JP3430014B2 - Aqueous silicone composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an aqueous silicone composition.
Material, especially for rubber and fiber materials
And useful, the adhesion of the coating layer to the substrate,
Water with excellent wear resistance and surface smoothness on the coating layer surface
The present invention relates to a water-soluble silicone composition. [0002] 2. Description of the Related Art Conventionally, the surface of various rubbers is smooth and wear-resistant.
It is necessary to apply a solvent-based composition to impart
Was common. However, due to safety and global environmental issues,
Sexual ones are required. So silicone resin set
A method of surface treatment with a composition has been proposed. For example, water
Acid-containing organopolysiloxanes and organohydrogens
Polysiloxane and amino-containing dialkoxysilane
For surface treatment with a composition comprising a hydrolysis-condensation product of
(See Japanese Patent Application Laid-Open No. 7-109440)
Luganopolysiloxane and epoxy or amino groups
Organopolysiloxanes containing water-decomposable groups and epoxy groups
Or a composition comprising an amino group-containing hydrolyzable silane
(Refer to JP-A-7-196984)
Although these methods have been proposed,
Inadequate adhesion to the material, abrasion resistance and surface smoothness
Was. Therefore, the present inventors have proposed a hydroxyl-containing organopolysiloxane.
Hydrolytic shrinkage of sun and epoxy-containing dialkoxysilanes.
Condensation of Compounds and Amino Group-Containing Dialkoxysilanes
Surface treatment with a composition consisting of
Methods (JP-A-7-233351, JP-A-8-120572,
Japanese Unexamined Patent Publication No. 8-245882), hydroxyl-containing organopoly
Hydrolysis of siloxane and dialkoxysilane containing epoxy group
Decomposed condensate, aqueous amino compound and silicone rubber fine powder
For surface treatment with a composition comprising: (JP-A-9-53047)
Gazette). These allow for some characteristics
Although the above was recognized, it was still insufficient. [0003] Problems to be Solved by the Invention Rubber and fiber materials
Good adhesion, excellent wear resistance and surface smoothness, folding
Good appearance without whitening due to bending operation etc.
Aqueous silicone group that forms a coating film to be applied
It provides a product. [0004] SUMMARY OF THE INVENTION The present invention addresses these problems.
An aqueous silicone composition that solves the above,
this is, (A) The following general formula (Formula 3) Embedded image (Here R¹Is one or more of substituted or unsubstituted monovalent carbons having 1 to 20 carbon atoms. Hydrogen group, R^TwoIs a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, p is 800 to 20,000 The complex viscosity at 25 ° C is 1 × 10^Four~ 1 × 10⁸Centipoise 100 parts by weight of a chain organopolysiloxane, (B) The following general formula (Formula 4) Embedded image (Here R^ThreeIs a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R^FourIs 1 carbon Organotrialkoxysilanes represented by the formulas (1) to (6) and / or 0.01 to 10 parts by weight of the partially hydrolyzed condensate, (C) amide group and carboxyl group-containing organoalkoxysilane and / or Is 1 to 10 parts by weight of the partially hydrolyzed condensate, (D) Epoxy group-containing organoalkoxysilane and / or partial hydrolysis thereof 1 to 10 parts by weight of decondensate, (E) curing catalyst 0.01 to 10 parts by weight,(F) 1 to 100 parts by weight of a spherical silicone rubber cured product having an average particle size of 0.1 to 100 μm Is an aqueous silicone composition containing, as a main component. [0005] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.
explain. Component (A) of the aqueous silicone composition of the present invention
Is the complex viscosity at 25 ° C represented by the general formula (Formula 1)
1 × 10^Four~ 1 × 10⁸ Centipoise linear organopoly
Siloxane. Here, the complex viscosity is a commercially available general viscosity.
It is easily measured by a simple measuring device. For example, "Control
Cold Stress Rheometer CS ”(Bolin Company)
), "Ares viscoelasticity measurement system (for fluid measurement)"
(Made by Rheometric Scientific)
Measurement at a low fixed frequency, for example, 0.1 rad / s.
