JPH0681811B2 - Emulsion type coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Purpose of the invention [Industrial field of application] The present invention is used as a pollution-free, resource-saving coating in place of an organic solvent-based coating, along with a powder coating and an ultraviolet-curable coating in the industrial field. It relates to a useful emulsion type coating composition.

[Conventional technology]

Emulsion type paints have been steadily increasing in consumption since they were put on the market after the war, and their share is gradually increasing. In particular, recently, as a pollution-free and resource-saving paint, it has become more and more important as well as powder paint and UV-curable paint. In the United States and West Germany, it already has a market share of more than 30%, and in Japan, the oil shock in 1973 has led to restrictions on the use of organic solvents from the perspective of resource problems and air pollution. It is thought that it will inevitably be converted to low-solvent type paints in the future.

When comparing emulsion type paints with solvent type paints,
Advantages are: 1) It is suitable for on-site painting because it is easily diluted with water, can be easily painted, and has good workability.

2) It can be applied to a slightly wet surface.

3) There is no fear of fire because it does not contain combustible materials.

4) Very low toxicity to the human body.

5) Low cost.

On the other hand, the disadvantages are: 1) The gloss is lower than that of the solvent type.

2) The coating film is soft and has problems in water resistance and stain resistance.

3) Blocking is likely to occur.

4) There is a problem in storage stability, especially freezing stability.

And so on.

Of these drawbacks, in particular, 2) is often a problem in practical use, and attempts for improvement have been actively made, but it is not easy to solve because it is an essential problem in emulsion type paints. .

In addition, various methods are currently being studied in order to impart water repellency, oil repellency, stain resistance and the like to the coating film surface of the paint.

For example, a method of surface-grafting a monomer by irradiation of radiation, light, or plasma onto the surface of a coating film, a method of coating a coating agent with a coupling agent such as an oligomer, a polymer, or silane, a polymer having a low surface energy such as a silicone resin or a fluororesin. Is added to the paint. Of these, the surface grafting method of the monomer by irradiation of radiation, light, or plasma on the surface of the coating film requires a special device, and the coating film with the improved surface becomes expensive. In the method of coating the coating film surface with a ring agent, the coating film surface is temporarily modified and the coating film surface modification effect is not durable, and the coated substance is easily removed, and a thin coating film is also used. There are many problems such as making it difficult. In addition, the method of adding a polymer having a low surface energy such as silicone resin or fluororesin to the coating material is not always satisfactory in the durability of the effect of modifying the coating film surface, and it is necessary to maintain a sufficient modifying effect of the coating film surface. Requires a large amount of addition, which may impair the original performance of the coating film. In particular, the adhesion between the coating film and the base surface becomes poor.

In addition to these methods, as a method of particular interest recently,
There is a method of modifying the surface of a coating material using a surface-migrating graft polymer (Japanese Patent Laid-Open Nos. 58-154766 and 58-164656).
issue). This method is a surface-migrating fluorine-based or silicone-based segment, and a graft polymer having an anchor segment in the same molecule that melts into the matrix resin of the coating in the same molecule, by adding a small amount to the organic solvent-based coating,
Properties such as water repellency and oil repellency and stain resistance can be easily imparted to the surface of the coating film.

[Problems to be solved by the invention]

In the conventional emulsion type paint, there is no effective means for surface modification of the coating film obtained from the emulsion type paint because of the complexity of the film forming process and the non-uniformity of the constituents.

The present invention provides an emulsion type coating composition capable of imparting properties such as water repellency, oil repellency, and stain resistance to a coating film surface, which has not been heretofore available.

(2) Structure of the Invention [Means for Solving Problems] The present inventors have used a graft copolymer having a molecular structure clearly regulated and having a surface migration property for surface modification of an aqueous emulsion type coating composition. As a result of earnest studies, the present invention has been achieved.

That is, the present invention provides (a) a film-forming polymer, (b) a fluorine-based and / or silicone-based graft polymer having a unit compatible with the film-forming polymer, and (c) a diethylene glycol monoalkyl ether acetate or Emulsion type coating composition which comprises 5 to 30% by weight of the component (c) based on the total amount of the component (a) and the component (b), with the film-forming aid composed of ethylene glycol monoalkyl ether as constituents. It is a thing.

