JPH07196984A - Film-forming silicone emulsion composition - Google Patents

Abstract

PURPOSE:To obtain a film-forming silicone emulsion composition, capable of providing a film excellent in gloss, water repellency, slipperiness, etc., and excellent in adhesion by mixing and dispersing a silicone emulsion containing a specific organopolysiloxane with a specified hydrolyzable silane. CONSTITUTION:This composition is obtained by mixing and dispersing (A) a silicone emulsion composed of (i) an organopolysiloxane, expressed by the formula [R<1> is a 1-20C monovalent hydrocarbon or H; R<2> is OH or a hydrolyzable group; R<3> is an amino group-containing group or an epoxy group-containing group; 0<(a)<3; 0<=(b)<2; 0<(c)<=1] and having amino groups or epoxy groups, (ii) an emulsifying agent (preferably a nonionic surfactant) and (iii) water and (B) a hydrolyzable silane having a functional group which is the epoxy group- containing group when R<3> in the component (i) is the amino group-containing group and the amino group-containing group when R<3> is the epoxy group- containing group (e.g. gamma-glycidoxypropyltrimethoxysilane or gamma- aminopropyltriethoxysilane).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention forms a film having excellent adhesion to rubber, plastic, cloth and the like, and having good gloss, water repellency, releasability, and excellent slipperiness. , A film-forming silicone emulsion composition.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Silicone emulsions have hitherto been widely used as mold release agents, polish agents, and fiber treatment agents for household products, bags, cloths, vinyl products for ships and automobiles, sports products and the like. Has been. However, in general, they have insufficient durability and have a drawback that they have to be recoated. Therefore, as a durable emulsion, an emulsion of amino-functional silicone is known (JP-A-60-1273).
No. 82, No. 62-116633, No. 63-66265), all of which are limited to use with cloth materials that have good adhesiveness and permeability, or materials that do not require close adherence, and are therefore durable. A silicone emulsion that has good properties and that also adheres well to materials such as rubber and plastic has been desired. It is also known to use a mixture of aminosiloxane and epoxysiloxane (see Japanese Examined Patent Publication No. Sho 48-17514) and a reaction product of aminosiloxane and epoxysilane (Japanese Examined Patent Publication No. 1-22390) as the fiber treating agent. However, improvement in adhesion and durability was further desired. In addition, rubber,
It is known to use a reaction product or a mixture of epoxy siloxane and aminosilane as a surface treatment agent for plastics and the like (JP-A Nos. 52-123394, 54-43891, 54-90375 and 54-90375). 56-78960 Publication, 61-
159427 and JP-A-2-233763), the compositions shown therein are generally organic solvent solutions, and emulsion compositions are not specifically shown. When using a composition comprising these organic solvent solutions, there are problems in terms of environmental hygiene and safety due to flammability, as well as problems such as alteration of the base material such as rubber and plastic. Further, it is difficult to obtain an emulsion composition having good properties by simply replacing the composition shown in these with an emulsion.

[0003]

OBJECTS OF THE INVENTION The present invention provides a film-forming silicone emulsion composition having excellent adhesion to various substrates, good water repellency, releasability, and excellent slipperiness. The purpose is to provide.

[0004]

As a result of intensive studies to achieve the above object, the present inventors have found that an emulsion of an organopolysiloxane having an amino group or an epoxy group is added to a silane having an epoxy group or an amino group, and optionally a hydroxyl group or a hydrolyzed group. By adding an organopolysiloxane emulsion having degradable groups, it exhibits excellent adhesion to materials such as fibers, rubber, and plastics, as well as non-adhesiveness, releasability, gloss, and water repellency on the surface. In addition, they have found that an emulsion composition can be obtained which forms a film having excellent abrasion resistance and slipperiness, and completed the present invention. That is, the film-forming silicone emulsion composition of the present invention is (A) (a) the general formula

[0005]

[Chemical 4]

(Here, R ¹ is the same or different carbon number 1
To 20 monovalent hydrocarbon groups or hydrogen atoms, R ² is a hydroxyl group or a hydrolyzable group, R ³ is an amino group-containing group or an epoxy group-containing group, and a, b and c are 0 <a <3,0. ≦ b <2,
0 <c ≤ 1) and an organopolysiloxane containing at least one amino group or epoxy group in one molecule (b) an emulsifier (c) a silicone emulsion consisting of water and (B) 1 Hydrolyzable silane having at least one functional group in the molecule (wherein the functional group is an amino group-containing group or an epoxy group-containing group, and R ^{3 of} component (A) (a) is an amino group-containing group). Is an epoxy group-containing group, and R ³ is an amino group-containing group when R ³ is an epoxy group-containing group), if necessary (C) (d)

[0007]

[Chemical 5]

(Here, R ⁴ has the same or different carbon number 1
To 20 monovalent hydrocarbon groups or hydrogen atoms, R ⁵ is a hydroxyl group or a hydrolyzable group, and d and e are 0 <d <3 and 0 <e <.
2, a number that satisfies 1.9 <d + e <2.2) and an organopolysiloxane containing at least one hydroxyl group or hydrolyzable group in one molecule (e) an emulsifier (f) a silicone emulsion comprising water Are mixed and dispersed.

