JPS58154766A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn. forming a coating film with excellent water and oil repellency and resistance to staining and abrasion, prepared by dissolving a specified silicone-based graft copolymer in an organic solvent solution of film-forming resin. CONSTITUTION:Acryl-modified silicone (A) is prepared by condensation reaction of 1mol of silicone of formulaI(where R<1> and R<2> are each a 1-10C univalent hydrocarbon group, phenyl or an univalent halogenated hydrocarbon group; n is 1-500) with 0.25-1mol of acrylic compd. of formula II (where R<3> is H or methyl; R<4> is methyl, ethyl or phenyl; X is Cl, methoxy or ethoxy). Then silicone-based radical copolymer with a silicone content (as SiO2) of 5-80wt% (C) is prepared by interaction of (A) and radical-copolymerizable monomer (B) (e.g. methacrylic acid). (C) is dissolved in an organic solvent solution of film-forming resin (e.g. acrylic resin) in an amount of 0.01-10wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies a silicone graft copolymer to a coating composition made of a film-forming resin, Organic Toko K, which improves the coating surface KII water and oil repellency. The object of the present invention is to provide a footwear article which is imparted with stain resistance and low friction properties and is capable of forming a coating film.

There is a strong interest in energy saving and capital saving, and there are great expectations for the production of higher performance paints, which provide oil resistance, stain resistance, and low friction properties to the coating surface. Various methods are being considered.

For example, the method of applying radiation, light, or plasma to the surface of the coating film, the method of applying a coupling steel such as a polymer in oligomer or 7Ran to the surface of the coating film, and the method of coating the surface of the coating film with fluorine resin in silicone resin. Methods such as adding low energy polymers to paints are being carried out.

Among these methods, the surface grafting method using radiation, light, or plasma irradiation on the surface of the coating film requires special equipment, the surface is modified, and the coating film is expensive. In the method of coating the coating surface with a coating agent, the modification of the coating surface is temporary and the modification effect on the coating surface is not durable, and the coated substance is removed and the coating becomes thin and thin. There are many problems, such as the difficulty of making a film. Also, polys with low surface energy such as silicone resin and 7-bulk resin! -The method of adding KFi to the paint (%) The durability of the modification effect on the surface of the paint film is never satisfactory. The original performance of the coating film may also be impaired.The adhesion between the 4Isc coating film and the underlying surface will be exposed.

In view of these conventional drawbacks, the present invention has been developed to suit K11, which has a tightening mechanism and a relaxed beak, after extensive research.

That is, the present invention uses a silicone-based graft copolymer obtained by radically polymerizing an acrylic-modified silicone and a radically polymerizable monomer in an organic solvent solution (hereinafter referred to as organic S) of a film-forming resin.
The acrylic-modified silicone undergoes a condensation reaction between a silicone represented by the general formula (A) and an acrylic compound α25 to 1 mole represented by the general formula (B) per 1 mole thereof. The product is a coating composition.

R Otori (A) HO (8i0). H (R' and R8 are carbon number I
1 to 10 monovalent aliphatic hydrocarbon groups, 7-enyl groups, or -valent halogenated hydrocarbon groups. n is a positive number of 1 or more. ) is a water bulk atom or a methyl group. 84 is a methyl group, ethyl group, or phenyl group. xh chlorine atom, methoxy group or ethoxy group. ) The present invention includes a polymeric additive that has an excellent effect of modifying the surface of a coating film obtained by using an organic solvent solution and its sustainability.
It is said that a graft copolymer with a special structure consisting of a silicone-based component and a film-forming tree 111 (hereinafter referred to as paint polymer) K@ soluble anchor component in organic solvent-based paints is useful. This was done based on fact IIK.