No. R in the formula (1)¹Is one or more carbon atoms
1-20 substituted or unsubstituted monovalent hydrocarbon groups,
Physically, methyl, ethyl, propyl, butyl
Group, pentyl group, hexyl group, heptyl group, octyl
Group, decyl group, dodecyl group, tetradecyl group, octade
Alkyl groups such as sil group; alke groups such as vinyl group and allyl group
An aryl group such as a phenyl group or a tolyl group; cyclo
Cycloalkyl groups such as hexyl group and the carbon of these groups
Part or all of the hydrogen atoms bonded to the atom
Substituents such as 3,3,3-trifluoropropyl
And a methyl group is particularly preferable. R^TwoIs
Hydrogen atom or methyl group, ethyl group, propyl group, butyl
Alkenyl, pentyl, hexyl, etc.
A alkyl group, and particularly preferably a hydrogen atom. [0006] The organopolysiloxane at 25 ° C
Complex viscosity is 1 × 10^Four Less than centipoise
Film does not adhere sufficiently to the substrate and does not show slipperiness
No. 1 × 10⁸Beyond centipoise, the resulting film
Because it does not show sufficient slipperiness, this organopolysiloki
Sun has a complex viscosity of 1 × 10 at 25 ° C.^Four~ 1 × 10⁸ C
It is necessary to be an inchpoise. Preferably 1 × 10
^Five ~ 1 × 10⁷ It is centipoise. [0007] Such organopolysiloxanes are publicly available.
Can be synthesized by known methods, such as alkali
In the presence of a catalyst such as a metal hydroxide, [R¹ _TwoSiO]
_m(Where m = 3 to 7) Cyclopolysiloxa
And water or R^TwoO [R¹ _TwoSiO]_nR^Two(Where n = 1 to 1,000
 The organopolysiloxane represented by
Obtained by The present invention is an aqueous composition
From the organopolysiloxane of component (A)
Liquid, but the organopolysiloxane viscosity
If it is high, it is difficult to obtain a stable emulsion.
It is good to produce by a known emulsion polymerization method. That is, [R¹ _TwoSi
O]_m(Where m = 3 to 7)
Sun or R as required^TwoO [R¹ _TwoSiO]_nR^Two(Where n = 1
~ 1,000) with an organopolysiloxane
Dispersing in water using an agent to remove catalysts such as acids and alkalis.
To carry out the polymerization reaction and neutralize the catalyst after polymerization to deactivate the catalyst
The organopolysiloxane which is the component (A) of the present invention
It can be an aqueous emulsion of oxane. In the aqueous silicone composition of the present invention,
The component (B) is a component of the organopolysiloxane of the component (A).
It functions as a cross-linking agent, and is represented in the above general formula (Chemical Formula 2).
The organotrialkoxysilane and / or
Is a partially hydrolyzed condensate. R in the formula^ThreeIs 1-20 carbon atoms
Is a substituted or unsubstituted monovalent hydrocarbon group,
Are methyl, ethyl, propyl, butyl, pen
Tyl, hexyl, heptyl, octyl, decyl
Group, dodecyl group, tetradecyl group, octadecyl group, etc.
Alkyl group; alkenyl group such as vinyl group and allyl group;
Aryl groups such as phenyl and tolyl groups; cyclohexyl groups
And other cycloalkyl groups and the carbon atoms of these groups
Part or all of the hydrogen atoms
Substitute with an organic group containing a mercapto group, acrylic group, etc.
Groups, for example, 3,3,3-trifluoropropyl group, γ-
Methacryloxypropyl group, γ-acryloxypropyl
And a γ-mercaptopropyl group. Further, R in the formula^FourRepresents a methyl group, an ethyl group,
Carbon such as pill, butyl, pentyl, hexyl, etc.
An alkyl group of the formulas 1 to 6, especially a methyl group, ethyl
Groups are preferred. In the aqueous silicone composition of the present invention,
Specific examples of the organotrialkoxysilane of the component (B)
As for methyltrimethoxysilane, methyltriethoxy
Sisilane, methyltripropoxysilane, methyltrib
Toxisilane, ethyltrimethoxysilane, ethyltri
Ethoxysilane, propyltrimethoxysilane, propylene
Rutriethoxysilane, butoxytrimethoxysilane,
Pentyltrimethoxysilane, hexyltrimethoxysi
Orchid, octyltrimethoxysilane, decyltrimethoxy
Sisilane, dodecyltrimethoxysilane, tetradecyl
Trimethoxysilane, octadecyltrimethoxysila
, Vinyl trimethoxy silane, vinyl triethoxy
Orchid, phenyltrimethoxysilane, phenyltriet
Xysilane, γ-methacryloxypropyltrimethoxy
Silane, γ-mercaptopropyltrimethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane, etc.