The organopolysiloxane of component (A) (a) used in the present invention is an organopolysiloxane containing at least one amino group or epoxy group in one molecule, and an emulsifier of component (b), ( c) It forms a silicone emulsion with the component water. In the general formula representing the component (a), R ¹ is the same or different and has 1 to 20 carbon atoms.
Represents a monovalent hydrocarbon group or a hydrogen atom of, specifically,
Examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group, an alkenyl group such as a vinyl group and a propenyl group, an aryl group such as a phenyl group, and an aralkyl group such as a β-phenylethyl group. Among these, a hydrogen atom, a methyl group, a vinyl group, and a phenyl group are preferable, and a methyl group is particularly preferable, because the obtained composition has good characteristics. R ² is a hydroxyl group or a hydrolyzable group, and as the hydrolyzable group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and an acyloxy group, an amino group, an aminoxy group, an oxime group and a ketoxime group. , An amide group and an alkenyloxy group are exemplified. Among these, hydroxyl groups from the ease of handling,
The alkoxy group is particularly preferably a hydroxyl group or a methoxy group.
R ³ is an amino group-containing group or an epoxy group-containing group, and as the amino group-containing group, an aminomethyl group, β-aminoethyl group, γ-aminopropyl group, δ-aminobutyl group,
A γ- (methylamino) propyl group, a γ- (ethylamino) propyl group, a γ- (β-aminoethylamino) propyl group and a part or all of these amino groups can be used as a fourth group.
Examples thereof include quaternary ammonium salts. From the viewpoint of stability during storage, those having an amino group bonded to a silicon atom via at least 3 carbon atoms, such as a γ-aminopropyl group, are preferable. Examples of the epoxy group-containing group include a hydrocarbon group substituted with a glycidoxy group or an epoxycyclohexyl group. The substituted hydrocarbon group is preferably one having 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms. R ³ is preferably an amino group-containing group from the viewpoint of good adhesion of the obtained composition to the substrate, and also has good coatability to the substrate of the obtained composition, particularly rubber and plastic. Epoxy group-containing groups are preferred from the viewpoint of exhibiting good releasability. R ³ is more than a mixture of an amino group-containing group and an epoxy group-containing group,
It is good that all of R ³ are in either substituent. In the general formula, a, b, and c are 0 <a <3, 0 ≦ b <2, 0 <
It is a number satisfying c ≦ 1, preferably 1.0 <a <2,
0 ≤ b <0.5, 0.1 ≤ c ≤ 0.5 and 1.9 <a + b + c
It is a number that satisfies <2.2. When the hydroxyl group or hydrolyzable group of R ² is present in excess, that is, when b is 2 or more, the cured film obtained is hard and brittle, which is not preferable. The organopolysiloxane of component (a) has a molecular weight of 500 to 500,000, preferably 1,000 to 10
It is preferable to use the one of 0,000.

The organopolysiloxane of component (a) of the present invention comprises a cyclic polysiloxane monomer such as octamethylcyclotetrasiloxane and water in the presence of an emulsifier and an amino-functional silane or an epoxy-functional silane. It can be easily synthesized in one step by carrying out a polymerization reaction using an acid or base catalyst. Further, the cyclic polysiloxane monomer is polymerized in the presence of water and a polymerization catalyst,
Next, it can also be obtained by adding an amino-functional silane or an epoxy-functional silane and further carrying out a polymerization reaction. It can also be obtained by equilibrating polysiloxane oil and amino-functional or epoxy-functional silane in the presence of a catalyst.

The emulsifier as the component (b) used in the present invention is
It functions to emulsify the organopolysiloxane of component (a) to form a stable and homogeneous silicone emulsion. Examples of such emulsifiers include the following nonionic surfactants, anionic surfactants, and cationic surfactants.When R ³ of the organopolysiloxane (a) is an amino group-containing group, , Nonionic surfactants and cationic surfactants are preferably used, and nonionic surfactants are preferably used regardless of R ³ . As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol, polyoxyalkylene alkyl ester,
Examples thereof include polyoxyalkylene sorbitan ester, polyethylene glycol, polypropylene glycol, and ethylene oxide adduct of diethylene glycol trimethylnonanol. As the anionic surfactant, hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, alkylbenzenesulfonic acid such as myristylbenzenesulfonic acid, CH ₃ (CH ₂ ) ₆ CH ₂ O (C ₂ H ₄ O) ₂ SO ₃ H, CH ₃ (CH ₂ ) ₈ CH ₂ O (C ₂
H ₄ O) ₈ SO ₃ H, CH ₃ (CH ₂ ) ₁₉ CH ₂ O (C ₂ H ₄ O) ₂ SO ₃ H, CH ₃ (CH ₂ ) ₈ C
Examples thereof include sulfuric acid esters of polyoxyethylene monoalkyl ethers such as H ₂ C ₆ H ₄ O (C ₂ H ₄ O) ₂ SO ₃ H, and alkylnaphthylsulfonic acid. As the cationic surfactant, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow trimethyl. Examples include ammonium hydroxide, quaternary ammonium hydroxides such as coconut oil trimethylammonium hydroxide, and salts thereof. The emulsifier (b) is used in an amount of 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the organopolysiloxane as the component (a) because a good emulsified state is obtained.