The present invention provides a coating composition in which a small amount of silicone-based graft copolymer, in which a part of the backbone polymer (anchor component) is the same component as the paint polymer or a component compatible with the paint polymer, is added and dissolved in an organic solvent solution. From this, the resulting coating film does not impair the original performance of the coating film, and has excellent water richness, oil repellency, stain resistance, and low friction properties on the coating surface, and is a To9 anchor component. Due to the presence of the silicone graft copolymer, the silicone-based graft copolymer that migrates and concentrates to the coating surface does not easily separate from the coating surface and maintains the effect of modifying the coating surface.

Modified VC on the coating film surface obtained by the coating composition of the present invention
The key to the migration (referred to as concentration) of the silicone-based graft copolymer used in the present invention to the coating surface is to place the coating surface in a hydrophobic environment (usually in contact with the atmosphere). ), and more specifically, the base for painting is metal, ceramics,
It is sufficient in the environment where ordinary paints for plastics and wood are used, that is, in the atmosphere. That is, a coating film obtained by applying the coating composition of the present invention to the intended base KIk, volatilizing the solvent in the air, and then carrying out an appropriate crosslinking reaction as necessary, can be obtained by The silicone-based graft copolymer is compressed onto the surface in contact with the surface, and the air-filled surface of the paint film exhibits excellent water and oil repellency, stain resistance, and low friction. In this case, the present-Akira silicone graft copolymer was hardly concentrated and 1. There is no adverse effect on the adhesion between the paint film and the base. Rather, adhesion may be improved depending on the structure of the anchor component.

As mentioned above, the paint bases that can be applied to the present invention include metals, ceramics, wood, and plastics, which are commonly used.
You can open it.

General formula (A) used in the present invention, ie I HO(SiO)! At present, various types of silicone represented by IH can be easily manufactured by hand, and the one suitable for the purpose can be used. group hydrocarbon group, phenyl group, or -valent halogenated hydrocarbon group, and has 1 to 10 carbon atoms.
Monovalent aliphatic hydrocarbon groups include, for example, methyl, ethyl, and decyl groups, and -valent halogenated hydrocarbon groups include, for example, 115-)lifluoropropyl and 4,44-trifluoropropyl groups. Examples include fluoro-45-difluorobutyl group and 2-chloroethyl group. Particularly preferred as R1 and R2 is a methyl group.

Regarding the influence of the molecular weight of the silicone represented by the general formula (A), the general number of Kn is 1o.

Copolymerization of an acrylic modified silicone derived from a silicone with a large molecular weight and a radically polymerizable monomer results in an oil-like product that tends to have a black color.
Copolymerization of acrylic-modified silicone derived from silicone with a small molecular weight of 100 or less and a radically polymerizable monomer produces oil-like, jelly-like, solid, and other forms of 1 mO each, depending on the type of hexamer used. Therefore, it is possible to obtain a silicone-based graft copolymer in a desired form. In general formula (A), On is 1 or more, but if n is too small, the effects of silicone, i.e., water richness, oil repellency, and low friction properties, cannot be obtained; n is 1 or more and 5o.

Hereinafter, n is more preferably 10 or more and 500 or less. R'X (Rs is a hydrogen atom or methyl group. R4 is a methyl group, ethyl group, or phenyl group.
Examples of the acrylic compound represented by include r-methacryloxyglobylmethyldichlorosilano, r-methacryloxyglobylmethyljethoxysilane, r-methacryloxypropylphenyldichlorosilane, r-methacryloxyglobyl ethyldichlorosilano, r- Acryloxypropylmethyldichlorosilane etc. can be used. These acrylic compounds are generally well known and can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method of Japanese Patent Publication No. 1855-9969. .

When the f4JLhypr) compound is .t-methacryloxyglobylmethyldicyclosilane, it can be obtained by reacting allyl methacrylate and methyldichlorosilano in the presence of chloroplatinic acid.