Is mentioned. In the aqueous silicone composition of the present invention,
The compounding amount of the component (B) is 0.1% based on 100 parts by weight of the component (A).
If the amount is less than 01 parts by weight, the film obtained will be sufficiently cured
However, if it exceeds 10 parts by weight, it will not show adhesion to the substrate.
Therefore, 0.01 to 10 parts by weight per 100 parts by weight of component (A)
And more preferably 0.1 to 5 parts by weight. In the aqueous silicone composition of the present invention,
The component (C) is a component for improving adhesion to a substrate.
And an amide group and carboxyl group-containing organoa
Alkoxysilane and / or its partially hydrolyzed condensate
is there. This amide- and carboxyl-containing organoa
Lucoxysilanes are used with alkoxysilanes containing amino groups.
It is obtained by reacting with a carboxylic anhydride.
The organoalcohol containing amide group and carboxyl group
Amino group containing as starting material to obtain xysilane
Specific examples of the alkoxysilane of γ-aminopro
Piltrimethoxysilane, γ-aminopropyltriet
Xysilane, γ-aminopropylmethyldimethoxysila
Γ-aminopropylmethyldiethoxysilane, γ-
(N-β-aminoethyl) aminopropyltrimethoxy
Silane, γ- (N-β-aminoethyl) aminopropyl
Triethoxysilane, γ- (N-β-aminoethyl)
Minopropylmethyldimethoxysilane, γ- (N-β-
Aminoethyl) aminopropylmethyldiethoxysilane
And the like, as specific examples of the dicarboxylic anhydride,
Phthalic anhydride, succinic anhydride, methyl succinic anhydride
Anhydride, maleic anhydride, glutaric anhydride, itaconic acid
Anhydride, adipic anhydride, pimelic anhydride, slippery
Acid anhydride, azelaic anhydride, sebacic anhydride,
Fumaric anhydride and the like. And the amide group
For organoalkoxysilane containing carboxylic and carboxyl groups
The chemical formulas of the examples are shown as the following (Chemical Formula 5) to (Chemical Formula 10). Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image In the aqueous silicone composition of the present invention,
Component (C) is a solvent that is a parent solvent for the starting material,
For example, in alcohol, the above two kinds of components are mixed
And can be easily obtained by mixing. This place
In this case, at least one amino acid is contained in one molecule of the reaction product.
Need to contain carboxylic acid group and carboxyl group
Amino-containing alkoxysilanes or their partial hydrolysis
Less than one NH group in one molecule of the decomposition condensate
At least one molecule of dicarboxylic anhydride
It is necessary to react. In the aqueous silicone composition of the present invention,
The amount of the component (C) is 1 to 100 parts by weight of the component (A).
If the amount is less than parts by weight, the resulting film shows adhesion to the substrate.
If the amount exceeds 10 parts by weight, there is no elongation
1 to 100 parts by weight of component (A)
0 parts by weight is preferred, and more preferably 3 to 7 parts by weight.
You. In the aqueous silicone composition of the present invention,
The component (D) is also a component for improving the adhesion to the substrate.
Yes, epoxy-containing organoalkoxysilane and
And / or partial hydrolysis condensates thereof. This epoxy
Specific examples of the group-containing organoalkoxysilane include:
β-glycidoxyethyltrimethoxysilane, β-gly
Sidoxyethyltriethoxysilane, γ-glycidoxy
Propyltrimethoxysilane, γ-glycidoxypropyl
Rutriethoxysilane, γ-glycidoxypropylmethyl
Rudimethoxysilane, γ-glycidoxypropylmethyl
Diethoxysilane, β- (3,4-epoxycyclohexyl
Sil) ethyltrimethoxysilane, β- (3,4-epo
(Xycyclohexyl) ethyltriethoxysilane
I can do it. In the aqueous silicone composition of the present invention,
The amount of the component (D) is 1 to 100 parts by weight of the component (A).
When the amount is less than parts by weight, the obtained film has an adhesive property with the substrate.
Not shown, if it exceeds 10 parts by weight, elongation without followability
(A) 100 parts by weight of component (A)
Preferably 10 to 10 parts by weight, more preferably 3 to 7 parts by weight.
is there. In the aqueous silicone composition of the present invention,
The component (E) is used for crosslinking and curing the components of the composition of the present invention.
Catalyst for curing, specifically, dibutyltin dilaurate
, Dibutyltin dioctate, dioctyltin dilau
Rate, dioctyltin diacetate, tin octylate, etc.
Organotin compounds, zinc laurate, zinc acetate, stearin
Organic zinc compounds such as zinc oxide and zinc octylate;
Lopir titanate and its partially hydrolyzed condensate, tetra
Butyl titanate and its partially hydrolyzed condensate, bisdi
Propoxy titanium, bis (acetylacetonate) tita
Oxide, titanium lactate, ammonium titanium
Organic titanium compounds such as citrate are exemplified. This hard
If the catalyst for emulsification is not water-soluble,
It is desirable to emulsify and disperse in
Good. (E) in the aqueous silicone composition of the present invention
The amount of the component is 0.01 weight per 100 parts by weight of the component (A).
If the amount is less than 10 parts, the resulting film is not sufficiently cured.
Even if it exceeds 10 parts by weight, the effect remains unchanged and uneconomical
Therefore, 0.01 to 10 parts by weight based on 100 parts by weight of the component (A)
And more preferably 0.1 to 2 parts by weight. [0018]In the aqueous silicone composition of the present invention
The component (F) is a spherical silicone having an average particle size of 0.1 to 100 μm.
It is a rubber cured product particle.By adding the component (F)
AndThe resulting film has improved slip and abrasion resistance
You. When the average particle size of the component (F) is less than 0.1 μm,
Film does not show sufficient slipperiness.
The resulting film has poor abrasion resistance, so 0.1 ~ 100μm
Is required, preferably in the range of 1 to 20 μm
is there. As a preferred embodiment of the component (F), the present composition
Since the product is aqueous, it is in the form of an aqueous dispersion of the component (F).
It is good to mix. Obtaining an aqueous dispersion of this component (F)
To do this, disperse the curable organopolysiloxane in water.
After that, a conventionally known method of curing may be performed. This hard
As a form of the chemical reaction, any method of addition and condensation can be used.
Good, but particularly preferred is an addition reaction. For example, in one molecule
At least an alkenyl group bonded to the silicon atom
Two organopolysiloxanes and one molecule of silicon
Having at least two hydrogen atoms bonded to the atoms
Olga comprising luganohydrogenpolysiloxane
The nopolysiloxane mixture is separated into water using a surfactant.
After the addition, an addition reaction is performed using a platinum catalyst.
Just do it. In addition, the above-mentioned organopolysiloxane mixture
And the complex tackiness ratio is 1 × 10^Two~ 1 × 10⁸ Centipo
Dialkyl polyblocked with trialkylsiloxy at both ends
The addition and blending of siloxane is also one preferred embodiment.
is there. The amount of component (F) is based on 100 parts by weight of component (A).
If the amount is less than 1 part by weight, the resulting film has sufficient slipperiness
Does not show, the film obtained when it exceeds 100 parts by weight is abrasion resistant
To 100 parts by weight of component (A)
1 to 100 parts by weight, more preferably 10 to 50 parts by weight
Department. The aqueous silicone composition of the present invention comprises:(A)
~ To mix the components of (F)Obtained by
Mixing stirrers with well-known paddle-type, anchor-type, etc. stirring blades
What is necessary is to use it. And (B), (C) and (D)
The minutes can be mixed as is, but as described above
The component (A) is emulsified and dispersed in water using an emulsifier in advance.
It must be prepared as an aqueous emulsion and the component (F) is water
If it is not soluble, use the emulsifier beforehand
It is preferable to use as an aqueous emulsion after dispersion.
And it is good to dilute with water as needed. The aqueous silicone composition of the present invention contains
As necessary, as long as the effects of
Bon black, fluororesin powder, melamine resin powder,
Krill resin powder, polycarbonate resin powder, silicone
Resin powder, nylon resin powder, paraffin wax,
Polyethylene wax, silicone oil, various organic
Or compound inorganic pigment, thickener, defoamer, preservative, etc.
It is optional. The aqueous silicone composition of the present invention comprises a substrate
Table of rubber materials with excellent adhesion, abrasion resistance and surface smoothness
Useful for surface coatings. This aqueous silicone pair
As a rubber material whose surface is coated with a product,
Natural rubber, EPDM, SBR, chloroprene rubber, iso
Prene-isobutylene rubber, nitrile rubber, etc.
The form of rubber products made of these rubber materials is sponge
Shape or solid shape. Also fiber
Materials include nylon, polyester, acrylic,
Synthetic fiber such as Niron or acetate, or cotton, silk, wool
And other natural fiber materials. In order to improve the adhesion to the substrate,
Before coating the bright aqueous silicone composition,
Apply primer such as silane coupling agent to the material
May be used. Of surface coatings on these materials
As a treatment method, brushing the aqueous silicone composition,
Spray coat, roll coat, dip coat, nail coat
Room temperature or warming
The film can be cured by drying.
The thickness is preferably 0.1-20 μm, more preferably 0.5-10
μm. The rubber product treated in this way has its surface
Has excellent abrasion resistance and surface smoothness.
Weather strip materials for cars, O-rings, gaskets,
As sealing materials for various packings, rubber hose materials
Useful. [0023] EXAMPLES Next, the components (A), (C) and
The present invention will be described with reference to Synthesis Examples, Examples and Comparative Examples of the component (F).
Will be described in more detail, but the present invention is not limited to these
Not something. The complex viscosity in the examples was determined by the following method.
The surface smoothness of the rubber product in the examples was measured by
The evaluation of the properties and abrasion resistance was performed by the following methods. Actual
All percentages in the examples are percentages by weight. (Method of Measuring Complex Viscosity) Controlled Stress Rheometer CS (Bo
20mmφ core as a fixture
0.1rad / sec at 25 ° C
The complex viscosity of the frequency was measured. (Evaluation of bending whitening property) Apply EPDM solid rubber (50mm x 50mm, thickness 2mm)
Bent by hand so that the work surface is outside and folded
It was visually observed whether or not the portion was whitened. (Evaluation of surface smoothness) 2 of EPDM solid rubber (10mm x 50mm, thickness 2mm)
Stick the pieces on a copper plate (50mm x 50mm) as shown in Fig. 1
The load is measured using the dynamic friction coefficient measuring device shown in FIG.
Weight is 1kg, and the pulling speed is 100mm / min.
The coefficient of kinetic friction with the steel plate was measured. (Evaluation of wear resistance) EPDM sponge rubber [15mm x 150mm, thickness 2mm, hard
(JIS A) 36, specific gravity 0.63] as shown in Fig. 3.
Glass cell (wire) whose surface is polished with a paper file AA80
Contact, line width 5 mm), apply a thrust load of 350 g,
Reciprocating at a friction speed of 60 reciprocations / minute and a friction stroke of 70 mm
When rubbing, the number of reciprocating friction until the rubber surface is scraped
It was measured. Synthesis Example 1 of Component (A) Octamethylcyclotetrasiloxane 350g, 10% dodeci
70 g of aqueous solution of benzenesulfonic acid in 1 liter glass
Charge into a beaker and stir at 6,000 rpm using a homomixer.
When the mixture is stirred, a phase inversion occurs from the W / O type to the O / W type,
Thickening was observed, but stirring was continued for another 10 minutes. One
While stirring at 2,000 rpm, add 280 g of water and pressurize.
 300kg / cm^TwoAfter passing through the high-pressure homogenizer twice,
A stable white emulsion was obtained. Next, this Emma
Volume with stirring device, thermometer, reflux condenser
Transfer to 1 liter glass flask and react at 70 ° C for 6 hours
After cooling to 15 ° C and aging for 12 hours, 10%
Add 13g of thorium aqueous solution, neutralize to pH = 6.6 and homogenize
A white turbid aqueous emulsion (emulsion A-1) was obtained. This water
The non-volatile content after drying the water-soluble emulsion at 105 ° C. for 3 hours is 45.7.
%, (A) component is 45.0% and dodecylbenzenes
It contained 10% sodium sulfonate. This aqueous milk
Add isopropyl alcohol to the suspension to form an emulsion
After breaking, the siloxane was extracted and dried at 105 ° C for 3 hours.
When measuring the complex viscosity, 2.3 × 10⁶Centipoise
Indicated. This organopolysiloxane was analyzed by GPC.
As a result, the following formula was shown. Embedded image Synthesis Example 2 of Component (A) In Synthesis Example 1, substitute “cooled to 15 ° C and aged for 12 hours”
Except that it was cooled to 25 ° C and aged for 12 hours.
And neutralized to pH = 6.4 to obtain a homogeneous cloudy aqueous emulsion (milk
A suspension A-2) was obtained. This aqueous emulsion at 105 ° C for 3 hours
The non-volatile content after drying was 45.7%, and component (A) 44.7% and
Contains 1.0% sodium dodecylbenzenesulfonate
Was. Add isopropyl alcohol to this aqueous emulsion
Extract the siloxane after breaking the emulsion with
After drying at ℃ for 3 hours and measuring the complex viscosity, 8.5 × 1
0^FiveIt was centipoise. This organopolysiloxane
Was as follows as a result of GPC analysis. Embedded image Synthesis Example 3 of Component (A) In Synthesis Example 1, "After reacting at 70 ° C. for 6 hours, 15 ° C.
And aged for 12 hours instead of 6 hours at 85 ° C
The reaction was carried out in exactly the same manner except that
A turbid aqueous emulsion (emulsion A-3) was obtained. This aqueous milk
The non-volatile content after drying the suspension at 105 ° C for 3 hours is 45.9%
(A) Component 44.9%, sodium dodecylbenzenesulfonate
1.0%. Add isopropyl to this aqueous emulsion
After destroying the emulsion by adding alcohol,
Extract the sun, dry at 105 ℃ for 3 hours and measure the complex viscosity
7.4 × 10^ThreeIt was centipoise. This Olga
The nopolysiloxane showed the following formula as a result of GPC analysis. Embedded image Example of synthesis of component (C) 1 liter capacity with stirrer, thermometer, reflux condenser
108 g of maleic anhydride and ethanol
After dissolving uniformly in 350 g of γ-aminopropyl
242 g of rutriethoxysilane was added dropwise at room temperature for 1 hour.
Was. After completion of the dropwise addition, stirring was continued for another 1 hour to carry out the reaction.
As a result, a pale yellow transparent solution (solution C) was obtained. Add this solution to 10
The non-volatile content after heating at 5 ° C for 3 hours was 49.5%.
The reaction product in the liquid is analyzed by equipment such as GPC, IR, NMR, etc.
As a result of analysis, it was a compound represented by the following formula. HOOCCH = CHCONHC_ThreeH₆Si (OC_TwoH_Five)_Three Synthesis Example 1 of F Component Embedded image Methyl vinyl siloxa with complex viscosity of 10cp
350g and formula Embedded image A methylhydrogen with a complex viscosity of 200 cp
100 g of polysiloxane and formula Embedded image , The complex viscosity is 5.8 × 10⁶cp dimethyl policy
50 g of roxane, 1 liter glass with stirrer
Stir for 8 hours at room temperature and dissolve uniformly
I let it. Next, 350 g of the melt was added to a 1-liter glass
To the polyoxyethylene (additional moles = 9
L) Add 2.8 g of lauryl ether and 35 g of water, and mix
When the mixture was stirred at 6,000 rpm using a
/ W type undergoes phase inversion, thickening is observed, and further 15 hours
Stirring was continued. Then, while stirring at 2,000 rpm,
When 307 g of water was added, a uniform white emulsion was obtained.
Was. The emulsion was added to a 1 liter capacity with stirrer.
Transfer to a glass flask of
Acid-olefin complex in toluene solution (platinum content 0.5
%) 1.1 g with polyoxyethylene (number of moles added: 9 mol)
A mixture of 4.2 g of lauryl ether is added and stirred for 12 hours.
Performed to obtain an aqueous emulsion F-1. Average of this aqueous emulsion
Use Multisizer II (Coulter product name) for particle size
Was 4 μm, and the number of this aqueous emulsion was measured.
g was dried to obtain an elastic white rubber powder.
Was. This aqueous emulsion is volatile after drying at 105 ° C for 3 hours.
The departure is 50.9%, the component (F) is 49.9% and polyoxo.
Cyethylene (addition mole number = 9 mole) lauryl ether
The content was 1.0%. Synthesis Example 2 of F Component The above complex viscosity is 5.8 × 10⁶cp dimethyl polysiloxy
Sun 50g formula Embedded image The complex viscosity is 3.0 × 10^Fourcp dimethyl poly
The procedure was the same as in Synthesis Example 1 for the F component except that the siloxane was 50 g.
Thus, an aqueous emulsion F-2 was obtained. Average grain of this aqueous emulsion
Use Multisizer II (Coulter product name) for the diameter
It was 2 μm when measured with a few g of this aqueous emulsion.
After drying, an elastic white rubber powder is obtained.
Was. This aqueous emulsion is non-volatile after drying at 105 ° C for 3 hours.