The component (c) water used in the present invention is (a)
It is a dispersion medium when the component organopolysiloxane is emulsified with the component (b) emulsifier, and is not particularly limited as long as it is water. The blending amount of water is 50 to 500 parts by weight, preferably 100 to 300 parts by weight, based on 100 parts by weight of the organopolysiloxane as the component (a) because a good emulsified state is obtained.

The silicone emulsion of the component (A) of the present invention is obtained by emulsifying the organopolysiloxane of the component (a) with the emulsifier of the component (b) in water as the component (c). Also, when the component (a) is synthesized, if the component (a) is obtained as an emulsion as in emulsion polymerization,
If necessary, an emulsifier or water may be added to use this as the component (A). In particular, an emulsion obtained by emulsion polymerization using a cyclic siloxane monomer has a small emulsion particle size and good stability. The resulting composition exhibits good characteristics and is preferably used in the present invention. The emulsification can be performed by using an emulsification / dispersion device such as a colloid mill, a homomixer, a homogenizer, a combimix, or a sand grinder.

The component (B) of the present invention is a hydrolyzable silane having at least one or more functional groups in one molecule, and imparts good adhesion to the composition of the present invention. Here, the functional group is an amino group-containing group or an epoxy group-containing group,
When R ³ of the organopolysiloxane of the component (a) is an amino group-containing group, it is an epoxy group-containing group, and when R ³ is an epoxy group-containing group, it is an amino group-containing group. Examples of the amino group-containing group and the epoxy group-containing group as the functional group of the component (B) are the same as those of R ^3, and the preferable ones are also the same. Further, the component (B) is a hydrolyzable silane that further contains a hydrolyzable group, and such a hydrolyzable group includes a hydrolyzable group represented by R ² of the component (a). The same thing is illustrated and a part may be a hydroxyl group.
Of these, an alkoxy group, particularly a methoxy group and an ethoxy group are preferable. Specific examples of the hydrolyzable silane as the component (B) include γ-glycidoxypropyltrimethoxysilane and γ.
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing alkoxysilane such as methyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, γ- [N- (β -Aminoethyl)
Amino] propyltrimethoxysilane, γ- [N- (β
-Aminoethyl) amino] propylmethyldimethoxysilane, N- (β-aminoethyl) aminomethyltributoxysilane, γ- [N- {β- (N- (β-aminoethyl) amino) ethyl} amino] propyltri Examples thereof include amino group-containing alkoxysilanes such as methoxysilane. Among these, those whose hydrolyzable group is a dialkoxy group or a trialkoxy group, and especially silane which is a trimethoxy group are preferable because a film having good adhesiveness and durability can be obtained. The component (B) is used in an amount of 5 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the organopolysiloxane of the component (a). If the amount is less than 5 parts by weight, good adhesion cannot be obtained, and if the amount is more than 300 parts by weight, the resulting film becomes hard and brittle, resulting in insufficient durability. The component (B) may be added as it is to the silicone emulsion of the component (A), but may be added after mixing with an appropriate emulsifier in order to improve dispersibility in the emulsion and stability in the emulsion. . Examples of the emulsifier include the same as the component (b).

