JP2001254045A - Nonaqueous coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel nonaqueous coating composition that furnishes a hydrophilic film surface, that is stain-resistant and that makes it possible for used painting tools and utensils to be washed with water. SOLUTION: This nonaqueous coating composition comprises, as a binder component, a copolymer of (A) a reactive surfactant having a polymerizable unsaturated group and (B) a (meth)acrylate ester, or a copolymer of (A), (B) and (C) another monomer that is copolymerizable with (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous paint composition having excellent stain resistance, and to a novel non-aqueous paint composition in which an instrument used for applying the non-aqueous paint composition can be washed with water. About.

[0002]

2. Description of the Related Art JP-A-7-331136 discloses a fluorine resin and JP-A-8-6002 discloses a silicone resin as a binder resin for a stain-resistant paint. And binder resins in this field, including silicone-modified resins. However, these resins are quite expensive and lack affinity with other materials, so the undercoat paint is also greatly restricted, and even when repainting, a paint made of such an expensive binder of the same type is used. A composition must be used.

[0003] On the other hand, it is known that if the surface of the paint is made hydrophilic, soot and oily smoke in the atmosphere hardly adhere, and even if it adheres, it is easily washed away by rainwater. JP-A-4-370
No. 176 discloses that a resin having a hydrophilic segment and a hydrophobic segment is blended. But,
When resins having different polarities are blended, there is a disadvantage that storage stability is deteriorated. As disclosed in Japanese Patent Application Laid-Open No. 9-24577, it has been known for some time that generally, when the surface hardness of a coating film is increased, the coating film is hardly stained. However, there is a disadvantage that the coating film becomes brittle.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel non-aqueous coating composition in which the surface of a coating film formed is hydrophilic and stain-resistant. A second object of the present invention is to provide a non-aqueous paint composition which allows used paint tools to be cleaned by washing with water.

[0005]

Means for Solving the Problems The first aspect of the present invention is that (A)
A reactive surfactant having a polymerizable unsaturated group and (B)
The present invention relates to a non-aqueous coating composition comprising a copolymer of (meth) acrylate and a binder component.

A second aspect of the present invention is that (A) a reactive surfactant having a polymerizable unsaturated group and (B) (meth) acrylate and (C) another monomer copolymerizable therewith, And a non-aqueous coating composition comprising a copolymer of the above as a binder component.

As the reactive surfactant having a polymerizable unsaturated group, an anionic surfactant, a cationic surfactant, a non-ionic surfactant and a non-ionic surfactant may be used as long as they have at least one polymerizable unsaturated group in a molecule. It may be an ionic surfactant or an amphoteric surfactant, and it is preferable to select and use one that is well matched to the system. An example of a reactive surfactant having a polymerizable unsaturated group is disclosed in JP-A-1-2421.
No. 32 (Japanese Patent No. 2597137),
No. 3082, JP-A-4-256429 (JP-B-6-65375), JP-A-7-185289, JP-A-7-284644, JP-A-8-33
No. 9083, JP-A-8-339085, JP-A-11-116892, JP-A-11-14010
No. 9 and the like can be mentioned. More specific examples of the reactive surfactant having a polymerizable unsaturated group include allyloxypolyethylene glycol monomethacrylate [Nippon Oil & Fat Co., Ltd. brand name: Blenmer PKE series], nonylphenoxy polyethylene glycol monomethacrylate [Nippon Oil & Fat Co., Ltd. ) Product name: Blemmer PN
E series], Nonylphenoxy polypropylene glycol monomethacrylate [Nippon Yushi Co., Ltd. brand name: Blenmer PNP series], Nonylphenoxy poly (ethylene glycol-propylene glycol) monomethacrylate [Nippon Yushi Co., Ltd. brand name: Blenmer PNEP-]
600], sulfosuccinate-type reactive activator latemul S-
180 [manufactured by Kao Corporation], ammonium sulfosuccinate-type reactive activator Latemul S-180A [manufactured by Kao Corporation],
Nonionic reactive surfactant Aqualon RN-10, RN
-20, RN-30 [manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], anion-reactive surfactant Aqualon HS-05, HS-10
[Daiichi Kogyo Seiyaku Co., Ltd.], bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate
[Japan Emulsifier Co., Ltd .: Antox MS-60],
Methacryloyloxyethyl sulfonate [Nippon Emulsifier Co., Ltd. product name: Antox MS-2N] and the like.