The reaction between the silicone represented by the general formula (M) and the acrylic compound represented by the general formula (B) proceeds very smoothly in accordance with ordinary organic chemical reaction operations. For example, general formula (B)
When X in the acrylic compound represented by is a chlorine atom, the acrylic compound represented by the general formula CB or When a solution of the acrylic compound represented by the general formula (B) dissolved in a suitable solvent is added dropwise at room temperature, the reaction proceeds immediately and smoothly. The desired acrylic-modified silicone can be obtained by separating F from the acid acceptor hydrochloride FjlK produced after the reaction, and then optionally washing with water and evaporating the solvent. The solvent that can be used in this reaction is preferably a solvent that dissolves both raw material components and is inert to both raw material components under the reaction conditions. Typical solvents include diethyl ether, detrahydrofurano, acetone, benozeno, and toluene. , xylene, mineral salts) I) 6. As acid acceptors, known amines are used when X in general formula (B) is a methoxy group or a methoxy group (in which case silicone represented by general formula (A) and acrylic compound represented by general formula CB) are combined. Then, a dealcoholization condensation reaction may be performed.

In this case, in order to accelerate the reaction, catalysts (catalysts conventionally used in transesterification reactions, such as inglobil orthinotitanoate, sulfuric acid, P-)luenesulfonic acid, trifluoroacetic acid, etc. can be used.

In this way, acrylic-modified silicone 7 can be obtained by the reaction of the silicone represented by the general formula (A) (hereinafter referred to as 1 mole of silicone) and the acrylic compound represented by the general formula (B) (hereinafter referred to as acrylic), but both The reaction molar ratio must be 125 to 1 mol of acrylic to 1 mol of silicone. When the amount of acrylic exceeds 1 mol per 1 mol of silicone, gelation occurs when the acrylic modified silicone is radically copolymerized with a radically polymerizable monomer, and it can be used as an organic III agent tumor layer coating agent. Silico
KFI to obtain a 7-based graft copolymer becomes difficult. Also, if the acrylic α is less than 25 moles per mole of silicone, the resulting acrylic modified silicone is used for radical copolymerization with a radical polymerizable monomer to obtain a silicone-based graft copolymer, and unreacted silicone becomes a silicone-based graft copolymer. This is because a large amount remains inside.

The acrylic-modified silicone obtained by oxidation has extremely high polymerizability, and copolymerization proceeds extremely smoothly with general radically polymerizable monomers, making it possible to obtain a silicone-based graft copolymer. can. Its molecular weight can be controlled by known polymerization techniques IfK. Radically polymerizable monomers that can be used in the present invention include methacrylic acid,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, methalyl@2-ethylhexful, citalohexyl methacrylate, stearyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, styrene substituted product 1. : Vinyl esters of organic acids such as vinyl acetate, low molecular weight linear hydrocarbons such as ethylene and propylene, vinyl chloride, vinylideno chloride, polyoxyethylene monomethacrylate and the like.

It is preferable to select the monomers so that the backbone polymer of the silicone-based graft copolymer produced from these monomers has the same or compatibility with the paint molecules. For example, if methyl methacrylate is selected as a monomer, a silicone-based graft copolymer having polymethyl methacrylate as the backbone polymer can be obtained, and a wrinkle graft copolymer can be obtained from a polymethyl methacrylate-based organic solvent IIIk family (coating). Membrane surface modification (polyvinyl chloride, which is not only effective but also compatible with polymethyl methacrylate).

It is also effective in modifying the surface of coating films obtained with polyethylenetere 7 tallate-based paints, epoxy resin-based organic solvent-based paints, etc. The monomers can be used alone or in combination of two or more types.

The copolymerization ratio of the acrylic-modified silicone and the radically polymerizable monomer is such that the silicone content (as 8i0°) in the resulting silicone-based graft copolymer is 5 to 80% by weight, preferably 10 to 70% by weight. It is preferable to decide so that Coated footwear made of a silicone-based graft copolymer with a silicone content of less than 5% by weight and an organic solvent Ill paint has a surface modification effect (11
(water/oil repellency, stain resistance, low friction) cannot be fully demonstrated, and if the weight exceeds 80%, the surface modification effect of the coating film cannot be improved, and the amount of expensive acrylic modified silicone used increases. Economically, it will lead to four uncertainties.

Conventionally known methods can be used for the radical copolymerization of the acrylic-modified silicone and the radically polymerizable monomer, such as the direct irradiation method and the method using a radical polymerization initiator. The method to be used is preferable in terms of nuisance of polymerization operation and molecular weight control of the silicone graft copolymer produced, and specifically, any method such as solution polymerization method using a solvent, bulk polymerization method, emulsion polymerization method, etc. 4. You will be able to hire people.

As the radical polymerization initiator that can be used in the production of the graft copolymer, commonly used radical polymerization initiators can be used, and an appropriate one can be selected depending on the polymerization method. Examples of inorganic radical polymerization initiators include persulfuric acid anomones, and organic radical polymerization initiators such as per-Φ siketal, hydroperoxide, sial-Φ ruber oxide, diacyl peroxide, peroxydicasenate, Any azo compound represented by peroxy ester or azobisisobutyronitrile can be used, but K to obtain a silicone-based graft copolymer with a relatively clear structure is an organic filtrate with a low fractionation temperature. Among the fluorides, an azo compound is preferable, and in 41, an azo compound is preferable. The azo compound is an azo compound in which both ON atoms of the azo bond are bonded to the 3rd carbon atom, and the remaining valency of the 5th carbon atom is preferably satisfied by a C1-taloalkylene or alkyl group. The most preferred compound is azobisisobutyronitrile (hereinafter abbreviated as AIBN).

When copolymerizing with ultraviolet irradiation (KXI), a known sensitizer is used as a radical polymerization initiator, and when copolymerizing with electron beam irradiation, it is not necessary to use a radical polymerization initiator M. The amount of the radical polymerization initiator is generally preferably 101 to 5 weight, more preferably α1 to 2 weight, based on the total amount of raw material components.

The silicone-based graft copolymer thus obtained is a graft copolymer in which the polymer obtained from the radically polymerizable monomer is the trunk and silicone is the branch, and the ToD, the number of branch points is used. It can be determined by the molecular weight of the acrylic-modified silicone, the molecular weight of the radically heavy monomer, the molecular weight of the silicone-based graft copolymer, and the silicone content in the silicone-based graft copolymer.

Examples of organic agent titins that can be used in the present invention include nitrocellulose lacquer, acrylic lacquer, vinyl resin paint (typified by *a, which forms a continuous coating film simply by volatilization of an organic solvent), oil-based paint, and alkali paint* *
After painting, side coating paints such as amino alkyd resin paints, unsaturated polyester paints, epoxy resin paints, and polyurethane coatings IIRI, etc., which form a continuous coating film through a side reaction due to oxygen in the atmosphere, catalysts, heating, etc. Organic solvent Kfj for polymers! These are paints, etc. that have been explained in detail.

The amount of the silicone graft polymer used in the present invention added to the organic solvent composition is determined by the non-volatile content (I) of the organic solvent-based paint.
jl form)! It is preferably 101 to 10% by weight, more preferably α05 to 5% by weight, relative to IC.

The method of adding the silicone-based graft copolymer used in the present invention to an organic solvent-based paint [11] or the method of adding the silicone-based graft copolymer used in the present invention to an organic solvent-based paint, or the method of adding the silicone-based graft copolymer used in the present invention to an organic solvent-based paint by dissolving the resulting solution in an appropriate solvent. Any method of adding may be used.

As described above, the coating composition of the present invention does not impair the original performance of the resulting coating film, and has excellent coating surface properties such as water-based water, rattan oil, etc.
It can provide stain resistance and low friction properties.

Next, examples and comparative examples will be given to further explain the present invention.

Example 1 and comparative example 1 α,·-DihydroxydimeOH as silicone.

Chilborisiloxane (HO(8i0)a HOm is flat CH
.

60], its 220F (0.1 mol) and 9.491 (α12 mol) of pyridine were mixed with ethyl ether 40
Add r-methacrylokidipropylmethyldichlorosilane + 2.06 # (l1054 l) to the solution dissolved in IK.
A diethyl ether solution of 10 g (weight -1 or less simply referred to as -) was gradually added dropwise at room temperature over 20 minutes.

The reaction proceeded at rt and white crystals of visazine hydrochloride were precipitated. After the dropwise addition is complete, stir for another 1 hour at room temperature to remove the crystalline f''aK of pyridinohydrochloride.Next, pour this liquid into a separating funnel, add 500 val of water, and shake well. After washing with water, the separatory funnel was left standing to separate the upper ether layer and the lower aqueous layer, and anhydrous sodium chloride was added to the obtained ether layer, which was then left at room temperature overnight to dehydrate.

Thereafter, filtration was performed to remove the sulfur sulfur, and the resulting P solution was distilled under reduced pressure to remove the ether, yielding 225 g of colorless and transparent acrylic-modified silicone.

Next, the obtained acrylic modified silicone and methyl methacrylate were copolymerized. Copolymerization: 1 50 parts of the acrylic modified silicone (parts by weight, hereinafter simply referred to as parts), 50 parts of methyl methacrylate, AIBNtOII,) 60 parts of luene
The mixture was placed in a flask equipped with a condenser and a stirrer, and reacted in a nitrogen atmosphere at a temperature of 80° C. for 24 hours.

After the reaction, toluene and unreacted methyl methacrylate were removed by vacuum distillation to obtain an isomeric reaction product. Next, unreacted acrylic-modified silicone was extracted from the reaction product with n-hexano, and when the mixture was subjected to vacuum imaging, 81 parts of a white powdery silicone-based graft copolymer was obtained. This silicone material is copolymer t! ) Lueno, xyleno, thinner [@ could be solved.

In addition, as a result of analysis, this silicone-based graft copolymer (
The amount of silicone contained (as 8i0.) is 40-T
o9, the number average molecular weight in terms of polystyrene was 90,000.

7'Zo, silicone analysis was performed by carefully evaluating approximately ♂21 silicone-based graft copolymer in a platinum crucible.

Add 5 ml of concentrated sulfuric acid and heat in an electric furnace at 700°C for 2 hours until the silicone is 8 i 0. I asked for it as.

Also, the molecular weight is a value determined by liquid chromatography. The 10-
Prepare a toluene solution9, apply the solution to acrylic paint (20-thinner solution of methyl methacrylate-doethyl acrylate copolymer), (Additionally, an acrylic clear m group containing a silicone-based graft copolymer was prepared.

Next, this acrylic clear paint containing the silicone graft copolymer was applied onto a glass plate using a percoater. If you air-dry it in a fume hood for a day, you will get a transparent coating film with a thickness of 50 degrees.

The surface of the coating film was smooth and free of pinholes.

The results of the contact angle with water on the surface of the paint film, the stain resistance of the paint film surface, the adhesion between the paint film and the glass plate base, and the static friction angle of the paint film surface are shown in Table 1 as Example 1. In addition, the surface properties of a coating film obtained from a wrinkled acrylic clear paint containing no silicone-based graft copolymer are also shown in Comparative Example 1 in j!-1.

(1) Air surface contact angle Air KI of coating film! L, Contact angle of water on the surface of the paint film (measured at 20°C with a goniometer set of pseudo-antenna column measuring device) I) Stain resistance Drop ~12ml of 5% water slurry of activated carbon onto the surface of the coating that is in contact with air. How the activated carbon comes together when it is washed with water after being air-dried.

O: No activated carbon remains ×: Adhesion (residual rate of goblin test) 2 with a knife
A cut was made in the shape of a goblin at the corner, and the goblin was removed with cellophane tape for evaluation.

(4) Teima IIs Negative A wear angle measuring machine manufactured by Toyo Seiki Tensakusho was used. A sample formed on a glass plate was attached to this angle meter, and an AIK soft polyvinyl chloride sheet was attached to the surface of the coating film to create a cube weighing 100 I (vertical x horizontal x height = 25 x 25 x 20 cabinets). The sample was tilted at a tilting speed of 27 γ seconds to set the angle at which the cube started sliding on the painted surface.

As shown in Table 1, the coating composition to which the silicone-based graft copolymer of the present invention was added was found to have a significantly modified coating film surface, and was surprisingly endowed with water richness, stain resistance, and low friction properties. It was also found that the adhesion was improved.

Example 2 and Comparative Example 2 One of the nine silicone-based graft copolymers obtained in Example 1
0s tolueno solution thermosetting acrylic clear paint (
Methyl memethacrylate/hydroxyethyl acrylate/styrene//acrylic IN/butyl acrylate copolymer and Melaricono-based graft copolymer are added to the paint polymer so that they are α5-, and silicone-based graft copolymer is included. A thermosetting acrylic clear paint was prepared, and the silicone-based graft copolymer-containing thermosetting acrylic clear paint was then applied onto a glass plate using a bar coater. Air dry for 1 day in a fume hood at 200℃
After baking for a minute, a transparent coating film with a thickness of 30μ can be obtained.
It was. The coating film *m was smooth and free of pinholes.

The results of the contact angle of the coating film surface with water, the stain resistance of the coating film surface, the adhesion between the coating film and the glass plate base, and the static friction angle of the surface are shown in 9-2 as Example 2. Table 2 also shows the surface properties of the coating film obtained from the thermosetting acrylic clear paint that does not contain the silicone graft copolymer.
This is shown as Comparative Example 2. The physical properties measurements shown in @-2 were carried out using the second son's method as shown in Example 1.

As shown in Table 2 @-2, the coating composition to which the silicone-based graft copolymer of the present invention was added had a significantly modified coating film surface and was endowed with water richness, stain resistance, and low friction properties. It was found that there was no decrease in adhesion.

Example 3 Silicone-based graft copolymer 1 obtained in Example 1
The tolueno solution was mixed with a polymer containing polymethyl methacrylate as the main component (3@V-Yon11II11,
A polymethyl methacrylate solution containing the silicone graft copolymer was prepared by adding the silicone graft copolymer to a 22-toluene solution of BR-60 (trade name) in such a manner that the silicone graft copolymer had α5 relative to the coating polymer.

Next (This silicone-based graft copolymer-containing polymethyl methacrylate solution was coated on a glass plate using a bar coater. When air-dried for one day in a fume hood, the thickness was 50%.
A transparent coating film of s was obtained. Paint film II! The image was smooth with no pinholes. The contact angle of the air-killed surface of the coating film to water was #195°. The coating film obtained from the polymethyl methacrylate solution containing no wrinkled silicone graft copolymer had a contact angle of 75° with water on both surfaces in contact with air.

Example 4 -1ω-dihydroxydimeCH as silicone 7.

Chylpolysiloxane (HO(8i0) fiHOa is
A bath solution of Kr-methacryloxyglovylmethyldichlorosilane 11108I (1075 mol) O10 was obtained by dissolving 02201 (α 1 mol) and pyridine 1424I (a 18 mol) in diethyl ether 440 JK@
The Is diethyl ether bath solution was gradually added dropwise over 20 minutes at room temperature.

Thereafter, the same operation as in Example 1 was performed to obtain 205 #ik% of acrylic modified silicone.

Next, the obtained acrylic-modified silicone and methyl methacrylate were copolymerized to form a comfy. Copolymerized armpit acrylic modified silicone 50 parts, methyl methacrylate 50 parts, AIBNtO
and 300 parts of toluene were placed in a flask equipped with a condenser and a stirrer, and reacted in a nitrogen atmosphere at a temperature of 80° C. for 24 hours. Thereafter, the same operations as in Example 1 were carried out to obtain 90 parts of a white powdery silicone-based graft copolymer.

This silicone-based graft copolymer was soluble in toluene, oxygen/thinner.

Furthermore, as a result of the analysis, a 10-toluene solution of this silicone-based graft copolymer was prepared.
In the acrylic clear paint using the wrinkle solution in Example 1, the Mukuro silicone-based graft copolymer has α
5- to prepare an acrylic clear paint containing a silicone graft copolymer.

Next (this acrylic clear paint containing silicone graft copolymer was coated on a glass plate (using a bar coater). After being air-dried for one day in a fume hood, a clear coat with a thickness of 55 μm was obtained.
A coating film was obtained.

Paint film lI! The image was smooth with no pinholes.

The air in the coating film is KII! The contact angle of the surface with water is 93'. In addition, the contact angle of the coating film obtained from the Vh acrylic resin film containing no silicone-based graft copolymer to water in contact with air was 74°.Example 5 Silicone as α,ω-dihydroxydimeCH.

Chill Polyshiro+? ”(HO(8i0)nHOfl is 'F
Using Sori 611 (α1 mole) and Pyridine 9
．． 491 (a 12 mol) ethyl ether 150
A toLs diethyl ether solution of 1gIIK@dissolved solution Kr-methacryloxypropylmethyldichlorosilano 12-061 (α05 mol) was gradually added dropwise at room temperature over 20 minutes.

Thereafter, the same operations as in Example 1 were performed to obtain acrylic modified silicone 67I.

Next, the obtained acrylic modified silicone and methyl methacrylate were copolymerized. Copolymerization was carried out using 50 parts of the acrylic modified silicone, 50 parts of methyl methacrylate, and AIBNtO.
and 300 parts of toluene were placed in a flask equipped with a CO/DEF f-1 stirrer and allowed to react in a nitrogen atmosphere at a temperature of 80°C for 24 hours.Then, the same operation as in Example 1 was carried out to form a white powdery silicone-based raft. This silicone-based graft copolymer containing 117 parts of copolymer was able to be dissolved into toluene, medium silene, and thinner.As a result of analysis, the amount of silicone contained in this silicone-based graft copolymer was found to be is 661! A 10-toluene solution of the silicone-based graft copolymer thus obtained was prepared, and the 9-plating bath was applied to the acrylic clear paint used in Example 1. The silicone-based graft copolymer was applied to the paint polymer. An acrylic clear Ik family containing a silicone graft copolymer was prepared by adding it to a concentration of 15%.

Next, this silicone-based graft copolymer-containing acrylic clear paint was applied onto a glass plate using a bar coater. After air drying in a fume hood for one day, a transparent coating film with a thickness of 50 μm was obtained.

Coating surface: 1liIri: Smooth with no pinholes etc.

The contact angle of the surface of the coating film exposed to air KWn to water was 92°.

Example 6 a,ω-dihydrox 7970M as silicone.

Using chloropolysiloxane (HO (8i 0 ), HOn average 300), its 22 (1 (α01 mol)) and pyridine α949I (0012 mol) were added to diethyl ether with 5
00 Tsuru
The 0-diethyl ether solution was gradually added dropwise over 20 minutes at room temperature.

Thereafter, the same operations as in Example 1 were performed to obtain acrylic modified silicone 2111.

Next, 50 parts of the obtained acrylic modified silicone and 50 parts of methyl methacrylate were copolymerized in the same manner as in Example 5 to obtain 80 parts of a white oily silicone graft copolymer.

This silicone-based graft copolymer has #11 resolution ability in toluene, xylene, and thinner.

Further, as a result of the analysis, a 10-toluene solution of the silicone graft copolymer thus obtained was prepared, and the solution was used in Example 1 to create a hazardous acrylic clear paint (scissors silicone graft copolymer). is IIi
An acrylic clear paint containing a silicone-based graft copolymer was prepared by adding α5- to the raw material polymer.

Next, this silicone-based graft copolymer-containing acrylic clear material was coated onto a glass plate using a bar coater. After air drying in a fume hood for one day, a transparent coating film with a thickness of 53 μm was obtained.

The membrane surface l1ii was smooth with no pinholes.

The contact angle of the air-containing surface of the coating film to water was 88°.

Example 7 and Comparative Example 3 1IIIA An acrylic clear paint containing the same silicone graft copolymer as in Example 1 was prepared according to the same method as in Example 1.

Next, an acrylic clear paint containing a conosilicone graft copolymer was applied onto the DEFRON sheet using a bar coater. When air-dried for one day in a draft, the thickness becomes 50 seconds.
A transparent coating film was obtained. The surface of the coating was smooth with no pinholes or the like. The contact angle of the air-killed surface of the paint film to water, the Teflon seam of the paint film) The contact angle of the air-killed surface of the paint film to water (the Ik film is peeled off from the Teflon sheet, and the contact angle of the paint film in contact with the Teflon sheet) The results of the contact angle with respect to water on the surface are shown in Table 3 as Example 7. In addition, the teflon seal of the coating film obtained by applying the acrylic clear paint that does not contain the silicone graft copolymer to the Defugino sheet using the same method is also known. ) The results of the contact angle with respect to water on the surface K* are also shown in Table 3 as Comparative Example 3.

-5 (1) Air surface contact angle The surface of the coating film that is in contact with the air,
Contact angle of the film from the Teflon sheet to water (Teflonosis) 11 Contact angle of the surface of the peeled coating that was in contact with the Teflon sheet to water As shown in Table 3, the coating base is like a Teflon sheet. It can be seen that in an extremely hydrophobic environment, the surface of the coating film in contact with the substrate is also modified.

Comparative example 4 α,ω-DihydroxydimeCH as silicone.

Chiropolysiloxane (HO(SiO)fiHOn is flat C
H.

2201Cα1 mol) and pyridine 2α88I (α264 mol) were dissolved in diethyl ether 400
A solution of m1Kflr dissolved bath liquid ic, -methacryloxyglobylmethyldichlorosilane 26511 ([111 mol) OIs diethyl ether] was gradually added dropwise at room temperature over 20 minutes.

Thereafter, acrylic modified silico-721 was prepared in the same manner as in Example 1.
I got 51. Next, 150 parts of the acrylic modified silico and 50 s of methyl methacrylate.

Parts of AIBNtO and 300 parts of toluene were placed in a flask equipped with a co/denoser and a stirrer, and copolymerization was initiated at a temperature of 80°C in a nitrogen atmosphere. However, 30 minutes after the start of copolymerization, the entire solution began to increase in viscosity, and after 1 hour, it was completely gelled, and the entire 9 solution became pudding-like, making it impossible to continue stirring.

Name of patent applicant: Toagosei Kagaku Kogyo Co., Ltd. Kinsha Procedural Amendment September 12, 1980 Patent Office Chief Tomishima 1) Haruki Tono1, Indication of the case 1982 Patent No. 358572, Invention title Machine composition 3, Relationship with the case of the person making the amendment Patent applicant address: 1-14-4 Nishi-Shinbashi, Minato-ku, Tokyo, Column 5 of the detailed description of the invention in the specification subject to the amendment, Contents of the amendment ( 1) Delete "r (as 5in2)" from the 3rd to 4th lines of page 14 of the specification.

(2) r (as SiO) on page 20, line 7 of the specification.”
The statement "(as a, ω-dihydroxydimethylpolysiloxane)" is corrected.

Claims (1)

[Scope of Claims] t A silicone-based draft copolymer obtained by radical polymerization of an acrylic-modified silicone and a radically polymerizable monomer is used as a film-forming resin organic A coating composition in which the modified silicone is a condensation reaction product of a silicone represented by the general formula (A) and 125 to 1 mol of an acrylic compound represented by the general formula CB) per 1 mol thereof. 1 (A) HO (containing 8i0) 1 (RITh and R 1 carbon number 1 to 10 monovalent O aliphatic hydrocarbon bulk group, 7 enyl group or frame -
halogenated hydrocarbon group. fi is a positive number of 1 or more. ) ha xOx is a water bulk atom or a methyl group, and 84 is a methyl group, an ethyl group, or a phenyl group. X is a chlorine atom, an ethoxy group, or an ethoxy group. )