By mixing and dispersing the above-mentioned component (A) and component (B), it exhibits excellent adhesion to rubber, plastic, cloth and the like, and also has good gloss, water repellency and releasability. A silicone emulsion composition which forms a film can be obtained, but when it is used as a surface treatment agent for weather strips of automobiles, etc., it is required to have better sliding properties. Therefore, as a result of further study by the present inventors, it was found that adding an emulsion of an organopolysiloxane having a hydroxyl group or a hydrolyzable group as the component (C) is effective for obtaining good slipperiness. . The organopolysiloxane of the component (C) (d) used in the present invention does not contain an amino group and an epoxy group, and
An organopolysiloxane having at least one hydroxyl group or hydrolyzable group in the molecule, which forms a silicone emulsion with an emulsifier as the component (e) and water as the component (f). In the general formula showing the component (d), R ⁴
Are the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms, and specific examples thereof include the same groups as R ¹ . Among these, a hydrogen atom, a methyl group, a vinyl group, and a phenyl group are preferable, and a methyl group is particularly preferable, because the obtained composition has good characteristics. R ⁵ is a hydroxyl group or a hydrolyzable group, and as the hydrolyzable group, the same groups as R ² are exemplified. Among these, a hydroxyl group and an alkoxy group are preferable from the viewpoint of easy handling, and a hydroxyl group and a methoxy group are particularly preferable. . In the general formula, d and e are 0 <d <3, 0 <e <2,
1.9 <d + e <2.2, preferably 1.0
It is a number that satisfies <d <2.0, 0 <e <0.5, and 1.9 <d + e <2.1. When e is 0, the curability of the film becomes insufficient,
When it is 2 or more, the cured film becomes hard and brittle, and good slipperiness cannot be obtained. Further, in order to obtain good slipperiness and wear resistance, it is necessary that 1.9 <d + e <2.2. The organopolysiloxane of component (d) has a molecular weight of 500 to 500,000, preferably 1,000 to 10
It is preferable to use the one of 0,000. The component (d) is generally used in an amount of preferably 5 to 200 parts by weight, particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane of the component (a). This is because 5 parts by weight or more is preferable in order to obtain good slipperiness and abrasion resistance, and 200 parts by weight or less is preferable in order not to lower the adhesion to the substrate. Used in the present invention (e)
Examples of the component emulsifier include those similar to the component (b), and among them, nonionic surfactants and cationic surfactants are preferable. The emulsifier (e) is similar to the component (b) in (d)
5 to 100 parts by weight of the component organopolysiloxane
100 parts by weight, preferably 10 to 50 parts by weight are used. or,
The water as the component (f) used in the present invention is used in the same manner as the component (c) in an amount of 50 to 100 parts by weight, preferably 100 to 300 parts by weight, based on 100 parts by weight of the organopolysiloxane as the component (d). It The silicone emulsion of the component (C) of the present invention can be obtained in the same manner as the component (A), and those obtained by emulsion polymerization are also preferably used.

The emulsion composition of the present invention is obtained by adding the component (A), and optionally the silicone emulsion of the component (C), and the hydrolyzable silane of the component (B), and mixing and dispersing. To be Conventionally, it is known to use a reaction product of an epoxy silicone and an aminosilane as a surface treatment agent, but in the present invention, the reaction of the component (A) and the component (B) is not carried out, and a mixture and dispersion is used. To do. For example, when a product obtained by reacting an epoxy group with an amino group is used, the effect of the present invention cannot be obtained.

The composition of the present invention may be further diluted with water in order to facilitate coating when it is used for treating various substrates. Silicon content is generally 5 to 60% by weight, especially 10 to
It is preferable to dilute to 50% by weight. Further, the composition of the present invention, for the purpose of further reinforcing, matting, improving lubricity, fumed silica, precipitated silica, ground quartz,
Inorganic fine powder such as diatomaceous earth, acrylic resin, styrene resin, ethylene resin, nylon resin, benzoguanamine resin, melanin resin, polytetrafluoroethylene resin, silicone resin such as polymethylsilsesquioxane, spherical or amorphous Organic fine powder may be added. Especially for improving lubricity, the average particle size is 0.01-10
It is preferable to use one having a particle size of 0 μm, particularly 0.05 to 20 μm, and among the above-mentioned materials, fine powder of nylon resin, polytetrafluoroethylene resin or silicone resin is preferable, and spherical one is preferable. Particularly, spherical fine particles of silicone resin are preferable. The amount of such fine powder is preferably 0.1 to 200 parts by weight, more preferably 5 to 50 parts by weight, relative to 100 parts by weight of the organopolysiloxane of component (a). The fine powder may be added as it is to the silicone emulsion of the component (A), but it may be added after mixing with an appropriate emulsifier in order to improve dispersibility in the emulsion and stability in the emulsion. As an emulsifier
Examples are the same as the component (b). In order to further improve the lubricity, an emulsion of unsubstituted polydimethylsiloxane may be added, and particularly, the viscosity of 1,000 to 10
The addition of an emulsion of high viscosity siloxane of 0,000 cP is preferred. Further, various additives such as a dye for coloring, a pigment, an ultraviolet absorber for preventing deterioration due to ultraviolet rays, an ultraviolet shielding agent and the like may be added within a range that does not impair the characteristics of the composition of the present invention.