The use amount of the reactive surfactant (A) having a polymerizable unsaturated group is 1 to 30% by weight, preferably 5 to 15% by weight based on all resin components.

The copolymerization of these reactive surfactants having a polymerizable unsaturated group with other polymerizable monomers is described, for example, in the aforementioned Japanese Patent Publication No. 6-65375. Although the component (A) has a polymerizable unsaturated group, it is a surfactant, so the polymerization system is carried out in an aqueous system in any technology, and the product is only in the form of an emulsion. There is no non-aqueous one. For example, in Reference Example 1 of JP-B-6-65375, reactive surfactant 40 having a polymerizable unsaturated group is used.
Polymerization was carried out using a monomer emulsion consisting of 9 g, 200 g of methyl methacrylate, 100 g of butyl methacrylate, 100 g of styrene, 8 g of azobisisobutyronitrile, and 820 g of deionized water to obtain a polymer emulsion without using other emulsifiers. It is a technique in which the point of the present invention exists in utilizing the performance of a reactive surfactant as an emulsion forming agent, and the purpose of the present invention is to
The effect is different.

The (meth) acrylate (B) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl methacrylate, hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) Acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, cyclohexyl (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, bisphenol A Ethylenoxide adduct di (meth) acrylate, propylene oxide adduct di (meth) acrylate of bisphenol A, trimethylolpropane tri (meth) acrylate, Tylene oxide-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Can be. One or more of these can be used.

The monomer (C) copolymerizable with the (meth) acrylic ester includes (meth) acrylic acid, acryloylmorpholine, N-vinylformamide, N-vinylpyrrolidone, dodecyl vinyl ether, hydroxybutyl vinyl ether, Styrene, vinyl toluene, α
There are methylstyrene, vinyl acetate, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, etc.
These may be used alone or in combination of two or more, if necessary, and the amount used is 0 to 70% by weight, preferably 10 to 50% by weight based on the total amount of the components (B) and (C). %.

In order to obtain the binder component of the present invention,
(A) a reactive surfactant having a polymerizable unsaturated group and (B) a (meth) acrylate or (B) a (meth) acrylate and (C) another monomer copolymerizable therewith. It can be obtained by polymerizing in an organic solvent in the presence of a polymerization initiator. The non-aqueous coating composition of the present invention can be prepared by blending the necessary dyes and pigments and other additives.

The polymerization initiator is not particularly limited. Examples thereof include benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, and the like.
There are t-butyl perbenzoate, azobisisobutylnitrile and the like.

The organic solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. Ethyl ether, ethylene glycol mono-n-propyl ether, etc. glycol derivatives; benzene, toluene, xylene, kerosene, naphtha, etc. hydrocarbons; methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc. esters; Acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and acetylacetone; ethers such as butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, tetrahydrofuran; These organic solvents can be used alone or in combination of two or more.