[Work]

In the present invention, a unit derived from a fluorine atom-containing monomer and / or a unit derived from an organic compound having a SiO bond as a polymer additive, and a film-forming polymer ( A graft polymer having a special structure having a unit compatible with (hereinafter referred to as a coating polymer) in the same molecule is important for the effect of modifying the surface of the film obtained by the emulsion type coating composition and its sustaining effect. It plays an important role.

Further, the graft polymer has a unit which is the same as or compatible with the coating polymer (hereinafter referred to as an anchor component) as a branch or trunk polymer unit, a unit derived from a fluorine atom-containing monomer and / or a SiO bond. A unit derived from an organic compound having a is a trunk or branch polymer unit, and the composition of the present invention is a coating composition containing a small amount of this in an emulsion type coating. The coating obtained by the coating composition of the present invention does not impair the original performance of the coating, and is provided with excellent water and oil repellency on the coating surface. The system- and / or silicone-based graft copolymer does not easily separate from the coating surface, and the effect of modifying the coating surface is maintained.

[Fluorine-based and / or silicone-based graft polymer]

The fluorine-based and / or silicone-based graft polymer used in the present invention can be synthesized by a conventionally known chain transfer method, radiation grafting method, mechanical or organic chemical reaction method, polymer initiator method or prepolymer. Join method,
Further, any of the macromonomer methods, which have recently received attention, can be used.

To describe the synthesis of the fluorine-based graft polymer preferably used in the present invention, a synthetic method by the macromonomer method of a hydrophobic graft polymer containing fluorine in the molecular chain can be mentioned. For example, methyl methacrylate can be prepared in the presence of thioglycolic acid. Radical polymerized to a molecular weight of 1,000 to 10,000
A one-terminal carboxylic acid prepolymer of 0 is obtained, and this is reacted with glycidyl methacrylate to obtain a macromonomer having a methacrylic acid ester type end group.

The macromonomer to the copolymerization component as a fluoroacrylate _{(CF 3 CF 2) n-} CH 2 CH 2 OCOCH = CH 2, n =
If a mixture of 4 to 12) is used, a graft polymer in which the trunk is a unit derived from fluoroacrylate and the branch is a unit derived from polymethylmethacrylate is obtained.

Contrary to this, fluoroacrylate is radically polymerized in the presence of thioglycolic acid to obtain a carboxylic acid prepolymer having a molecular weight of 1,000 to 10,000 at one end, and the methacrylic acid ester type end group is similarly reacted by reacting with glycidyl methacrylate. If the macromonomer is present and is copolymerized with methyl methacrylate, a graft polymer having a unit whose backbone is derived from methyl methacrylate and a branch whose unit is derived from fluoroacrylate is obtained.

As the fluorine-containing monomer unit, in addition to the unit derived from fluoro (meth) acrylate, a unit derived from chloroethylene trifluoride, dichloroethylene trifluoride, tetrafluoroethylene, vinylidene fluoride or the like can be used. .

As a method for synthesizing a silicone-based graft polymer containing silicone in its molecular chain, some conventionally proposed methods can be used. For example, Japanese Patent Publication 32-68
As disclosed in JP-B No. 96, JP-B-47-16199 and JP-A-48-28389, an active group is formed by hydrogen abstraction from a lower alkyl group bonded to a silicon atom of silicone, and A method for obtaining a silicone-based graft polymer by grafting an organic polymer to the organic polymer, as described in JP-B-46-9355, reacting a silicone having an active group with a living polymer obtained by anionic polymerization to give a silicone-based graft polymer. How to obtain
As disclosed in Japanese Patent Publication No. 91, a polysiloxane polyester containing maleic acid in the main chain is synthesized, and maleic acid and an electron-donating monomer that easily forms a charge transfer complex are mixed and graft-polymerized to obtain a silicone-based graft. Method for obtaining polymer by radical copolymerization of silicone macromonomer obtained by condensation reaction from 0.25 to 1 mol of γ-methacryloxypropylmethyldichlorosilane per mol of α, ω-dihydroxydimethylpolysiloxane and radically polymerizable monomer Examples thereof include a method for obtaining a silicone-based graft polymer (hereinafter abbreviated as a method by radical copolymerization of a silicone macromonomer and a monomer). Among these methods, as a method for producing a silicone-based graft polymer that has excellent solubility in an organic solvent and is excellent in the effect of modifying a coating surface, among these production methods, a silicone macromonomer and a radical copolymerization of a monomer are used. The method is preferred. The content of fluorine or silicone in these hydrophobic graft polymers is preferably 10 to 80% by weight, preferably 20 to 70% by weight in the hydrophobic graft polymer.