The emulsion composition of the present invention also comprises
You may mix | blend the hardening catalyst used for the condensation hardening reaction of silicone. Examples of this curing catalyst include metal fatty acid salts, amines, and ammoniums, and these may be used in combination. As the metal fatty acid salt, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin distearate, tributyltin acetate, tributyltin octoate, tributyltin laurate, dioctyltin diacetate, dioctyltin dilaurate,
Those having an organic group directly bonded to a metal atom, such as diethyltin dioleate and monomethyltin dioleate,
And those having no organic group directly bonded to a metal atom such as zinc octenoate, iron octenoate and tin octenoate. The amines include organic amines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine, and hexamethyltetraamine and salts thereof, and the ammoniums include tetramethylammonium, dimethylbenzylammonium and salts thereof. It is illustrated.

The emulsion composition of the present invention has a good curability even if it does not contain a curing catalyst, and has a cured film excellent in adhesion and durability to various substrates. give. However, the adhesion and durability of the cured film to the substrate may differ depending on the type of substrate, the type of filler compounded in the substrate, and the surface condition of the substrate. The required adhesion and durability will differ depending on the purpose. Therefore, when particularly good adhesion and durability are required in the emulsion composition of the present invention, it is preferable to add a curing catalyst as described above, and the amount of this curing catalyst is the amount of the organoa component (a). 0.1 to 10 parts by weight, especially 0.5 to 100 parts by weight of polysiloxane
It is preferable to add 5 parts by weight. On the other hand, when a good pot life is required for the emulsion composition, it is preferable not to add the curing catalyst as described above. The curing catalyst may be added as it is to the silicone emulsion as the component (A), but may be added after mixing with an appropriate emulsifier in order to improve the dispersibility in the emulsion and the stability in the emulsion. Examples of the emulsifier include the same as the component (b).

In the emulsion composition of the present invention, in addition to the emulsifier of the component (b), the emulsifier of the component (e), and the emulsifier to be mixed with the component (B) if necessary, the emulsion composition is coated on a substrate. In order to improve workability, an emulsifier may be further added, and when the emulsion composition of the present invention is prepared, it may be added in the same manner as other components. Examples of this emulsifier include those similar to the component (b), and among them, nonionic surfactants are preferable. The emulsion composition of the present invention has good coatability without adding an emulsifier, but when the surface of the substrate has high water repellency, the concentration of the composition, the coating amount, the coating amount It is preferable to further add an emulsifier as described above so that good coatability can be obtained even when the equipment is changed. The amount of this emulsifier is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the organopolysiloxane as the component (a).

The substrate of the composition of the present invention is treated by dip coating, spray coating, brush coating, knife coating, roll coating on various substrates such as paper, rubber, cloth, plastic, metal and ceramics. It is applied by a method such as the above, water is removed by drying, and the mixture is allowed to stand at room temperature for 10 minutes to several hours, or is slightly heated depending on the substrate to be cured.

[0022]

EFFECTS OF THE INVENTION The composition of the present invention, when treated on various base materials, is superior to conventional silicone emulsion compositions.
Provides a cured film with excellent adhesion and durability to the substrate. In particular, it is possible to provide a cured film having excellent adhesion to rubber, plastic, etc., which could not be obtained with conventional silicone emulsion. In addition, the composition of the present invention can be applied to various substrates better than conventional silicone emulsions, and has excellent appearance, releasability, and water repellency, and has excellent lubricity and abrasion resistance. Shows the feature of providing a film. The composition of the present invention, surface protection of automobiles, furniture, building materials, etc., gloss, water repellency,
It can be used for the purpose of imparting lubricity. Also, fibers,
It is also used for surface treatment of paper, film and metal foil, and for polishing shoes and bags. In particular, it is most suitable for applications such as imparting slipperiness to rubber such as weather strips of automobiles. The weather strip obtained by treating the composition of the present invention has good slipperiness, no abnormal noise is generated when the door is opened or closed, or when the vehicle is running at a low speed. There is nothing to do. Furthermore, sticking due to freezing at low temperatures is also improved.

[0023]

The present invention will be described in detail below with reference to Examples and Comparative Examples. All "parts" in the examples are "parts by weight".
"%" Means "% by weight", and the viscosity shows a value at 25 ° C. Synthesis Example 1 600 parts of water, octadecyldimethylammonium chloride
50 parts and 4 parts of KOH were put into a reaction vessel and mixed well, and 400 parts of octamethylcyclotetrasiloxane was further added and mixed. The mixture was emulsified by passing it through a colloid mill set at a mill spacing of 10 mil and further heated at 90 ° C. for 4 hours to carry out polymerization. Next, 4 parts of octadecyldimethylammonium chloride was added to γ- [N-
What was dissolved in 30 parts of (β-aminoethyl) amino] propyltrimethoxysilane was added and mixed, and the polymerization reaction was continued at 50 ° C. for 2 hours. Then add acetic acid to neutralize the catalyst,
A silicone emulsion A was obtained. The silicone content in the emulsion was about 40%.

Synthesis Example 2 800 parts of water, dihexadecylmethylammonium chloride
70 parts and 500 parts of octamethylcyclotetrasiloxane were put into a reaction vessel and mixed well, and 3 parts of KOH was further added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and heated at 95 ° C. for 4 hours for polymerization. Next, 30 parts of γ- [N- (β-aminoethyl) amino] propyltrimethoxysilane and γ- [N- (β-aminoethyl)
A solution prepared by dissolving 7 parts of dihexadecylmethylammonium chloride in 30 parts of amino] propylmethyldimethoxysilane was added and mixed, and the polymerization reaction was continued at 50 ° C. for 2 hours.
Thereafter, acetic acid was added to neutralize the catalyst to obtain a silicone emulsion B. Silicone content in emulsion is about 40%
Met.

Synthesis Example 3 600 parts of water, octadecyldimethylammonium chloride
50 parts of KOH and 4 parts of KOH were put into a reaction vessel and mixed well, and further 400 parts of octamethylcyclotetrasiloxane, γ
30 parts of [N- (β-aminoethyl) amino] propylmethyldimethoxysilane were added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and further heated at 90 ° C. for 4 hours for polymerization. Thereafter, acetic acid was added to neutralize the catalyst to obtain a silicone emulsion C. The silicone content in the emulsion was about 40%.

Synthetic Example 4 1000 parts of octamethylcyclotetrasiloxane, 20 parts of hexamethyldisiloxane and 6 parts of potassium silanolate were added to a reaction vessel and mixed well, followed by heating and stirring at 165 ° C. for 2 hours to carry out polymerization and equilibration. went. Furthermore, γ- [N-
150 parts of (β-aminoethyl) amino] propyltrimethoxysilane was added, and the mixture was heated and stirred at 165 ° C. for 6 hours for polymerization and equilibration. After cooling the mixture, 40 parts of water was added and mixed and stirred to completely hydrolyze the remaining methoxy group. Next, 0.5 part of KOH was added and the mixture was heated and stirred.
Equilibration was carried out at 0 ° C until the distillation of methanol was completed.
After that, acetic acid was added to neutralize the catalyst and the reaction mixture was adjusted to 5 mm.
Stripping was performed at 200 ° C. for 30 minutes in Hg to obtain an amino group-containing polysiloxane. The obtained polysiloxane is 150c
The viscosity of P is shown. 100 parts of this polysiloxane, 30 parts of dihexadecylmethylammonium chloride, and 120 parts of water were mixed and further emulsified in the same manner as in Example 1,
A silicone emulsion D was obtained. The silicone content in the emulsion was 40%.

Synthesis Example 5 600 parts of water, octadecyldimethylammonium chloride
50 parts and 4 parts of KOH were put into a reaction vessel and mixed well, and 400 parts of octamethylcyclotetrasiloxane was further added and mixed. The mixture was emulsified by passing it through a colloid mill set at a mill spacing of 10 mil and further heated at 90 ° C. for 4 hours to carry out polymerization. Next, 4 parts of octadecyldimethylammonium chloride dissolved in 30 parts of γ-glycidoxypropyltrimethoxysilane was added and mixed, and the polymerization reaction was continued at 50 ° C. for 2 hours.
Thereafter, acetic acid was added to neutralize the catalyst to obtain a silicone emulsion E. Silicone content in emulsion is about 40%
Met.

Synthesis Example 6 800 parts of water, dihexadecylmethylammonium chloride
70 parts and 500 parts of octamethylcyclotetrasiloxane were put into a reaction vessel and mixed well, and 3 parts of KOH was further added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and heated at 95 ° C. for 4 hours for polymerization. Next, 30 parts of γ-glycidoxypropyltrimethoxysilane, γ
A solution of 7 parts of dihexadecylmethylammonium chloride in 30 parts of glycidoxypropylmethyldimethoxysilane was added and mixed, and the polymerization reaction was continued at 50 ° C. for 2 hours. Thereafter, acetic acid was added to neutralize the catalyst to obtain a silicone emulsion F. The silicone content in the emulsion was 40%.

Synthesis Example 7 600 parts of water, octadecyldimethylammonium chloride
50 parts and 4 parts of KOH were put into a reaction vessel and mixed well, and 400 parts of octamethylcyclotetrasiloxane and 30 parts of γ-glycidoxypropyltrimethoxysilane were added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and further heated at 90 ° C. for 4 hours for polymerization. After that, acetic acid is added to neutralize the catalyst and silicone emulsion G
Got The silicone content in the emulsion was 40%.

Synthesis Example 8 Average Formula

[0031]

[Chemical 6]

An epoxy group-containing polysiloxane represented by
100 parts, dihexadecylmethylammonium chloride 20
Part, polyoxyethylene (9) nonylphenyl ether 10
Parts and 120 parts of water were mixed and then emulsified in the same manner as in Synthesis Example 1 to obtain a silicone emulsion H.
The silicone content in the emulsion was 40%.

Synthesis Example 9 600 parts of water and 6 parts of dodecylbenzenesulfonic acid were added to a reaction vessel and mixed well, and further 400 parts of octamethylcyclotetrasiloxane was added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and further heated at 90 ° C. for 4 hours for polymerization. Next, 4 parts of polyoxyethylene (9) nonylphenyl ether dissolved in 30 parts of γ-glycidoxypropyltrimethoxysilane was added and mixed, and
The polymerization reaction was continued at 1.5 ° C for 1.5 hours. Then, an aqueous solution of sodium hydrogen carbonate was added to neutralize the catalyst to obtain a silicone emulsion I. Silicone content in emulsion is about 40
%Met.

Synthesis Example 10 600 parts of water, octadecyldimethylammonium chloride
50 parts and 4 parts of KOH were added to a reaction vessel and mixed well, and further 400 parts of octamethylcyclotetrasiloxane and 10 parts of methyltrimethoxysilane were added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and further 4 minutes at 90 ° C.
Polymerization was carried out by heating for a period of time. Then, acetic acid was added to neutralize the catalyst to obtain a silicone emulsion J. The silicone content in the emulsion was 40%. The average molecular weight of silicone was 15,000.

Synthesis Example 11 700 parts of water and 50 parts of dodecylbenzenesulfonic acid were added to a reaction vessel and mixed well, and 400 parts of octamethylcyclotetrasiloxane was further added and mixed. This mixture was emulsified in the same manner as in Synthesis Example 1 and further heated at 90 ° C. for 4 hours for polymerization. Then, triethanolamine was added to neutralize the catalyst to obtain a silicone emulsion K.
The silicone content in the emulsion was 30%. Also,
The average molecular weight of the silicone was 20,000.

Synthesis Example 12 100 parts of polydimethylsiloxane having both ends blocked with dimethylhydrosilyl groups and having an average molecular weight of 50,000, 30 parts of polyoxyethylene (9) nonylphenyl ether and 12 parts of water.
Silicone emulsion L was obtained by mixing 0 parts and then emulsifying in the same manner as in Synthesis Example 1. The silicone content in the emulsion was 40%.

Example 1 To 100 parts of Silicone Emulsion A, 30 parts of γ-glycidoxypropyltrimethoxysilane and 100 parts of water were added and mixed with stirring to prepare an emulsion composition of the present invention. This composition was applied to a sample nylon cloth by dipping,
It was cured by heating at 110 ° C. for 5 minutes. Then, after being left for 1 day at room temperature, the characteristics of this coated cloth were evaluated as follows. The results are shown in Table 1. Appearance: The sample before coating was compared with gloss and evaluated as follows. 1 ... Good gloss 2 ... Slight gloss 3 ... No gloss Adhesion: The sample was strongly squeezed with a finger, and the surface condition was evaluated as follows. 1 ... No dropout and excellent adhesion 2 ... Slight dropout or cloudiness occurs 3 ... Dropdown Water repellency: Drop water droplets on sample, and leave for 3 minutes evaluated. 1 ... It becomes a polka dot shape and repels water well 2 ... Water droplets spread a little, but it repels water well 3 ... Water droplets spread and the degree of repelling water is also weak Releasability: A commercially available adhesive tape ( Nichiban, width 12
18 mm) and apply a load of 1 kg / cm ² and cure for 1 day.
The force required to peel the tape in the 0 ° direction was measured by an autograph and evaluated as follows. 1 ... Peeling force was 10 g / 12 mm or less and showed good releasability 2. Peeling force was 10 to 50 g / 12 mm 3. Peeling force was peeling larger than 50 g and slightly heavy. Comparative Example 1 γ- An emulsion composition was prepared in the same manner as in Example 1 except that glycidoxypropyltrimethoxysilane was not added. This composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

Example 2 The emulsion composition prepared in Example 1 was brushed on an EPDM foamed rubber sheet and heated at 150 ° C. for 2 minutes to cure. Then, after being left at room temperature for 1 day, the characteristics of this coating rubber were evaluated in the same manner as in Example 1. Furthermore, apply a load of 50 g to the coating rubber and level it horizontally on the glass plate.
The stress when moved by cm was measured by an autograph, and the dynamic friction coefficient was determined from the average value of the stress. The results are shown in Table 2. Comparative Example 2 The emulsion composition of Comparative Example 1 was evaluated in the same manner as in Example 2. The results are shown in Table 3. Examples 3 to 10 Emulsion compositions having the compositions shown in Table 2 and Table 3 were prepared,
Evaluation was performed in the same manner as in Example 2. The results are shown in Tables 2 and 3. Comparative Example 3 100 parts of Silicone Emulsion A and 30 parts of γ-glycidoxypropyltrimethoxysilane were heated and stirred at 80 ° C. for 3 hours to cause reaction, and 100 parts of water was further added and mixed by stirring to prepare an emulsion composition. . This composition was evaluated as in Example 2. The results are shown in Table 3. Comparative Example 4 40 parts of the amino group-containing polysiloxane obtained in Synthesis Example 4,
γ-glycidoxypropyltrimethoxysilane 30 parts, water
150 parts, octadecyl dimethyl ammonium chloride 10
The parts were mixed and stirred, and then emulsified using a colloid mill in the same manner as in Synthesis Example 1 to prepare an emulsion composition. This composition was evaluated as in Example 2. The results are shown in Table 3. Comparative Example 5 An emulsion composition was prepared in the same manner as in Comparative Example 4 except that the epoxy group-containing polysiloxane used in Synthesis Example 8 was used instead of γ-glycidoxypropyltrimethoxysilane. This composition was evaluated as in Example 2.
The results are shown in Table 3. Comparative Example 6 Epoxy group-containing polyorganosiloxane used in Synthesis Example 40 40 parts, γ-aminopropyltriethoxysilane 30
Parts, water 150 parts, and octadecyldimethylammonium chloride 10 parts were used to prepare an emulsion composition in the same manner as in Comparative Example 4. This composition was evaluated as in Example 2. The results are shown in Table 3.

[0040]

[Table 2]

[0041]

[Table 3]

Example 11 To 100 parts of Silicone emulsion A, 50 parts of Silicone emulsion J, 30 parts of γ-glycidoxypropyltrimethoxysilane and 100 parts of water were added and mixed by stirring to prepare an emulsion composition. This composition was evaluated as in Example 2. The results are shown in Table 4. Examples 12 to 15 Emulsion compositions having the compositions shown in Table 4 were prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 2. The results are shown in Table 4.

[0043]

[Table 4]

Example 16 100 parts of Silicone emulsion A, 30 parts of γ-glycidoxypropyltrimethoxysilane and 1.0 part of dibutyltin dilaurate
And 100 parts of water were added and mixed with stirring to prepare an emulsion composition. This composition was evaluated as in Example 2.
Further, the coatability was evaluated as follows. The results are shown in Table 5.
Shown in. Applicability: The appearance of the sample was visually observed and evaluated as follows. 1 ... showed a uniform coating appearance. 2 ... Slight repelling occurred and uneven coating was partially formed. 3 ... Repelling occurred, and uneven coating was formed on the entire surface. Examples 17 to 19 Emulsion compositions having the compositions shown in Table 5 were prepared in the same manner as in Example 16 and evaluated in the same manner. The results are shown in Table 5. In the evaluation of the coating properties of Examples 16 to 19, samples were prepared in the same manner as in Example 2 except that the composition was applied to the substrate by spraying instead of brush coating, and the coating properties were evaluated. As a result, all showed a uniform coating appearance.

[0045]

[Table 5]

Claims (2)

[Claims] 1. A general formula of (A) (a): (Here, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom, R ² is a hydroxyl group or a hydrolyzable group, and R ³ is an amino group-containing group or an epoxy group-containing group. , A, b, c are 0 <a <3, 0 ≦ b <2, 0 <c ≦ 1
At least 1 in one molecule represented by
Organopolysiloxane containing one amino group or epoxy group (b) emulsifier (c) silicone emulsion consisting of water and (B) hydrolyzable silane having at least one or more functional groups in one molecule (here, The functional group is an amino group-containing group or an epoxy group-containing group, (A) (a) is an epoxy group-containing group when R ³ is an amino group-containing group, R ³ is an epoxy group-containing group A film-forming silicone emulsion composition, which is obtained by mixing and dispersing an amino group-containing group). 2. A general formula of (A) (a): (Here, R ¹ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom, R ² is a hydroxyl group or a hydrolyzable group, and R ³ is an amino group-containing group or an epoxy group-containing group. , A, b, c are 0 <a <3, 0 ≦ b <2, 0 <c ≦ 1
At least 1 in one molecule represented by
Organopolysiloxane containing one amino group or epoxy group (b) emulsifier (c) silicone emulsion consisting of water and (B) hydrolyzable silane having at least one or more functional groups in one molecule (here, The functional group is an amino group-containing group or an epoxy group-containing group, (A) (a) is an epoxy group-containing group when R ³ is an amino group-containing group, R ³ is an epoxy group-containing group An amino group-containing group) and (C) (d) the general formula: (Here, R ⁴ is the same or different monovalent hydrocarbon group having 1 to 20 carbon atoms or hydrogen atom, R ⁵ is a hydroxyl group or a hydrolyzable group, and d and e are 0 <d <3, 0 < e <2, 1.9 <d
+ E <representing a number satisfying 2.2) is mixed and dispersed with an organopolysiloxane having at least one hydroxyl group or a hydrolyzable group in one molecule (e) an emulsifier (f) a silicone emulsion consisting of water. A film-forming silicone emulsion composition comprising: