JPS6126627A - Water-dispersible silicon-modified vinyl polymer - Google Patents

Abstract

PURPOSE:The titled polymer having improved surface lubricating properties, heat resistance, weather resistance, water repellency, etc., obtained by reacting a water-dispersible vinyl copolymer consisting of a specific organosilicon monomer with a specified organopolysiloxane. CONSTITUTION:A water-dispersible vinyl copolymer consisting of (i) an organosilicon monomer containing one polymerizable unsaturated groups and one or more polymerizable unsaturated groups and one or more hydrolyzable groups directly bonded to silicon atoms in the molecule and (ii) another polymerizable monomer copolymerizable with the component i is reacted with (B) an organopolysiloxane containing one or more hydrogen atoms directly bonded to the silicon atoms in the molecule, having an average composition formula (R is 1-10C monofunctional hydrocarbon; 0.2<=a<=2.50; 0.0005<=b<=1.0, and 0.3<=a+b<=3.0), to give the aimed polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to water-dispersible silicone-modified vinyl polymers. More specifically, the present invention relates to a water-dispersible silicone-modified vinyl polymer having excellent surface lubricity, heat resistance, weather resistance, water testability, water resistance, and mechanical strength.

Organopolysiloxane, so-called silicone resin, has long been known as a material with excellent surface lubricity, heat resistance, weather abrasion resistance, water testability, and water resistance, but in addition to being generally expensive, silicone resin has various Because of its poor adhesion to substrates, it is used in a variety of applications by being mixed with other vinyl polymers. However, with long-term use, the silicone resin gradually disappears from the surface of the coating, and the effect often does not last. These improvements can be achieved by modifying the vinyl polymer using a condensation reaction using a silicon-based reactive group, or by introducing monounsaturated groups into the silicon resin and combining it with other vinyl yarn monomers. Copolymerized so-called silicon-modified vinyl polymers are effective. Moreover, the aqueous dispersion of the resin is particularly preferable from the viewpoint of resource saving and occupational health, since the volatile substance is water.

The aqueous dispersion of silicone-modified vinyl polymer proposed in this paper and L7 are produced by producing a vinyl polymer having carboxyl groups and hydroxyl groups in a water-dilutable organic solvent, and adding hydroxyl groups or Aqueous dispersion obtained by reacting an organopolysiloxane having an alkoxyl group and then diluting with water (JP-A-5O-95388)
An aqueous dispersion obtained by emulsion polymerization of an organopolysiloxane having a polymerizable unsaturated group and other vinyl monomers in an aqueous medium in the presence of an emulsifier (Japanese Patent Application Laid-Open No. 51-146525)
etc. are known. However, in these methods, since the reactivity of organopolysiloxane is low, modification is often incomplete, and in some cases, phenomena such as separation and aggregation are likely to occur during the reaction. Therefore, the reality is that there are compositional constraints in order to stably obtain a water-dispersible silicone-modified vinyl polymer that exhibits excellent a-performance.

In view of the current situation, the present inventors have conducted extensive research and have arrived at the present invention.

That is, the present invention provides an organosilicon monomer (Al) having at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom in the molecule, and A water-dispersible vinyl copolymer (11) obtained from other polymerizable monomers ω) having at least one hydrogen atom directly bonded to a silicon atom in the molecule and having an average compositional formula of It is an unsubstituted monovalent hydrocarbon group, and a and b are each 0.2≦a≦2.5.0.0005≦b≦
1.0, and a+b satisfies 0.3≦a+b≦3.0. ) The present invention relates to a water-dispersible silicone-modified vinyl polymer obtained by reacting with an organopolysiloxane represented by:

The water-dispersible vinyl copolymer (1) used to obtain the water-dispersible silicone-modified vinyl polymer of the present invention has at least one polymerizable unsaturated group and at least one silicon-based hydratable group in the molecule. It is obtained from an organosilicon monomer (A) having a decomposable group and another polymerizable monomer that can be copolymerized with the monomer surface.