When a hydrophobic graft polymer having a fluorine or silicone content of less than 10% by weight is used in the coating composition,
The effect of modifying the surface of the obtained coating film cannot be fully exerted, and when a hydrophobic graft polymer having a fluorine or silicone content of more than 80% by weight is used in the coating composition, the solubility in the coating polymer becomes poor. Furthermore, the obtained hydrophobic graft polymer becomes expensive. This is because most of the raw material cost of the hydrophobic graft polymer used in the present invention is occupied by the price of the raw material containing fluorine or silicone.

In the case of the above-mentioned graft polymer, a unit derived from polymethylmethacrylate is used as an anchor component, which has a unit derived from polymethylmethacrylate as a film-forming polymer as a main component or one component. Not only effective for modifying the coating surface obtained with emulsion type paints, but also effective for modifying the coating surface surface obtained with emulsion type paints that consist of coating polymers that have an affinity for polymethylmethacrylate. .

When it is applied to an actual emulsion type paint, the anchor component may be appropriately selected according to the coating polymer of the emulsion type paint. The types of anchor components that can be used include (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, styrene, styrene substitution products,
Examples thereof include vinyl esters of organic acids such as vinyl acetate, low molecular weight linear alkenes such as ethylene, vinyl chloride, vinylidene chloride, and polyoxyethylene monomethacrylate.

[Emulsion type coating composition]

The emulsion-type coating composition of the present invention comprises an emulsion-type coating composition (hereinafter referred to as an emulsion-type coating material) containing a coating-forming polymer as a constituent, the fluorine-based and / or silicone-based graft polymer, and a film to be described later. It is obtained by adding a specific amount of the auxiliary agent.

The above-mentioned emulsion type paint is an aqueous emulsion type paint, and as the solvent of the emulsion type paint, water alone or a mixed solvent of water and an aqueous organic solvent such as methanol or ethanol is used.

The addition amount of the fluorine-based and / or silicone-based graft polymer in the present invention to the emulsion type coating is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the nonvolatile content (solid content) of the emulsion type coating. It is extremely effective. In the coating composition in which the amount of the fluorine-based and / or silicone-based graft polymer added is less than 0.01% by weight, the effect of modifying the surface of the obtained coating film is not sufficiently exerted,
Further, the relationship between the increase in the amount of the fluorine-based and / or silicone-based graft polymer added and the surface-modifying effect (water / oil repellency) of the coating film obtained is such that the fluorine- and / or silicone-based graft polymer is several wt% or more. If so, the surface modification effect does not improve so much, and becomes a substantially constant value. or,
When a large amount of hydrophobic graft polymer is added, the original performance of the coating film is adversely affected and the cost is increased.

Therefore, the upper limit of the amount of the hydrophobic graft polymer added to the coating composition is 10% by weight with respect to the nonvolatile content of the emulsion type coating.

The method for adding the fluorine-based and / or silicone-based graft polymer to the emulsion-type coating material in the present invention is to dissolve the fluorine-based and / or silicone-based graft polymer in the monomer mixture during emulsion polymerization of the coating polymer, After that, a method of polymerizing a monomer to form a vehicle for coating (hereinafter abbreviated as a method of adding a graft polymer during polymerization), an organic solvent solution of a fluorine-based and / or silicone-based graft polymer is added to an emulsion-type coating, A method in which emulsion particles of a coating polymer are absorbed (hereinafter, abbreviated as a method of absorbing a graft polymer solution in an emulsion), an organic solvent solution of a fluorine-based and / or silicone-based graft polymer is emulsified in water, and then an emulsion-type coating material is obtained. Examples of the method of addition include polymerization A particularly preferred method of absorbing the graft polymer solution method and emulsion addition the graft polymer is.

When the method of absorbing the emulsion graft polymer solution is adopted, first, the fluorine-based and / or silicone-based graft polymer is dissolved in an appropriate solvent, this solution is added to the emulsion-type paint, and the mixture is stirred for several minutes to several tens of minutes. Then, the graft polymer is absorbed by the coating polymer together with the solvent. As the solvent that can be used, any solvent can be used as long as it dissolves the fluorine-based and / or silicone-based graft polymer and has a good affinity for the coating polymer, but one having a boiling point of 100 ° C. or higher is particularly preferable.

In the present invention, the two components of the coating polymer and the fluorine-based and / or silicone-based graft polymer added thereto are not separately dispersed in the emulsion, but the above-mentioned two components are contained in each emulsion particle. It is necessary to mix so as to coexist, and for that purpose, based on the total amount of the coating polymer and the graft polymer, 5 to 30% by weight of a film-forming aid comprising diethylene glycol monoalkyl ether acetate or ethylene glycol monoalkyl ether. % Is added in the emulsion type coating composition.

As described above, the film forming aid is not only for mixing the coating polymer and the graft polymer as described above, but also when the coating composition is formed from the coating composition, the coating polymer is plasticized so that the graft polymer forms a coating film. It also helps to get to the surface,
As is clear from the comparison between Comparative Example 1, Comparative Example 3 and Example 1 described below, according to the present invention, an excellent water-repellent film can be obtained by only drying at room temperature without heating and drying. Examples of preferable film forming aids include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and the like, and diethylene glycol monobutyl ether acetate (hereinafter referred to as butyl carbitol acetate) is particularly preferable. .

The amount of film forming aid used is 5 to 30% by weight based on the coating vehicle.
Is. When the film-forming auxiliary is less than 5% by weight, for example, as is clear from the comparison between Comparative Example 1 and Example 1 described later, the surface modification of the coating film with the fluorine-based and / or silicone-based graft polymer is insufficient, On the other hand, if the amount exceeds 30% by weight, the film forming aid remains in the film for a long period of time, and the film surface is easily contaminated.

In the present invention, the type of emulsion paint to be modified with the fluorine-based and / or silicone-based graft polymer is not particularly limited. For example, vinyl acetate emulsion paint, acrylic emulsion paint, urethane emulsion paint, styrene-butadiene emulsion paint, vinyl chloride emulsion paint, vinylidene chloride emulsion paint, etc. can be applied to all available emulsion paints.

The coating composition of the present invention is a coating in which a water- and oil-repellent fluorine-based and / or silicone-based polymer chain is concentrated on the surface by any method of room temperature drying or heat drying after coating on a substrate. To form.

The drying condition is preferably from room temperature to 200 ° C. for several minutes to several hours, and heat treatment at a temperature exceeding 200 ° C. or for several hours or more is not preferable because it may cause thermal deterioration of the coating.

[Reference Example, Example, Comparative Example]

Next, in order to specifically describe the present invention, reference examples, examples,
A comparative example will be given.

All% in each example represent% by weight, and parts represent parts by weight.

The water repellency of the coating film was evaluated by measuring the contact angle with distilled water, and the oil repellency was evaluated by measuring the contact angle with n-decane.

Reference Example 1 Synthesis of Methyl Methacrylate Macromonomer In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a gas inlet, 10 parts of methyl methacrylate (hereinafter abbreviated as MMA) and acetone (17.5 %)
-Prepare 100 parts of a toluene mixed solvent, introduce N ₂ , and under reflux, use azobisisobutyronitrile as a polymerization initiator (hereinafter
A mixed solution of 2 parts of AIBN (abbreviated as AIBN), 9.2 parts of thioglycolic acid as a chain transfer agent, and 90 parts of MMA was continuously added dropwise over 4.5 hours, and further refluxed for 2 hours to complete the polymerization.

Next, after part of the acetone was distilled off from the above reaction solution, triethylamine 0.5% as a catalyst, hydroquinone monomethyl ether 200 ppm as a polymerization inhibitor, and 17 parts of glycidyl methacrylate were added, and the mixture was reacted under reflux for 8 hours.
The reaction rate calculated from the decrease in acid value was 96%. The reaction solution
The mixture was poured into 10-fold amount of n-hexane, precipitated and dried under reduced pressure at 80 ° C. to obtain 90 parts of solid MMA macromonomer. The polystyrene reduced molecular weight was 1,050 (number average) and 1,700 (weight average) by gel permeation chromatography (hereinafter referred to as GPC).

Reference Example 2 Synthesis of Fluorine-based Graft Polymer In a glass flask equipped with a stirrer, a reflux condenser, a thermometer and a gas inlet, 56 parts of the MMA macromonomer produced in Reference Example 1 and a fluoroacrylate having the structural formula shown below. 24 parts, benzotrifluoride 215 parts, AIBN 0.6 parts, t
-Prepare 15.8 parts of dodecyl mercaptan and 100 with N ₂
Polymerization was carried out at ℃ for 6 hours.

Next, the solvent is distilled off from the reaction solution, and the obtained powder is n-
After extracting with hexane for 20 minutes, it was dried under reduced pressure to obtain 64.6 parts of MMA-fluoroacrylate graft polymer.

The molecular weight by GPC was 4,000 (number average) and 5,800 (weight average).

_{CF 3 CF 2 nCH 2 -CH 2} -OCO-CH = CH 2 n = mixture of 4-12 (mean about 7 n) Synthesis of 2-ethylhexyl acrylate emulsion paint vehicle containing Production Example 1 fluorine graft polymer After dissolving 1 part of the graft polymer produced in Reference Example 2 in a monomer mixture liquid consisting of 2.6 parts of acrylate, 25.4 parts of acrylonitrile and 2.0 parts of methacrylic acid, 30.2 parts of distilled water, anionic emulsifier Lebenol WZ
(Kao Atlas Co., Ltd. product 25% aqueous solution) 8.0 parts, nonionic emulsifier Emulgen 935 (Kao Atlas Co., Ltd. product 50)
% Aqueous solution) to prepare a pre-emulsion liquid.

A glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a gas inlet was charged with 36.6 parts of distilled water and then heated under N ₂ introduction to keep the liquid temperature at 65 ° C. The above pre-emulsion liquid was continuously added thereto over 5 hours, 0.38 parts of Perbutyl H (manufactured by NOF CORPORATION) as a polymerization initiator was dividedly charged over 7 hours (added every 1 hour),
20.4 parts of an aqueous solution containing 0.4 part of the reducing agent Rongalit was continuously added over 7 hours to complete the reaction to obtain an emulsion type coating vehicle (polymerization time: 7 hours).

Production Example 2 Synthesis of Vehicle for Acrylic Emulsion Coating without Graft Polymer An emulsion type vehicle for coating was obtained by the same method as in Production Example 1 except that the fluorine-based graft polymer was not dissolved in the pre-polymerization monomer mixture.

Reference Example 3 Synthesis of Silicone Macromonomer α, ω-dihydroxydimethylpolysiloxane Of silicone of 220 g (0.1 mol) and pyridine of 9.49 g (0.12 mol) in 400 ml of diethyl ether was added.
Methacryloxypropyl methyldichlorosilane 12.06g
(0.05 mol) of 10% diethyl ether solution was gradually added dropwise at room temperature over 20 minutes.

The reaction proceeded immediately and white crystals of pyridine hydrochloride precipitated. After completion of dropping, the mixture was further stirred at room temperature for 1 hour, and crystals of pyridine hydrochloride were removed by filtration. Next, this filtration was put into a separating funnel, 500 ml of water was further put therein, and the mixture was shaken well and washed with water. After washing with water, the separating funnel was allowed to stand, the upper ether layer and the lower aqueous layer were separated, anhydrous Glauber's salt was added to the obtained ether layer, and the mixture was left at room temperature overnight for dehydration.

Thereafter, anhydrous Glauber's salt was removed by filtration, and the obtained filtrate was distilled under reduced pressure to remove ether to obtain 225 g of a colorless and transparent silicone macromonomer.

Reference Example 4 Synthesis of Silicone-Based Graft Polymer The silicone macromonomer obtained in Reference Example 3 was copolymerized with MMA. For the copolymerization, 50 parts of the silicone macromonomer, 50 parts of MMA, 1.0 part of AIBN 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. After the reaction, toluene and unreacted MMA were removed by vacuum distillation to obtain a solid reaction product. Next, unreacted acrylic modified silicone was extracted from the reaction product with n-hexane and dried under reduced pressure to obtain 81 parts of a white powdery silicone-based graft polymer.

The silicone-based graft polymer was soluble in toluene, xylene, and thinner, and the result of analysis showed that the silicone content in the silicone-based graft polymer was 40% as dimethylpolysiloxane. Was 90,000.

For the silicone analysis, about 0.2 g of a silicone-based graft polymer was precisely weighed in a platinum crucible, about 3 ml of concentrated sulfuric acid was added, and the mixture was placed in an electric furnace and heated at 700 ° C. for 2 hours to obtain silicone as SiO ₂ . The molecular weight is a value measured by liquid chromatography.

Comparative Example 1 A vehicle for emulsion type coating containing the graft polymer obtained in Production Example 1 and a glass plate were coated with a bar coater and left at room temperature for 3 days to obtain a transparent coating film having a thickness of 30 μm. The contact of the coating film surface with water was measured with a goniometer.

The contact angle of water on the surface of the coating film was 100 °.

COMPARATIVE EXAMPLE 2 The emulsion polymer Bihilck containing no graft polymer obtained in Production Example 2 was coated on a glass plate using a bar coater and left at room temperature for 3 days to obtain a transparent coating film having a thickness of 30 μm. . The contact angle of water on the surface of the coating film was measured with a goniometer.

The contact angle of water on the surface of the coating film was 90 °.

Comparative Example 3 A vehicle for emulsion type coating containing the graft polymer obtained in Production Example 1 and a glass plate were coated with a bar coater and left at room temperature for 3 days to obtain a transparent coating film having a thickness of 30 μm. After heat treatment at 50 ° C. for 2 hours, the contact angle of water on the surface of the coating film was measured by a goniometer to be 106 °.

Example 1 5 parts of butyl carbitol acetate was added to 100 parts of the vehicle for emulsion type coating containing the graft polymer obtained in Production Example 1, and the mixture was stirred with a stirrer for 10 minutes to be absorbed by emulsion particles. Next, a glass plate was coated with a bar coater and left at room temperature for 3 days to obtain a transparent coating film having a thickness of 30 μm. The contact angle of water on the surface of the coating film measured with a goniometer was 106 °, which was the same as that of the coating film of Comparative Example 1 using the vehicle for coating material obtained in Production Example 1 as in this Example. Larger than a contact angle of 100 °. Further, when compared with the same Comparative Example 3, the contact angles are
Although it is the same at 106 °, in this example, the heat treatment of maintaining at 50 ° C used for Comparative Example 3 for 2 hours is not necessary.

Example 2 The procedure of Example 1 was repeated, except that the amount of butyl carbitol acetate added to the emulsion was 15 parts, and the coating film was vacuum dried at room temperature for 3 days. The contact angle of water on the surface of the coating film was 115 °.

Example 3 20 parts of a 2.5% butyl carbitol acetate solution of the fluorine-based graft polymer obtained in Reference Example 2 was added to 100 parts of the vehicle for emulsion-type coating material containing no graft polymer obtained in Production Example 2 and stirred for 10 minutes. The emulsion particles were absorbed by stirring. This product is coated on a glass plate with a bar coater and left for 1 week, the thickness is 50μ.
A transparent coating film was obtained. The contact angle of water with respect to the coating film was 115 °. The contact angle with n-decane was 71 °.

Example 4 The procedure of Example 3 was repeated except that the silicone-based graft polymer obtained in Reference Example 4 was used instead of the fluorine-based graft polymer.

The contact angle of water with respect to the coating film is 99 °, which is
The contact angle of the coating film of Comparative Example 2 using only the coating vehicle obtained in Production Example 2 was much larger than 90 °.

(3) Effect of the Invention The emulsion-type coating composition of the present invention forms a coating film having excellent water repellency, oil repellency, and stain resistance by applying it to a substrate and drying at room temperature or under heating.

It can be applied to substrates such as metals, ceramics, wood, polar plastics, and glass, but it can be applied to structures that are usually difficult to heat because it forms an excellent film even when dried at room temperature. Extremely useful.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-58-154766 (JP, A) JP-A-58-164656 (JP, A) JP-A-51-126220 (JP, A)

Claims (1)

[Claims] 1. (a) a film-forming polymer, (b) a fluorine-based and / or silicone-based graft polymer having a unit compatible with the film-forming polymer, and (c) a diethylene glycol monoalkyl ether acetate or Emulsion type coating composition which comprises 5 to 30% by weight of the component (c) based on the total amount of the component (a) and the component (b), with the film-forming aid composed of ethylene glycol monoalkyl ether as constituents. object.