20 ° C., the pH was 2.1. While stirring the liquid temperature at 15 to 25 ° C., 148 g of methyltrimethoxysilane was added dropwise over 4 hours, and then 2 g of trimethylsilanol was added and stirred for 1 hour. Further, the mixture was stirred for 1 hour while maintaining the liquid temperature at 50 to 60 ° C., and then neutralized by adding 1 g of triethanolamine, and an aqueous dispersion (fine particle dispersion) of polymethylsilsesquioxane fine particles whose particle surface was trimethylsilylated. F-3) was obtained.
As a result of measurement in the same manner as in Preparation Example 1 of the component (F), the content of the treated polymethylsilsesquioxane fine particles in this aqueous dispersion was 8.0% by weight, and the treated polymethylsilsesquioxane. The average particle size of the oxane fine particles was 26 nm.
[0073]
[Preparation Example 4 of component (F)] (for comparison)
An aqueous dispersion (fine particle dispersion F-4) of silica-polyvinylsilsesquioxane fine particles was obtained in the same manner as in Preparation Example 2 for the component (F) except that 2 g of trimethylsilanol was not used.
As a result of measuring in the same manner as in Preparation Example 1 for the component (F), the content of the silica-polyvinylsilsesquioxane fine particles to be treated in this aqueous dispersion was 21.3% by weight, and the obtained silica- The average particle diameter of the polyvinyl silsesquioxane fine particles was 21 nm.
[0074]
[(F) Component Preparation Example 5] (for comparison)
Aqueous dispersion of polymethylsilsesquioxane fine particles in the same manner as in Preparation Example 3 of component (F) except that 2 g of trimethylsilanol is not used and the amount of methyltrimethoxysilane used is changed from 148 g to 150 g. A liquid (fine particle dispersion F-5) was obtained.
As a result of measuring in the same manner as in Preparation Example 1 for the component (F), the content of the polymethylsilsesquioxane fine particles to be treated in this aqueous dispersion was 8.1% by weight, and the obtained polymethylsil The average particle size of the sesquioxane fine particles was 26 nm.
[0075]
Examples 1-9
Ingredients (A), (C) and (F) obtained in the above preparation examples, and the following (B), (D), (E) and (G) components are shown in Table 1. An aqueous silicone resin composition as a surface treating agent composition was prepared by mixing in an amount / composition ratio, and these were prepared as an EPDM porous material strip and sheet (thickness 2 mm, hardness (JIS K 6301 A) 36, specific gravity 0.63) ) With a brush and left in a hot-air circulating thermostatic chamber adjusted to 105 ° C. for 2 minutes to form a film, and the adhesion, surface smoothness and wear resistance are evaluated according to the evaluation methods 2 and 3 above. did. The results are shown in Table 1.
[0076]
・ (B) component
Silane B-1: Phenyltriethoxysilane
Silane B-2: Methyltriethoxysilane
・ (D) component
Silane D: γ-Glycidoxypropyltrimethoxysilane
・ (E) component
Aqueous Emulsion E: 30% by weight emulsion of dibutyltin dilaurate
・ (G) component
Organic resin powder G-1: Acrylic urethane fine particles BC-79 (trade name, manufactured by Gifu Shellac Co., Ltd., average particle size = 8 μm)
Organic resin powder G-2: Nylon fine particles SP-500 (trade name, manufactured by Toray Industries, Inc., average particle size = 5 μm)
[0077]
[Table 1]

[0078]
Comparative Examples 1 to 12
Component (A), Component (C) and Component (F) obtained in the above Preparation Example, Component (B), Component (D), Component (E) and Component (G) in the above Examples, and Component (F) below An aqueous silicone resin composition as a surface treating agent composition was prepared by mixing the components and silicone rubber fine particle dispersion at the blending amounts and composition ratios shown in Table 2, and using these, the EPDM product was prepared in the same manner as in the Examples. The surface treatment of the porous sheet was performed and evaluated. The results are shown in Table 2.
[0079]
・ (F) component
Fine particle dispersion F-6: Colloidal silica slurry Snowtex O (trade name, manufactured by Nissan Chemical Industries, Ltd., concentration = weight 20%, particle size = 10-20 nm)
・ Silicone rubber fine particle dispersion
X-52-1539 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., concentration = 50% by weight, average particle size = 5 μm)
[0080]
[Table 2]

* Not evaluated because the film is sticky.
[0081]
[Evaluation]
When the complex viscosity of the organopolysiloxane of component (A) is low as in Comparative Example 1, the surface slipperiness and wear resistance are poor, and the organotrialkoxysilane of Component (B) as in Comparative Example 2. Is not blended, the film is insufficiently cured, and as in Comparative Example 3, the amide group and carboxyl group-containing organoalkoxysilane of component (C) and the epoxy group of component (D) are contained. When the organoalkoxysilane is not blended, the surface slipperiness and wear resistance are poor. As in Comparative Example 4, the amide group and carboxyl group-containing organoalkoxysilane of the component (C) and ( When the amount of the epoxy group-containing organoalkoxysilane of component D) is large, the wear resistance is poor, and the hydrophobic fine particles of component (F) as in Comparative Example 5 If they are not combined, the surface slipperiness and wear resistance will be poor, and if the amount of the hydrophobic fine particles of the component (F) is large as in Comparative Example 6, the wear resistance will be poor. It turns out that it becomes.
[0082]
Further, when the organic resin fine particles of the component (G) are not blended as in the comparative example 7, the surface slipperiness and the wear resistance are poor, and the organic component of the (G) component as in the comparative example 8. When the amount of resin fine particles added is large, the wear resistance is poor, and the component (F) is a fine particle not hydrophobized with a trimethylsilyl group as in Comparative Example 9, Comparative Example 10 and Comparative Example 11. It can be seen that surface slipperiness and wear resistance are poor.
Next, it can be seen that when silicone rubber fine particles are used instead of the component (G) as in Comparative Example 12, the surface slipperiness is poor.
[0083]
【The invention's effect】
The aqueous silicone resin composition of the present invention is a coating formed on the surface of a base material made of a rubber material or a fiber material and cured to form a film, and the obtained film has excellent adhesion to the base material, and Excellent slipperiness and wear resistance can be imparted to the substrate surface.
[Brief description of the drawings]
FIG. 1 is a perspective view showing a specimen used for evaluating the surface smoothness of a film in Examples and Comparative Examples.
FIG. 2 is a diagram showing a method for measuring a dynamic friction coefficient using the test specimen.
FIG. 3 is a diagram showing a method for measuring the wear resistance of a film in Examples and Comparative Examples.
[Explanation of symbols]
1,1 'EPDM porous strip
2 Iron plate
3 holes
4 Thongs
5 Glass plate
6 Load 6
7 Tensile direction
8 Glass cell
9 EPDM porous sheet

Claims (7)

(A) Units represented by the formula: [R ¹ ₂ SiO _2/2 ] (R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and the formula: [R ² SiO _3/2 ] (R ² has the same definition as that for R ¹ ) as a constituent unit, and the molar ratio of both units: [R ¹ ₂ SiO _2/2 ] / [ R ² SiO _3/2 ] = 1 / (0 to 0.01), a terminally hydroxyl-blocked organopolysiloxane having a complex viscosity at 25 ° C. of 1 × 10 ⁴ mPa · s or more: 100 parts by weight
(B) Formula: R ³ Si (OR ⁴ ) ₃ (R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms which does not contain any amide bond, carboxyl group or epoxy group, R ⁴ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms) and / or a partial hydrolysis condensate thereof: 0.01 to 10 parts by weight,
(C) an organoalkoxysilane containing an amide bond and a carboxyl group and not containing an epoxy group and / or a partial hydrolysis condensate thereof: 1 to 20 parts by weight,
(D) an organoalkoxysilane containing an epoxy group and containing neither an amide bond nor a carboxyl group and / or a partial hydrolysis condensate thereof: 1 to 20 parts by weight,
(E) Curing catalyst: effective amount,
(F) (F1) Formula: Silica fine particles composed of structural units represented by [SiO _4/2 ], (F2) Formula: units represented by [SiO _4/2 ] and formula: [R ⁶ SiO _3/2 ] (R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms) as a constituent unit, and (F3) formula: [R ⁶ The surface of at least one fine particle selected from the group consisting of polyorganosilsesquioxane fine particles having a unit represented by SiO _3/2 ] (R ⁶ is as described above) as a structural unit is represented by the formula : [R ⁵ ₃ SiO _1/2 ] (R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms). 5 to 1000 nm hydrophobic fine particles: 5 to 150 parts by weight, and
(G) Spherical organic resin fine particles having a melting point of 150 ° C. or higher and an average particle diameter of 0.5 to 50 μm: An aqueous silicone resin composition containing 5 to 100 parts by weight. The fine particles of (F2) are represented by the unit represented by the formula: [SiO _4/2 ] and the formula: [R ⁷ SiO _3/2 ] (R ⁷ is a group selected from a methyl group and a vinyl group). The aqueous silicone resin composition according to claim 1, wherein the composition is a fine particle having a unit as a structural unit. The polyorganosilsesquioxane fine particles of the above (F3) have a unit represented by the formula: [R ⁷ SiO _3/2 ] (R ⁷ is a group selected from a methyl group and a vinyl group). 2. The aqueous silicone resin composition according to claim 1, which is an organosilsesquioxane fine particle. The hydrophobic fine particles of the component (F) are those obtained by organosilylation with a unit represented by the formula: [(CH ₃ ) ₃ SiO _1/2 ]. 2. The aqueous silicone resin composition according to item 1. The hydrophobic fine particles of the component (F) were obtained by a method of treating the surface of fine particles by adding trialkylalkoxysilane or trialkylsilanol to an aqueous dispersion of fine particles containing an anionic surfactant and an acidic catalyst. The aqueous silicone resin composition according to claim 1, wherein the aqueous silicone resin composition is one. The hydrophobic fine particles of the component (F) were obtained by a method of treating the surface of fine particles by adding trialkylalkoxysilane or trialkylsilanol to an aqueous dispersion of fine particles containing a cationic surfactant and an alkaline catalyst. The aqueous silicone resin composition according to claim 1, wherein the aqueous silicone resin composition is one. The aqueous silicone resin composition according to any one of claims 1 to 6, wherein the organic resin as the component (G) is a polyamide resin, an acrylic urethane resin, or a fluororesin.

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