The dye / pigment used in the non-aqueous coating composition of the present invention is not particularly limited as long as it is used in a general non-aqueous system. Examples thereof include extenders such as talc, silica, mica, kaolin, clay, alumina, aluminum hydroxide, calcium carbonate, barium sulfate, and zinc stearate; titanium oxide, zinc oxide, basic lead carbonate, basic sulfate, Carbon black, pine salt, graphite, iron black, graphite, synthetic iron oxide yellow, transparent red iron oxide, titanium yellow, zinc yellow, strontium chromate, red iron oxide, lead red, molybdate orange, cuprous oxide, basic lead chromate, lead Inorganic coloring pigments such as cyanamide, chromium oxide, chrome green, dark blue, ultramarine, cobalt blue, etc .; madder lake, rockwood lake, cochineal lake, naphthol green B,
Naphthol Green Y, Naphthol Yellow S, Lithol First Yellow 2G, Permanent Red 4R, Brilliant Fast Scarlet, Hanser Yellow, Benzidine Yellow, Lisor Red, Lake Red C, Lake Red D, Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, Bordeaux 10B, phthalocyanine blue, phthalocyanine green, sky blue, rhodamine lake, malakato green lake, methyl violet lake, peacock blue lake, eosin lake, quinoline nilow lake, indanthrene blue, thioindigo maroon, alizani lake, quinacridone red, quinacridone bio Red, perylene red, perylene car red, isoindolinone yellow, Oxane violet, aniline black, organic fluorescent pigments such as organic coloring pigments; and the like.

The non-aqueous dye composition of the present invention contains a plasticizer, a stabilizer (storage), a dispersant, an antifoaming agent, a leveling agent, a wetting agent, a turbulence, which can be generally used in a non-aqueous coating composition. Agents, flame retardants, coupling agents, and the like.

[0017]

EXAMPLES The present invention will be described below with reference to production examples and examples, but the present invention is not limited thereto. Hereinafter, all “parts” indicate parts by weight.

Preparation Example of Resin 1 A flask equipped with a nitrogen inlet tube, a reflux condenser, a thermometer, a dropping funnel, and a stirrer was charged with 800 parts of toluene and 200 parts of butyl acetate. 300 parts of methacrylate, 150 parts of styrene, n-
450 parts of butyl methacrylate, Aqualon RN-20
[Reactive surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] A mixture of 100 parts of benzoyl peroxide and 12 parts of benzoyl peroxide was added dropwise over 4 hours, and the mixture was kept at the same temperature for 6 hours. The obtained copolymer resin had a resin content of 50% and a viscosity of 2,300 mPa · s.

Production Example of Resin 2 Instead of Aqualon RN-20 used in Production Example of Resin 1,
The procedure was the same as in Resin 1 Production Example, except that Latemul S-180A [reactive activator manufactured by Kao Corporation] was used.

Production Example of Resin 3 Production Example of Resin 1 except that Antox MS-60 [reactive activator manufactured by Nippon Emulsifier Co., Ltd.] was used instead of Aqualon RN-20 used in Production Example of Resin 1. The same was done.

Comparative Production Example of Resin 4 Aqualon RN-20 used in Resin 1 Production Example was omitted,
Resin 1 except that 550 parts of n-butyl methacrylate were used.
Performed in the same manner as in the production example.

EXAMPLE 100 parts of copolymer resin "1 to 4" were mixed with 40 parts of titanium oxide, 20 parts of thinner (xylene), and glass beads (diameter: 1 m).
m) 80 parts were added and dispersed by a paint conditioner for 30 minutes, and the glass beads were filtered to obtain a paint. This paint was spray-coated on a slate plate which had been diluted with a thinner and treated with a primer. The dried coating film (white) after one day at room temperature was 50 μm. The painted slate was exposed outdoors to observe the degree of dirt. Table 1 shows the results.

[0023]

[Table 1]

Various devices used for applying the non-aqueous coating composition using the resins 1 to 3 as a binder include:
Although it could be easily washed off by washing with water, the equipment used for the resin 4 could not be cleaned without washing with an organic solvent.

[0025]

(1) According to the present invention, a novel non-aqueous coating composition excellent in stain resistance can be provided. (2) All the instruments used for applying the non-aqueous coating composition of the present invention can be cleaned by washing with water.

Claims (2)

[Claims] 1. A non-aqueous coating composition comprising, as a binder component, a copolymer of (A) a reactive surfactant having a polymerizable unsaturated group and (B) a (meth) acrylate. 2. A copolymer of (A) a reactive surfactant having a polymerizable unsaturated group and (B) a (meth) acrylate and (C) another monomer copolymerizable therewith. A non-aqueous coating composition comprising a binder component.