As the organosilicon monomer (5), for example, vinyl) IJ
Methoxysilane, vinyltriethoxysilane, vinyltriptoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, trimethoxysilylpropylamine, r-C meta)acryloxypropyltrimethoxysilane, r-( meth)acryloxypropyltriethoxysilane, r (meth)acryloxypropylmethyldimethoxysilane, r-(meth)acryloxypropylmethyljethoxysilane, r-
(Meth)acryloxyglobiltris(β-meth-5=xyethoxy)silane, N-B-(N-vinylbenzylamino)ethyl-r-aminopropyltrimethoxysilane, N-vinylbenzyl-r-aminopropyltrimethoxysilane Ethoxysilane, 2-styrylethyltrimethoxysilane,
3-(N-styrylmethyl-2-amineethylamine)
Propyltrimethoxysilane, (meth)acryloxyethyldimethyl (3-)! J methoxysilylpropyl) ammonium chloride, vinyltriacetoxysilane,
Examples include vinyltrichlorosilane, and one type selected from these groups or a mixture of 2" or more of 1M or more can be used. In the present invention, the organosilicon monomer surface is a water-dispersible vinyl copolymer. It is an essential component for the reaction between (1) and organopolysiloxane (1).The amount of organosilicon monomer used in the monomer mixture is not particularly limited, but it depends on the reaction efficiency and water dispersibility. Considering the price of silicone-modified vinyl polymer, preferably 0.1~
50 weight ratio, preferably 0.5 to 20 weight ratio.

In the present invention, other polymerizable monomers copolymerizable with the organosilicon monomer surface (B1 includes unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc.) : Carbon number is 1 to 18
Esters of linear or branched aliphatic or cycloaliphatic alcohols with unsaturated carboxylic acids: polyvalents such as ethylene glycol, diethylene glycol, propylene glycol, chrycerol, trimethylolpropane, pentaerythritol, etc. Esters of alcohols and unsaturated carboxylic acids: (meth) allyl alcohol, crotonaldehyde, etc. Unsaturated alcohols: polyhydric alcohols, unsaturated 7, 2-,! Ethers of: Olefinic hydrocarbons such as ethylene, chlorostyrene, styrene, etc.; Vinyl aromatic hydrocarbons such as styrene, chlorostyrene, vinyltoluenate; Vinyl halides such as vinyl fluoride, vinyl chloride, vinyl bromide, etc. Vinylidene halides such as vinylidene fluoride, vinylidene chloride, vinylidene bromide, etc.; unsaturated nitriles such as (meth)acrylonitrile, crotonitrile, inglovir cyanoacrylate, methylene glutaronitrile, vinylidene cyanide, etc.; acetic acid, propionic acid, butyric acid, Vinyl esters of monohydric carboxylic acids such as benzoic acid; vinyl ethers of monohydric alcohols such as methyl alcohol, ethyl alcohol, furoyl alcohol, and fluoroalcohol; unsaturated aldehydes such as (meth)acrolein, crotonaldehyde; dimethylamine; Methyl (meth)
Acrylate, diethylaminomethyl acrylate: Unsaturated glycidyl esters such as glycidyl (meth)acrylate; Unsaturated glycidyl ethers such as (meth)allyl glycidyl ether; Unsaturated acid amides such as (meth)acrylamide, diacetone acrylamide, etc.: Methylol unsaturated acid amide derivatives such as acrylamide, diene hydrocarbons such as butadiene and isoprene, divinyl aromatic hydrocarbons such as divinylbenzene, divinyltoluene, etc.; Species or mixtures of two or more species can be used.

In order to obtain the water-dispersible vinyl copolymer (I), it is preferable to use an emulsion polymerization method, considering the ease of controlling the polymerization reaction and the usage form of the ultimately obtained water-dispersible silicone-modified vinyl polymer. . Examples of emulsion polymerization methods include under normal pressure,
organosilicon monomers under autogenous pressure or under artificial pressure in the presence or absence of emulsifiers and/or colloids with polymerization initiators and optionally accelerators, preferably in an inert atmosphere. The body surface and the polymerizable monomer (2) may be emulsion copolymerized according to a known procedure. In this case, it is free to use additives customary in emulsion polymerization technology, such as chelating agents, buffering agents, salts of mineral or organic acids, pH regulating aids, chain transfer agents, etc. The water-dispersible vinyl copolymer (11) can also be obtained by polymerizing by a known polymerization method other than the emulsion method, such as bulk polymerization or solution polymerization in an organic solvent, and then dispersing it in water.

For example, if the copolymer itself has self-emulsifying properties, it can be dispersed in water by simply blending it with water, or if the copolymer does not have self-emulsifying properties, it can be dispersed in water using an emulsifier and/or a protective agent. It can be dispersed in water in the presence of colloids.

The organopolysiloxane (Il) used to obtain the water-dispersible silicone-modified vinyl polymer of the present invention has at least one hydrogen atom directly bonded to a silicon atom in the molecule and has an average compositional formula of RB HbS i Oa-a-b)/
2 (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a and b#'i each 0.2
≦a≦2.5.0.0005≦b≦1.0, and a+b is 0.3≦a+b≦3.0. ) is an organopolysiloxane represented by The hydrogen atom directly bonded to the silicon atom is essential for the reaction with the silicon hydrolyzable group contained in the water-dispersible vinyl copolymer (I), and at least one hydrogen atom is present in one molecule of organopolysiloxane (It). 1, preferably 100 or more silicon atoms. On the other hand, if the number of hydrogen atoms directly bonded to silicon atoms exceeds 100-10 = 9100 per silicon atom, #aggregation occurs during the reaction with the water-dispersible vinyl copolymer (1'). It is easy to break and is not desirable. The number of silicon atoms contained in one molecule is not particularly limited, but preferably 4 or more and 2000 or less, and if it is less than 4, the characteristics of silicon are difficult to exhibit, and 2001 or more. In the case of , there are disadvantages of low reactivity and separation and aggregation. Organopolysiloxane (1
) can be suitably used in liquid form as it is or in the form of emulsification and dispersion in an aqueous medium in the presence of an emulsifier.

The water-dispersible silicone-modified vinyl polymer of the present invention comprises a water-dispersible vinyl copolymer (1) and an organopolysiloxane (I).
It is obtained by reacting with l). The reaction may be carried out by mixing the water-dispersible vinyl copolymer (I) obtained by the above polymerization and the organopolysiloxane (11), or the reaction may be carried out by mixing the water-dispersible vinyl copolymer (I) obtained by the above polymerization with the organopolysiloxane (11). Monomer (A) and other polymerizable monomers (6
), and the reaction may be carried out simultaneously with the polymerization.

In the latter method, the method of mixing the organopolysiloxane (phase) includes, for example, (a) a method of dropping the polymerizable monomer mixture into a medium containing the organopolysiloxane (■) and polymerizing it; Polysiloxane (II
) and a WiFMIC-composable monomer mixable monomer mixture x are added dropwise to polymerize, and (c) organo can be employed.

The water-dispersible silicone-modified vinyl polymer is prepared by combining the water-dispersible vinyl copolymer (I) and organopolysiloxane (lj) at room temperature to 1 (10'c%) under a temperature condition of preferably 50 to 85°C. , is obtained by reacting while removing hydrogen by-product during the reaction from the system, but in order to shorten the reaction time, it is preferable to use an appropriate reaction catalyst.As the reaction catalyst,
Metal salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, stannous acetate, lead naphthenate, zinc caprylate, zirconium acetate, iron 2-ethylhexane, cobalt naphthenate, etc.; tetrabutyl titanate ester, titanium Titanate esters such as acid tetranonyl esters and their polymers; silicon-based hydrolyzable substances such as basic substances such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, ammonia, triethylamine, triethanolamine, etc. Conventional reaction catalysts are effective for the condensation reaction between the group and the hydrogen atom directly bonded to the silicon atom, and one type or a mixture of two or more types selected from these groups can be used. A preferred method for using the catalyst is to use a metal salt of a carboxylic acid such as dibutyltin diacetate, zinc caprylate, iron 2-ethylhexane, etc. together with a basic substance such as sodium hydroxide, ammonia, triethylamine, etc. It is. There is no particular restriction on the amount of reaction catalyst used, but as a rough guide, it can be 0.05 to 10 parts by weight per 100 parts by weight of nonvolatile content of the water-dispersible silicone-modified vinyl polymer. The reaction catalyst can be used before or after mixing the water-dispersible vinyl copolymer (I) and the organopolysiloxane (11).

As the polymerization method for the water-dispersible vinyl copolymer (1), it is preferable to use the emulsion polymerization method, as described above,
In this case, the reaction between the water-dispersible vinyl copolymer (1) and the organopolysiloxane (1) is performed by emulsion polymerizing the water-dispersible vinyl copolymer (1) and the organopolysiloxane in the same manner as above. (Ill), or a method of emulsion polymerization of water-dispersible vinyl copolymer (1) in the presence of organopolysiloxane (Ill). Organopolysiloxane (II)
The components are easily localized, and for example, when a film is formed, more organopolysiloxane components can be concentrated on the surface.
) can be used effectively. The emulsion polymerization method used in the latter method is organopolysiloxane (lI
) Any conventionally known emulsion polymerization method can be applied, as in the case where the polymer is not coexisting. In this case, as mentioned above, additives customary in emulsion polymerization technology may be used freely.

The water-dispersible silicone-modified vinyl polymer of the present invention has excellent surface lubricity, heat resistance, weather resistance, water comfort, water resistance, and mechanical strength, as well as repellency that volatilizes volatile components at room temperature or under heated conditions. It can be made into a film, sheet, or molded product. In addition, the water-dispersible silicone-modified vinyl polymer of the present invention can be applied to a wide variety of applications, such as enrichment agents or adhesives for metals, plastics, wood, inorganic substrates, etc., and processing agents for paper, fibers, etc. It is Noh. At this time, pigments, toners, crosslinking agents, viscosity modifiers, wetting agents, plasticizers, rust preventives, antifoaming agents, antistatic agents, etc. known to those skilled in the art are free to be added.

The water-dispersible silicone-modified vinyl polymer of the present invention is composed of a water-dispersible vinyl copolymer (11) and an organopolysiloxane (11).
), and has excellent sanding surface lubricity, heat resistance, weather resistance, water testability, ml water resistance, mechanical strength, and excellent adhesion to various substrates. There is. Moreover, the silicon hydrolyzable group contained in the water-dispersible vinyl copolymer (1) and the organopolysiloxane (I
The water-dispersible vinyl copolymer (1) and organopolysiloxane (Ill) are bonded together through a reaction with the hydrogen atoms directly bonded to the silicon atoms contained in Ill, so the advantage is that the initial performance can be maintained for a long period of time. In addition, it is possible to localize the organopolysiloxane () by selecting the reaction method, and for example, when it is formed into a film, more organopolysiloxane components can be concentrated on the surface. , a small amount of organopolysiloxane (
n) can be used effectively. Furthermore, since the water-dispersible silicone-modified vinyl polymer of the present invention can be easily produced by emulsion polymerization, the volatile component can be completely reduced to water, saving resources and labor. It is also preferable from the viewpoint of hygiene.

It has the characteristic that it is not subject to any compositional restrictions during the reaction between the water-dispersible vinyl copolymer (I) and the organopolysiloxane (Il).

The embodiments of the present invention will be explained below by way of examples.
The invention is not limited by the following examples. In the Reference Examples, Comparative Reference Examples, Examples, and Comparative Examples, all parts refer to parts by weight, and all fc% refers to i% by weight. The organopolysiloxanes used in the examples are as follows.

Organopoly average composition formula (CHi)t,ts
Ho, *5SiOo)s Siloxane (1) Average molecular weight 2500 Organopolymer Average composition formula (
CHa) o,s (CsHs) t,oHo,s Siloxane (A) 5iO0,.

Average molecular weight 1500 Organopolymer Average composition formula (CHs) 1. I
IHo, I S tO'. Kisa' (3) Average molecular weight 30,000 Aqueous emulsion of organopolysiloxane Methylhydrodiene polysiloxane emulsion (trade name, Boron MR, manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 60%)
) Reference Example 1 154 parts of deionized water, 1 part of sodium lauryl sulfate, and 3 parts of polyoxyethylene oleate (HLB=9) were placed in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser. part and potassium persulfate 0.
Add 4 parts and slowly blow in nitrogen gas until 75.
℃ and stirred to form a homogeneous aqueous solution. Next, a mixture of polymerizable monomers consisting of 5 parts of vinyltrimethoxysilane, 3 parts of acrylic acid, 25 parts of methyl methacrylate, and 67 parts of butyl acrylate was added dropwise through the dropping funnel over a period of 2 hours. After that, stirring was continued for 1 hour while maintaining the temperature at 75°C, and then after cooling to room temperature, 28% ammonia water was added to adjust the pH to about 8, and the water-dispersible vinyl copolymer (1 ) was obtained.

Reference Examples 2 to 4 A water-dispersible vinyl copolymer was prepared by following the same procedure as in Reference Example 1, except that the polymerizable monomer mixture, emulsifier, polymerization catalyst, water, and neutralizing agent were as shown in Table 1. Union (A
) to (4) were obtained. Its properties are summarized in Table 1.

Reference Example 5 80 parts of isopropyl alcohol was charged into the same flask as used in Reference Example 1, and heated to 80° C. while gently blowing nitrogen gas. Next, a polymerizable monomer mixture consisting of 3 parts of vinyltritoxysilane, 6 parts of acrylic acid, 40 parts of methyl methacrylate, 51 parts of butyl acrylate, and 0.7 parts of azobisisobutyronitrile, and a mixture of a polymerization initiator were added. was added dropwise from the dropping funnel over a period of 4 hours.

After the dropwise addition was completed, stirring was continued for an additional 2 hours while maintaining the temperature at 81°C, and then the mixture was cooled to room temperature. Next, after adding 5 parts of Section 28 ammonia water and 210 parts of deionized water,
The mixture was heated again and the entire amount of isopropyl alcohol and a total of 145 parts of deionized water were distilled off to obtain a water-dispersible vinyl copolymer (5) having a pH of about 8.0 and a non-volatility of about 40%.

Comparative Reference Example 1 A water-dispersible vinyl copolymer (6) was obtained by following the same procedure as in Reference Example 1 except that the polymerizable monomer mixture was outside the scope of the present invention as shown in Table 1. Ta. Its properties were as shown in Table 1.

Example 1 Into the same flask as used in Reference Example 1, 258 parts of the water-dispersible vinyl copolymer (]) obtained in Reference Example 1 and 0.3 parts of diptyltin diacetate were charged and mixed with 7 parts while stirring.
Heated to 5°C. Next, the average composition formula is (CHa)5+5H
o, 5ssiOo)s 3 parts of organopolysiloxane (1) having a % average molecular weight of 2500 were added dropwise from the dropping funnel over 30 minutes. After that, while keeping the temperature at 75℃,
Stirring was continued for a period of time, and then the mixture was cooled to room temperature to obtain a water-dispersible silicone-modified vinyl polymer (1).

Water-dispersible silicone-modified vinyl polymers (A) to (5) were prepared according to the same procedure except that the polymer, organopolysiloxane, reaction catalyst, and reaction conditions were as shown in Table 2.
I got it.

2. 154 parts of surface water, 1 part of sodium lauryl sulfate, 3 parts of polyoxyethylene oleate (HLB=9), 3 parts of organopolysiloxane (1), 0.3 parts of dibutyltin dilaurate, and 0.4 parts of potassium persulfate. A uniform aqueous solution was prepared by heating to 75° C. and stirring while gently blowing nitrogen gas. Next, a polymerizable monomer mixture consisting of 5 parts of vinyltrimethoxysilane, 3 parts of acrylic acid, 25 parts of methyl methacrylate, and 67 parts of butyl acrylate was added dropwise from the dropping funnel over a period of 2 hours. After that, stirring was continued for 2 hours while maintaining the temperature at 75°C, and then after cooling to room temperature, 28% ammonia water was added to adjust the pH to about 8.
A water-dispersible silicone-modified vinyl polymer (6) was obtained.

Example 7 Into the same flask used in Reference Example 1, 11 g of deionized water was added.
0 parts, sodium dodecylbenzenesulfonate 1.0 parts, sorbitan monostearate (HLB=4.7) g,
0 parts, 0.6 parts of tetrabutyl titanate, and 0.5 parts of ammonium persulfate were added, heated to 75° C. while gently blowing nitrogen gas, and stirred to obtain a uniform aqueous solution. Next, a polymerizable monomer consisting of 3 parts of r-methacryloxypropyltrimethoxysilane, 10 parts of hydroxyethyl acrylate, 21 parts of methyl methacrylate, 66 parts of ethyl acrylate and 6 parts of organopolysiloxane (A) and organopolysiloxane were added. The mixture was added dropwise from the dropping funnel over a period of 2 hours. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 75°C, and then the mixture was cooled to room temperature to obtain a water-dispersible silicone-modified vinyl polymer (7).

Example 8 Into the same flask used in Reference Example 1, add 15 ml of deionized water.
4 parts of sodium lauryl sulfate, 1 part of sodium lauryl sulfate, 3 parts of polyoxyethylene oleate (HLB=9) and 0.4 parts of potassium persulfate were heated to 75°C while gently blowing nitrogen gas, and stirred. A homogeneous aqueous solution was obtained.

Next, a first polymerizable monomer mixture consisting of 3 parts of acrylic acid, 13 parts of methyl methacrylate, and 34 parts of butyl acrylate was added dropwise from the dropping funnel over 1 hour, and stirring was continued for an additional 30 minutes. Next, 5 parts of vinyltrimethoxysilane prepared in advance and 1 part of methyl methacrylate)
A mixture of a polymerizable monomer, an organopolysiloxane, and a reaction catalyst consisting of 2 parts of butyl acrylate, 33 parts of organopolysiloxane (1), and 0.3 parts of diptyltin dilaurate was added dropwise over 1 hour. Thereafter, the temperature was adjusted to be maintained at 75°C to obtain a water-dispersible silicone-modified vinyl polymer (8).

Example 9 Into the same flask used in Reference Example 1, add 15 ml of deionized water.
2 parts of sodium lauryl sulfate, 1 part of sodium lauryl sulfate, 5 parts of an aqueous emulsion of organopolysiloxane (active ingredient 60%), and 0.4 parts of potassium persulfate, heated to 75°C while gently blowing nitrogen gas, and stirred. to make a homogeneous aqueous solution. Next, a polymerizable monomer mixture consisting of 3 parts of vinyltrimethoxysilane, 1 part of acrylic acid, 30 parts of methyl methacrylate, and 66 parts of butyl acrylate was added dropwise from the dropping funnel over a period of 2 hours. Next, 0.3 part of diptyltin dilaurate was added and stirring was continued for 2 hours while keeping the temperature at 75°C, followed by cooling, and a 5-functional sodium hydroxide aqueous solution was added to adjust the pH to about 7 to obtain a water-dispersible silicone modified product. A vinyl polymer (9) was obtained.

Example 1O The silicon-modified vinyl polymers obtained in Examples 1 to 9 were applied to a polished mild steel plate degreased with xylene using a No. 32 bar coater, and the physical properties of the coating film were evaluated after drying by heating at 150°C for 10 minutes. The results are summarized in 3 tables.

Comparative Examples 1 to 5 Water-dispersible vinyl copolymers (1) obtained in Reference Examples 1 to 5
Table 3 shows the physical properties of the coating film obtained by using (5) without modification with organopolysiloxane and coating it with an Nα32 bar coater on a polished mild steel plate degreased with xylene and heating and drying it at 150°C for one part. It was shown to.

Comparative Example 6 In the same flask as used in Reference Example 1, 258 parts of the water-dispersible vinyl copolymer (6) obtained in Comparative Reference Example 1 and 0.3 part of diptyltin diacetate were charged and heated to 75°C with stirring. heated to. Next, organopolysiloxane (1
) was added dropwise from the dropping funnel over 30 minutes. After that, stirring was continued for 2 hours while maintaining the temperature at 75°C.
After cooling, a water-dispersible vinyl copolymer containing organopolysiloxane for comparison was obtained. This was applied to a polished mild steel plate degreased with xylene using a No. 32 bar coater, and the physical properties of the coating film after drying by heating at 150° C. for 10 minutes are shown in Table 3.

Note) Test method for physical properties of paint film Appearance of paint film: Observe the surface condition of the paint film after heating and drying at 150°C for 10 minutes Adhesion: Testing of the physical properties of the paint film at l+mn intervals After making 100 squares by making cuts vertically and horizontally, apply Chiban cellophane tape 'Nal 8 to the cellophane tape on this side.
00) and then peel it off and check the peeling state of the coating film.
Scoring was done using an O-point scale.

Heat resistance...Temperature 250℃, load] Fyg
/cvr'', a stainless steel plate was pressed onto the surface of the coating film and left for 10 seconds, and then the peelability of the stainless steel plate and changes in the coating film were examined.

Weather resistance: Irradiation was performed for 1000 hours using a sunshine type etherometer, and the gloss retention rate was determined from the gloss before and after irradiation.

Masatsu coefficient: Load 100 t, moving speed 150 wm/Mi using HEIDON-14 type surface property measuring machine
A Teflon-treated surface indenter (63,5×6
3.5 mm) was determined.

The smaller the value, the better the surface lubricity.

Repellent Water properties: Drop a small amount of deionized water onto the paint film to see the water droplets and coating needles Water properties: Soak the sample plate in deionized water for 3 days at room temperature, We investigated changes in

Patent applicant: Nippon Shokubai Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. An organosilicon monomer (A) having in its molecule at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom, and the monomer A water-dispersible vinyl copolymer (I) obtained from other polymerizable monomers (B) that can be copolymerized with (A) and at least one hydrogen atom directly bonded to a silicon atom in the molecule. And the average compositional formula is R_aH_bSiO_(_4_-_a_-_b_)_/
_2 (R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a and b are each 0.2≦
a≦2.5, 0.0005≦b≦1.0, and a+
b is 0.3≦a+b≦3.0. ) A water-dispersible silicone-modified vinyl polymer obtained by reacting with organopolysiloxane (II) represented by