50.6%, 49.6% of component (F) and polyoxy
Ethylene (additional mole number = 9 moles) lauryl ether
The content was 1.0%. Synthesis Example 3 of F component Methyl vinyl siloxane 35 with a complex viscosity of 10 cp
Methyl hydrogen policy with 0g and complex viscosity of 200cp
Roxane 100g and complex viscosity 5.8 × 10⁶cp
50 g of siloxane, methyl complex viscosity of 10 cp
390 g of vinyl siloxane and 200 cp of complex viscosity
Other than using 110 g of methyl hydrogen polysiloxane,
An aqueous emulsion F-3 was obtained in the same manner as in Synthesis Example 1 of the components.
The average particle size of this aqueous emulsion was determined using Multisizer II (Cole
It was 2 μm when measured using
After drying several grams of this aqueous emulsion,
A white rubber powder was obtained. This aqueous emulsion contains 105
The nonvolatile content after drying for 3 hours at 5 ° C. was 50.1%,
49.1% and polyoxyethylene (additional moles = 9
L) 1.0% lauryl ether
Was. [0034]Examples 1 to 7In the synthesis example described above,
The obtained component (A), component (C), component (F) and
Table 1 shows the components (B), (D), and (E).
Mixing with the combination composition of the combination, water for the surface treatment agent composition
A water-soluble silicone composition was prepared and these were
Rubber (thickness 2mm) and sponge rubber made of EPDM [thickness
2mm, hardness (JIS A) 36, specific gravity 0.63]
Cloth, and release for 2 minutes in a hot air circulating thermostat adjusted to 150 ° C.
And surface treatment, and evaluate the surface smoothness according to the method described above.
Valued. The results are shown in Table 1. [B component] Silane B-1: phenyltriethoxysilane Silane B-2: methyltriethoxysilane Silane B-3: n-decyltrimethoxysilane Silane B-4: vinyltriethoxysilane [D component] Silane D: γ-glycidoxypropyltrimethoxysila
N [E component] Emulsion E: 30% emulsion of dibutyltin dilaurate [0035] [Table 1][0036]For Comparative Examples 1 to 5,In the above synthesis example
The obtained component (A), component (C), component (F) and the aforementioned
Table 2 shows the components (B), (D), and (E).
Aqueous silica as a surface treatment agent composition
A corn composition was prepared and used in the same manner as in the Examples.
Surface treatment of EPDM rubber by the method
To evaluate the surface smoothness. The results are shown in Table 2. ratio
Amide group and carboxyl of component (C) as in Comparative Example 3.
Group-containing organoalkoxysilane and component (D)
Not more than 1 part by weight of organoalkoxysilane containing a oxy group
If full or not blended, surface slip,
It becomes poor in abrasion. As in Comparative Example 5, (F)
If the blending amount exceeds the limit,
It becomes white and has poor abrasion resistance. [0037] [Table 2][0038] The coating film of the aqueous composition of the present invention
Has excellent adhesion to the substrate surface and is coated
Rubber and fiber materials have excellent surface smoothness and wear resistance.
It becomes

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a combination sample of solid rubber and a copper plate for measuring a dynamic friction coefficient. FIG. 2 is a schematic longitudinal sectional view of a dynamic friction coefficient measuring device. FIG. 3 is a schematic diagram of a wear resistance measuring device. [Description of Signs] 1 Solid rubber, 2 Sponge rubber, 3 Ground glass, 4 Copper plate, 5 Glass plate.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 83:08) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 83/00-83/16 C08K 3 / 00-13/08

Claims (1)

(57) [Claims 1] (A) The following general formula (Chemical formula 1) (Where R ¹ is one or two or more substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, p is 100 parts by weight of a linear organopolysiloxane having a complex viscosity of 1 × 10 ⁴ to 1 × 10 ⁸ centipoise at 25 ° C., (B) the following general formula (Formula 2) 2] [Where R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms] and / or a part thereof. (C) 1 to 10 parts by weight of an organoalkoxysilane containing an amide group and a carboxyl group and / or 1 to 10 parts by weight of a partially hydrolyzed condensate thereof; and (D) an organoalkoxysilane containing an epoxy group. Or 1 to 10 parts by weight of a partially hydrolyzed condensate thereof; (E) 0.01 to 10 parts by weight of a curing catalyst ; Aqueous silicone composition comprising: