JP2002146294A - Resin composition for stainproof coating, composite material having stainproof surface and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material having a stainproof surface which is hard for stains to adhere and easy to clean and remove the stains even if they adhere and, simultaneously, has strong adhesion to a base material and the long-term durability of its performance. SOLUTION: The composite material having a stainproof surface is obtained by coating a composition comprising (A) a fluorine-containing radically polymerizable unsaturated compound, (B) a radically polymerizable unsaturated compound having a functional group selected from carboxyl group, isocyanate group, epoxy group, and amino group, and optionally (C) a copolymer of other radically polymerizable compounds on the surface of the composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating resin composition used for coating components of household equipment such as bathroom products and water-related products, a composite material having an antifouling surface, and a method for producing the same. Things.

[0002]

2. Description of the Related Art Fiber-reinforced plastics such as SMC and BMC, and resin-based artificial marbles are often used for household equipment such as vanities, bathtubs and bathroom counters. It easily accumulates on the surface of the molded article, causing mold, dirt, bacteria and the like. Also, when the accumulated water evaporates, a trace called "water residue" remains, and once adhered, it becomes a stubborn dirt that cannot be easily removed, which has troubled many consumers.

As a means for solving such a problem, a method of coating a material such as a fluorine resin or a silicon resin is known. This lowers the surface free energy of the base material, improves water repellency and oil repellency, and reduces interaction with water stain components, thereby greatly improving antifouling properties.
Furthermore, the growth of bacteria and mold is also suppressed. However, although these coating methods have good antifouling properties at the initial stage after the coating process, the adhesion between the substrate and the coating material is weak, so that the coating material peels off during use or during manufacture, and the substrate is exposed. Therefore, there is a disadvantage that the antifouling property does not last long.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to prevent dirt from adhering easily, to easily remove the dirt even if it adheres, to have a strong adhesion to a substrate, and to improve its performance. Is to provide a resin composition for antifouling coating having long-term durability, a composite material having an antifouling surface, and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a resin composition for antifouling coating, a composite material having an antifouling surface, and a method for producing the same having the above-mentioned problems. A composition comprising a copolymer of a polymerizable unsaturated compound and a radical polymerizable unsaturated compound having another specific functional group has excellent antifouling properties as a coating material and excellent durability. And arrived at the present invention. That is, the present invention provides (1). (A) a radically polymerizable unsaturated compound having one or more fluorine atoms in the molecule: 1 to 99 mol%, and (B) one or more selected from a carboxyl group, an isocyanate group, an epoxy group, and an amino group in the molecule. A radical-polymerizable unsaturated compound having a functional group of 1 to 99 mol%, and (C) another radical-polymerizable unsaturated compound: 0 to 98 mol%. (2). (A) the antifouling coating resin composition according to (1), wherein the radically polymerizable unsaturated compound having at least one fluorine atom in the molecule is an ethylenically unsaturated compound having a fluoroalkyl group having 1 to 10 carbon atoms;
(3). (4) A composite material having an antifouling surface, wherein the antifouling resin composition according to (1) or (2) is coated on the surface of the composite material. The composite material
(3) a composite material having an antifouling surface, which is a resin-based composite material comprising a resin component and a fiber reinforcing material and / or a filler;
(5). (3) The composite material having an antifouling surface according to (3) or (4), wherein the composite material forms a part of a component of the housing equipment. The resin composition for antifouling coating according to (1) or (2) is diluted in a solvent and uniformly applied to the surface of the composite material.
(7) A method for producing a composite material having an antifouling surface according to any one of (3) to (5), wherein the method comprises heat treatment. The resin composition for antifouling coating described in (1) or (2) is applied to the surface of a mold for molding a composite material, and the composite material is molded using the mold. ) To (5) a method for producing a composite material having any of the antifouling surfaces, (8).
(3) The antifouling surface according to any one of (3) to (5), wherein a sheet having a surface layer comprising the antifouling coating resin composition according to (1) or (2) is bonded to the composite material surface. A method for producing a composite material comprising (9). (1) or (2)
A sheet having a surface layer made of the antifouling coating resin composition according to the above is disposed on the surface of the mold for forming a composite material such that the antifouling surface layer becomes the surface of the molded article, and using the mold A method for producing a composite material having an antifouling surface, wherein the sheet and the composite material are integrally formed.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As the monomer (A) used in the present invention, known radically polymerizable unsaturated compounds having one or more fluorine atoms in the molecule can be used, and ethylene having a fluoroalkyl group having 1 to 10 carbon atoms can be used. Those which are unsaturated compounds are preferred. Specifically, (perfluorobutyl) ethylene,
(Perfluorohexyl) ethylene, (perfluorooctyl) ethylene, (perfluorodecyl) ethylene,
2,2,2-trifluoroethyl acrylate, 2,
2,2-trifluoroethyl methacrylate, 2,
2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth)
Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl)
Ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2
-(Perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyloctyl) ethyl acrylate, 2- (perfluorooctylsulfonamido-N-butyl) ethyl acrylate,
Examples thereof include 2- (perfluorooctylsulfonamido-N-ethyl) ethyl acrylate, and these compounds may be used alone or in combination. As the α, β-unsaturated group of these monomers, any of a vinyl group, an acryloyl group, and a methacryloyl group can be used. However, an acryloyl group or a methacryloyl group is excellent in terms of polymerization reactivity. Is particularly preferable.

The monomer (B) used in the present invention is a radically polymerizable unsaturated compound having at least one functional group selected from a carboxyl group, an isocyanate group, an epoxy group and an amino group in the molecule. Known ones can be used. Specifically, those having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxypropyl acrylate maleate Acid adducts, dicyclopentadiene maleic acid adducts, etc.
Those having an isocyanate group include 2-methacryloyloxyethyl isocyanate, those having an epoxy group include glycidyl acrylate and glycidyl methacrylate, and those having an amino group include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and morpholinoethyl methacrylate. Is mentioned. There is no particular limitation as long as it is a radical polymerizable unsaturated compound having each functional group, and these compounds may be used alone or in combination.

As the monomer (C) used in the present invention, another radically polymerizable unsaturated compound, a functional group other than the monomer (A) or the monomer (B) may be used in the molecule. Any radically polymerizable unsaturated compound may be used, and there is no particular limitation. These compounds may be used alone or in combination. Specifically, styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, t-butylstyrene, vinyltoluene, vinyl acetate, (meth) acrylate, etc .; methyl (meth) acrylate, (meth) acrylate Ethyl, butyl (meth) acrylate,
Hexyl (meth) acrylate, decyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
Examples thereof include cyclohexyl (meth) acrylate, benzyl meth) acrylate, stearyl meth) acrylate, and tridecyl (meth) acrylate.

The antifouling coating resin composition of the present invention comprises a copolymer obtained by polymerizing the monomers (A) and (B) and, if necessary, the monomer (C). Things. The monomers (A) and (B) of the copolymer in the present invention,
The composition ratio of the monomer (C) is (A) :( B):
(C) = 1 to 99 mol%: 1 to 99 mol%: 0 to 98 mol%, but (A): (B): (C) = 1 to 40 mol%: 10 to 40 mol: 20 to Particularly preferred is about 89 mol%. The molecular weight (Mw) of the copolymer in the present invention is:
It is preferably from 5,000 to 50,000, especially 8,000
0 to 15,000 is particularly preferred.

As a method for producing the antifouling coating resin composition of the present invention, a known radical polymerization method is simple and industrially preferable. In this case, examples of the polymerization initiator include known organic peroxide catalysts and azo compounds classified as diacyl peroxide, peroxyester, and peroxydicarbonate. Specific examples include, for example, benzoyl peroxide, lauryl peroxide, stearyl peroxide, octanoyl peroxide, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy -2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3- Tetramethylbutylperoxyneodecanate, cumylperoxyneodecanate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, diisopropylperoxydicarbonate, azobisiso Chironitoriru, azo-bis-carboxylic amide can be used. Polymerization can be carried out by any of solution polymerization, emulsion polymerization, bulk polymerization, etc.
Solution polymerization and emulsion polymerization are preferred from the viewpoint of workability. Solvents for solution polymerization include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and 1,1,1- General-purpose solvents such as halogen solvents such as trichloroethane and chloroform; cyclic ethers such as dioxane and tetrahydrofuran; and aromatic solvents such as toluene and xylene. Emulsion polymerization is a known method in which an aqueous phase containing an emulsion stabilizer such as a surfactant and a water-soluble polymer compound is mixed with an oil phase composed of a radically polymerizable monomer, a polymerization initiator is added thereto, and the mixture is stirred at a predetermined temperature. Done in In addition, as a production method other than the radical polymerization method, a known cation polymerization method, anion polymerization method, or the like can be used.

[0011] The composite material having an antifouling surface of the present invention comprises:
The above antifouling coating resin composition is a base material (referred to as a composite material)
Is coated on the surface. The composite used in the present invention is preferably a resin-based composite comprising a resin component and a fiber reinforcing material and / or a filler. As the resin component, a radical-curable resin such as an unsaturated polyester resin, a vinyl ester resin, or an acrylic resin is used. Is used. Examples of the method for producing the composite material include a manual molding method, a cast molding method, and a press molding method. Also, a heat and pressure molding method using a sheet molding compound (SMC) or a bulk molding compound (BMC), a heat casting molding method using a resin compound containing an inorganic filler such as aluminum hydroxide, glass powder, and the like can be suitably used.
In addition, a composite material having an unsaturated polyester resin gel coat layer, an acrylic sheet layer, a urethane coating layer, or the like on the surface layer is also applicable.

The composite material having an antifouling surface according to the present invention comprises:
Bathtubs, wall panels, floor pans,
It is suitable for use in products around water such as washing places, counters and wash basins.

The method for producing a composite material having an antifouling surface according to the present invention comprises applying the antifouling coating resin composition used in the present invention to the surface of the composite material and subjecting the composition to a heat treatment. A method of bonding the functional group of the composition to the surface of the composite material may be used. Specifically, the antifouling coating resin composition used in the present invention is diluted to 1% to 30% solids with the solvent used in the polymerization or another solvent, and then applied to the surface of the composite material, and the solvent is evaporated. Heat treatment is performed later. The heat treatment temperature is preferably about 25 to 180 ° C., especially 40 to 100 ° C.
C is particularly preferred. By this treatment, the functional group of the antifouling coating composition is chemically bonded to the surface of the composite material, so that the antifouling property of the surface has long-term durability. The method for applying the resin composition for antifouling coating to the surface of the composite material may be a commonly used method such as a spray coating method, a brush coating, and a sponge coating, and is not particularly limited. Further, as a method of bonding the resin composition for antifouling coating and the composite material, curing at room temperature is also possible, but the above heat treatment is preferable from the viewpoint of bonding strength with the substrate and productivity.

Further, as another method for producing the composite material having the antifouling surface of the present invention, the antifouling coating resin composition of the present invention is applied to the surface of a molding die, and the die is used. In other words, there is a method in which the resin composition for antifouling coating is transferred to the surface of the composite material, and the functional group of the resin composition for antifouling coating is bonded to the surface of the composite material. For example, after applying the resin composition for antifouling coating to the surface of a mold for molding, evaporating the solvent and drying, the material forming the composite material is placed on the mold, and the mold is closed. By holding for a certain time, the resin composition for antifouling coating is transferred to the surface of the composite material, and a composite material having an antifouling surface can be manufactured. In this case, it is preferable to apply a mold release agent to the mold in advance before applying the antifouling coating resin composition. As the release agent to be used, various release agents generally used can be used, and examples thereof include fluorine-based, silicone-based, wax-based, and fatty acid-based release agents, and these can also be used in combination. In addition, when the film of the release agent can be cured by performing the baking treatment,
It may be used after being cured. Examples of a method of applying the resin composition for antifouling coating to the surface of a molding die include a spray coating method, a brush coating method, a sponge coating method, and the like. Raw materials for forming a composite material arranged in a molding die include SMC and BMC as heating and pressing molding materials, and materials for pressure casting include vinyl ester resins and acrylic resins.

The effect of previously treating the surface of the mold with a release agent is as follows. The surface free energy of the mold surface is reduced by performing the release agent treatment. Is applied, the fluoroalkyl group in the antifouling coating resin composition is efficiently oriented toward the mold.
In the production method of the present invention, the functional group of the resin composition for antifouling coating and the surface of the composite material are chemically bonded at the same time as the radical polymerization curing of the resin proceeds by the heating and pressurizing treatment in the mold. Therefore, it is possible to obtain a molded article having long-term durability, reducing the number of steps, and having excellent appearance.

Another method for producing the composite material having the antifouling surface of the present invention is a method of bonding a sheet having a surface layer made of the antifouling coating resin composition of the present invention to the surface of the composite material. Can be More specifically, the resin composition for antifouling coating used in the present invention is diluted to a solid content of 1% to 30% and then applied or impregnated on a sheet. Then, the resin composition layer for antifouling coating can be formed on a sheet by evaporating the solvent and then performing a heat treatment. Next, the sheet is bonded to the surface of the base material by thermocompression bonding or an adhesive to obtain a composite material having an antifouling surface.

The sheet to be coated or impregnated with the resin composition for antifouling coating is in the form of a film, fabric, or cloth. In addition to resin film sheets of polyester, polyethylene, polypropylene, acrylic, etc., glass mats, Glass cloth, non-woven fabric, paper base, or the like can be used. Also, a prepreg sheet with a pattern called a decorative sheet can be used. Examples of a method for applying the resin composition for antifouling coating to the surface of these sheets include a spray coating method, a dip coating method, a roll coating method, a brush coating, a sponge coating, and the like.

As another method for producing the composite material having the antifouling surface of the present invention, a sheet having a surface layer made of the antifouling coating resin composition of the present invention is applied to the surface of a composite material forming mold. Arranged so that the antifouling surface layer becomes the surface of the molded article,
There is a method of integrally molding a composite material thereon. In this case, the sheet having a surface layer comprising the antifouling coating resin composition of the present invention has a film-like, woven,
A cloth-like thing is used. Specifically, the antifouling coating resin composition of the present invention is diluted to a solid content of 1% to 30%, and then applied or impregnated on a sheet. Thereafter, after evaporating the solvent, heat treatment is performed as necessary, whereby a resin composition layer for antifouling coating can be formed on the sheet. Next, the sheet is disposed on the surface of a mold for molding a composite material such that the antifouling surface layer is the surface of the molded article. Next, the material forming the composite material is placed on the mold, and the mold is closed and held for a certain period of time, whereby the sheet and the composite material previously placed on the mold are cured and integrated, and the antifouling property is improved. A composite with a surface can be produced.

[0019]

EXAMPLES Next, the contents of the present invention will be described in detail with reference to synthesis examples, examples and comparative examples. However, the present invention is not limited to these examples. "Part" in each example,
“%” Indicates a weight basis.

Synthesis Example 1 (Synthesis of Polymer 1) Stirrer, dropping funnel, cooling condenser, gas inlet tube,
Using a glass flask equipped with a thermometer, 162.0 g of ethyl carbitol acetate was charged into the flask.
Next, 2- (perfluorobutyl) ethyl acrylate 6
3.6 g (20 mol%), 56.8 g (40 mol%) glycidyl methacrylate, 41.6 g (4
Permolester peroxide catalyst: perbutyl O (manufactured by NOF CORPORATION) as a polymerization initiator
86 g were mixed, uniformly dissolved, and charged into a dropping funnel.
The flask was set in an oil bath at 120 ° C., and stirring was started while flowing nitrogen gas. When the internal temperature of the flask reached 120 ° C., the monomer was dropped into the flask from the dropping funnel and ended in 1 hour. did. 120 ° C for an additional 2.5 hours
After maintaining the temperature at １２５125 ° C., 216.0 g of ethyl carbitol acetate was added thereto, and the mixture was cooled uniformly to obtain polymer 1. The average molecular weight (Mw) of this polymer 1 in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) was 12,500.

Synthesis Example 2 (Synthesis of Polymer 2) Using the same apparatus as in Synthesis Example 1, 196.1 g of ethyl acetate was charged into a flask. Next, 53.2 g of 3- (perfluorooctyl) ethyl methacrylate (10 mol
%) 2-methacryloyloxyethyl isocyanate 46.5 g (40 mol%), n-butyl methacrylate 56.8 g (40 mol%), 2-ethylhexyl methacrylate 39.6 g (20 mol%), diacyl par as a polymerization initiator Oxide-based peroxide catalyst: 3.92 g of Parloyl IB (manufactured by NOF Corporation) was mixed, uniformly dissolved, and charged into a dropping funnel. The flask was set in a 60 ° C. oil bath, stirring was started while flowing nitrogen gas, and after the internal temperature of the flask reached 60 ° C., the dropping of the monomer from the dropping funnel into the flask was started and completed in one hour. did. After maintaining the temperature at 60 ° C. to 63 ° C. for an additional hour, 261.5 g of ethyl acetate was added thereto, and the mixture was made uniform and cooled. Gel permeation chromatography (hereinafter abbreviated as GPC) of this polymer 2 GPC
The average molecular weight (Mw) in terms of polystyrene is 10,3.
00.

Synthesis Example 3 (Synthesis of Polymer 3) Using the same apparatus as in Synthesis Example 1, 131.0 g of ethyl carbitol acetate was charged into a flask. Then 2,
50.4 g of 2,2-trifluoroethyl methacrylate
(30 mol%), 25.6 g of glycidyl acrylate
(20 mol%), styrene 20.8 g (20 mol%)
%), 34.2 g (30 mol) of ethyl methacrylate
%) And 2.62 g of perbutyl O as a polymerization initiator were mixed, uniformly dissolved, and charged into a dropping funnel. The flask was set in an oil bath at 120 ° C., and stirring was started while flowing nitrogen gas. When the internal temperature of the flask reached 120 ° C., the monomer was dropped into the flask from the dropping funnel.
Finished in time. 120 ° C to 125 ° C for an additional 2.5 hours
, And 174.7 g of toluene was added thereto, and the mixture was made uniform and cooled, to obtain Polymer 3. The average molecular weight (Mw) of this polymer 3 in terms of polystyrene by GPC.
Was 8,500.

Synthesis Example 4 (Synthesis of Polymer 4) Using the same apparatus as in Synthesis Example 1, 141.4 g of isopropyl alcohol was charged into a flask. Next, 53.2 g of 2- (perfluorooctyl) ethyl methacrylate
(10 mol%), 25.8 g of methacrylic acid (30 mol
1%), 62.4 g (60 mol%) of styrene, and 2.82 g of azobisisobutyronitrile as a polymerization initiator were uniformly dissolved and charged into a dropping funnel. Set the flask in a 75 ° C oil bath and start stirring while flowing nitrogen gas. When the internal temperature in the flask reaches 75 ° C, start dropping monomers into the flask from the dropping funnel and finish in 1 hour did. After maintaining the temperature at 75 ° C. to 85 ° C. for an additional hour, 113.2 g of isopropyl alcohol was added thereto, and the mixture was cooled uniformly to obtain polymer 4. The average molecular weight (M
w) was 9,300.

Synthesis Example 5 (Synthesis of Polymer 5) Using the same apparatus as in Synthesis Example 1, 187.9 g of ethyl carbitoacetate was charged into a flask. Next, 61.9 g of 2- (perfluorodecyl) ethyl methacrylate
(10 mol%), 74.0 g (40 mol%) of diethylaminoethyl methacrylate, 52.0 g of styrene
(50 mol%), verbutyl O as a polymerization initiator
3.76 g were mixed, uniformly dissolved, and charged into a dropping funnel. The flask was set in an oil bath at 120 ° C., and stirring was started while flowing nitrogen gas. When the internal temperature of the flask reached 120 ° C., the monomer was dropped into the flask from the dropping funnel and ended in 1 hour. did. 1 hour at 120 ° C
After maintaining the temperature at ~ 123 ° C, 563.7 g of ethyl carbitol acetate was added thereto, and the mixture was cooled uniformly to obtain polymer 5. The average molecular weight (Mw) of this polymer 5 in terms of polystyrene by GPC was 10,300.

Comparative Synthesis Example 1 (Synthesis of Polymer 6) Using the same apparatus as in Synthesis Example 1, 159.6 g of isopropyl alcohol was charged into a flask. Next, 54.6 g (10 mol%) of (perfluorodecyl) ethylene, 62.4 g (60 mol%) of styrene, and methacrylic acid-n
42.6 g (30 mol%) of butyl and 3.19 g of azobisisobutyronitrile as a polymerization initiator were mixed, uniformly dissolved, and charged into a dropping funnel. Set the flask in a 75 ° C oil bath and start stirring while flowing nitrogen gas. When the internal temperature in the flask reaches 75 ° C, start dropping monomers into the flask from the dropping funnel and finish in 1 hour did. After maintaining the temperature at 75 ° C. to 80 ° C. for an additional hour, 212.8 g of isopropyl alcohol was added thereto, and the mixture was cooled uniformly to obtain polymer 6. G of this polymer 6
The average molecular weight (Mw) in terms of polystyrene by PC is 1
It was 1,000.

Comparative Synthesis Example 2 (Synthesis of Polymer 7) Using the same apparatus as in Synthesis Example 1, 120.7 g of ethyl carbitol acetate was charged into a flask. Next, 46.5 g (30 mol%) of glycidyl methacrylate, 60 g (60 mol%) of methyl methacrylate, 14.2 g (10 mol%) of isobutyl methacrylate, and 2.41 g of perbutyl O as a polymerization initiator are mixed, uniformly dissolved, and added to a dropping funnel. I charged. The flask was set in an oil bath at 120 ° C., and stirring was started while flowing nitrogen gas. When the internal temperature of the flask reached 120 ° C., the monomer was dropped into the flask from the dropping funnel and ended in 1 hour. did. After maintaining the temperature at 120 ° C. to 123 ° C. for 1.5 hours, 238.3 g of ethyl carbitol acetate was added thereto, and the mixture was cooled uniformly to obtain polymer 7. The average molecular weight (M
w) was 9,500.

Next, a composite material was coated with the above polymer (Examples 1 to 8 and Comparative Examples 1 and 2), and an evaluation test was performed by the following method. Table 1 and Table 2 show the results.
Shown in

Evaluation of Contact Angle 20 mm × 1 from the composite materials prepared in Examples and Comparative Examples
A test piece having a size of about 0 mm was cut out, and the contact angle of water and oleic acid was measured using a goniometer-type contact angle measuring device manufactured by Elma Optical Co., Ltd. to evaluate water repellency and oil repellency.

Stain test 200 mm × from composite materials prepared in Examples and Comparative Examples
A test piece having a size of 200 mm is cut out and left at an inclination of 5 ° with respect to a horizontal plane. The remaining hot water in the bath tub in which three adults bathed in the test piece was sprinkled with a shower at a flow rate of 0.8 L / min for 1 minute, and then dried at 30 ° C. for 1 hour. This operation is repeated 30 times. The stainability was evaluated by visually observing the degree of adhesion of water scale on the test piece. (Evaluation of water drainage property) Further, the test piece was scrubbed and washed with a sponge impregnated with tap water, and the extent to which the attached scale was removed was also evaluated. (Evaluation of Removability) The criteria for the evaluation of dirt removal were as follows. ◎: Very good fall ○: Good fall △: Slight stain remains ×: Stain remains even after strong wiping

Hot water immersion test The composite materials prepared in Examples and Comparative Examples were 200 mm ×
A test piece having a size of 200 mm is cut out and placed in a sealable glass container. After immersing 95 ° C warm water in this container to a height at which the entire test piece can be immersed, seal and place in a 95 ° C oven, evaluate the appearance one month after immersion, and perform a stain test (water drainage, removability). Evaluation).

Cross-cut peel test of antifouling coating film (layer) Cross-cut peel test of the composite materials prepared in Examples and Comparative Examples was performed, and the adhesion of the antifouling resin layer was evaluated according to the following criteria. ：: No peeling △: Slight peeling ×: Peeling all over

Antifouling coating film (layer) strength test The composite materials prepared in Examples and Comparative Examples were 200 mm ×
A test piece having a size of 200 mm was cut out and subjected to JIS-K5
400 (pencil scratch tester) A strength test of the antifouling resin layer was performed.

Antifouling coating film (layer) durability test 200 mm × composite material prepared in Examples and Comparative Examples
A test piece having a size of 200 mm is cut out and rotated at a speed of 60 rotations per minute for 10 minutes while applying a total load of 0.5 kg using a commercially available polyurethane sponge. The stain test (evaluation of drainage and removability) was performed using the test piece that had been subjected to this treatment.

Example 1 Isophthalic unsaturated polyester resin: Rigolac M
-531-3X (manufactured by Showa Polymer Co., Ltd.), 75 parts by weight, polystyrene-based low-shrinking agent: Rigolac M5582 (manufactured by Showa Polymer Co., Ltd.), 25 parts by weight, calcium carbonate as filler as additive: KS-1300 (Manufactured by Dowa Calfine) 150 parts by weight, zinc stearate: ZNS-P (Adeka Fine Chemical Co., Ltd.) as an internal release agent
6 parts by weight, magnesium oxide as thickener: 1 part by weight, Magmic (manufactured by Kyowa Chemical Industry Co., Ltd.), and a peroxyester-based peroxide catalyst as a curing agent: Perbutyl Z (manufactured by NOF Corporation) 1 After mixing the parts by weight and stirring thoroughly,
Roving glass fiber: R2400LBD166W (manufactured by Asahi Fiberglass Co., Ltd.) cut into 1 inch (25.4 mm) lengths is impregnated with an SMC impregnating device, wrapped in a polyethylene film and aged. did. 300mm length using this SMC
× flat plate of width 220 mm × thickness 3 mm is heated to upper mold temperature 140
° C, lower mold temperature 135 ° C, pressure 70 kg / cm ² (6.
It was cured by heating for 5 minutes under the conditions of 86MPs) to obtain an SMC molded product. After degreasing the surface of the molded body with acetone, a polymer prepared by adding ethyl carbitol acetate to polymer 1 to a solid content of 1% was spray-coated,
A heat treatment was performed at 0 ° C. for 3 hours to obtain a composite material having an antifouling surface.

Example 2 A silicon-based release agent: Shin-Etsu Sepacoat SEPA COATH (manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly spray-coated on the surface of the mold on which the SMC was molded in Example 1. Next, a solution prepared by adding ethyl carbitol acetate to polymer 1 to a solid content of 1% was spray-coated on the surface of the mold, and after the solvent was volatilized, the mold was used and the same method as in Example 1 was used. To form a composite material having an antifouling surface.

Example 3 Isophthalic unsaturated polyester resin: Rigolac M
553 parts by weight of a diacyl peroxide-based peroxide catalyst as a curing agent per 100 parts by weight of -531-3X: Parkmill D (manufactured by NOF Corporation), and ZNS-P10 as an internal release agent
After adding parts by weight, aluminum hydroxide: Heidilite H-32 (manufactured by Showa Denko KK) 19 as a filler
5 parts by weight, glass fiber (fiber length 9 mm): ECS09B
100 parts by weight of -601 / P (manufactured by Nippon Electric Glass Co., Ltd.) were added and kneaded with a kneader for 10 minutes to obtain BMC. This BMC was filled into a molding die, and the upper die temperature was 140 ° C., the lower die temperature was 125 ° C., and the pressure was 100 kg / cm ² (9.8 M
Ps), heat-cured for 10 minutes, length 300 mm
A flat BMC molded product having a width of 220 mm and a thickness of 4 mm was obtained. After degreasing the surface of this molded body with acetone, ethyl acetate was added to polymer 2 to adjust the solid content to 5%, and KS-1260 was added in an amount of 0.1 part by weight. After that, heat treatment was performed at 120 ° C. for 3 hours to obtain a composite material having an antifouling surface.

Example 4 A fluorine-based release agent: Mold Spud MR K-652 is uniformly spray-coated on the surface of the mold on which the BMC was molded in Example 3. Next, on the surface of this mold, a solution obtained by adding ethyl carbitol acetate to the polymer 3 to a solid content of 3% was applied by spraying to volatilize the solvent, and then the solvent was volatilized using this mold in the same manner as in Example 3. BMC was molded to obtain a composite material having an antifouling surface.

Example 5 Surfing glass mat (30 g / m ² ): Nitto Boss Glass Fiber MF30P (manufactured by Nitto Boseki Co., Ltd.) was prepared, and ethyl acetate was added to polymer 4 to this mat to contain solids. Apply the solution prepared to an amount of 5%. After the solvent was volatilized and left at 25 ° C. for 5 hours, the surfacing glass mat was placed so that the surface of the bathtub molding die coated with the polymer 4 faced the die surface side, and Example 1 was placed thereon. The SMC prepared with the same composition as that used in the above was placed, the upper mold temperature was 140 ° C., the lower mold temperature was 135 ° C., and the pressure was 7
Heat-cured for 5 minutes under the condition of 0 kg / cm ² (6.86 MPs).
And a composite material having an antifouling surface was obtained.

Example 6 Light-colored vinyl ester resin: Lipoxy RF-312-7
Aluminum hydroxide powder: H-320ST (manufactured by Showa Denko KK) 200 per 100 parts by weight (manufactured by Showa Denko KK)
Parts by weight and 2 parts by weight of Percure WO (manufactured by NOF CORPORATION) as a curing agent were mixed, and vacuum degassing was performed with stirring. This vacuum degassed mixture was injected under pressure into a nickel electroforming mold and cured at 80 ° C. for 1 hour to obtain a vinyl ester artificial marble molded product. After applying isopropyl alcohol to the polymer 4 and diluting it to a solid content of 3%, the surface of the molded body was coated, and the solvent was volatilized.
The composite material was obtained by performing a heat treatment for an hour.

Example 7 A surface of the mold on which the SMC was molded in Example 2 was spray-coated uniformly with a fluorine-based release agent: Mold Spad MR K-652. Next, onto the surface of this mold, a solution obtained by adding ethyl carbitol acetate to the polymer 5 to a solid content of 3% was sprayed to evaporate the solvent, and the solvent was volatilized. The SMC was molded to obtain a composite material.

EXAMPLE 8 Isophthalic unsaturated polyester resin: Rigolac M
-531-3X 100 parts by weight, calcium carbonate: KS
-1300 150 parts by weight, zinc stearate: ZNS
-P 6 parts by weight, magnesium oxide as a thickener: 1 part by weight of magmic, hexamethylene diisocyanate:
8 parts by weight of Coronate HX, Perptyl Z as a curing agent
1 part by weight, 0.1 part by weight of gray mica as a pattern material,
After mixing 0.2 parts by weight of white mica and 0.1 parts by weight of black mica and sufficiently stirring, the PET film is 500 m wide.
m and a thickness of 1 mm. Non-woven cloth (210g
/ M ² ): Set by Toyo Spunbond Co., Ltd., and impregnated with a roll to prepare a sheet with a non-woven cloth ratio of 20%, PE
It was wrapped with a T film to obtain a decorative sheet composition, which was aged at 50 ° C. for 3 days to obtain a decorative sheet. Next, to the decorative sheet, a polymer obtained by adding ethyl acetate to polymer 2 to adjust the content of the intrinsic component to 3% and applying 0.1 parts by weight of KS-1260 was applied, and the solvent was volatilized. For 1 hour. The decorative sheet coated with the polymer 2 and the SMC molded product prepared in the same manner as in Example 1 were placed so that the surface coated with the polymer 2 was on the top, pressed, and cured at 120 ° C. for 2 hours to prevent protection. A composite with a soiled surface was obtained.

Comparative Example 1 An artificial marble of vinyl ester was molded in the same manner as in Example 6, and the surface of the molded article was diluted with isopropyl alcohol to 3% by adding isopropyl alcohol to the polymer 6. Then, after the solvent was volatilized, a heat treatment was performed at 120 ° C. for 2 hours to obtain a composite material.

Comparative Example 2 A fluorine-based release agent: Daifree (manufactured by Daikin Industries, Ltd.) is uniformly spray-coated on the surface of the mold on which the SMC was molded in Example 1. Next, on the surface of this mold, a substance adjusted to a solid content of 1% by adding ethyl carbitol acetate to polymer 7 was spray-coated and the solvent was volatilized. Then, SMC was prepared using this mold in the same manner as in Example 1. Was molded to obtain a composite material.

Comparative Example 3 In the step of producing the composite material having the antifouling surface of Example 3, application of the polymer 2 was not performed.

[0045]

[Table 1]

[0046]

[Table 2]

As is clear from Tables 1 and 2, the composite material of Comparative Example 1 has the same water repellency, oil repellency, and stain resistance at the initial stage as compared with the composite materials of Examples. Poor in hot water immersion, antifouling coating film (layer) cross-cut peeling test, antifouling coating film (layer) strength, and antifouling coating film (layer) durability. This is probably because the coating film (layer) and the composite material are not chemically bonded. Further, the composite material of Comparative Example 2 is inferior in water repellency, oil repellency and stain resistance from the initial stage. This is probably because the polymer 7 constituting the coating film (layer) does not contain a radically polymerizable unsaturated compound having a fluoroalkyl group.
Furthermore, the composite material of Comparative Example 3 is inferior in water repellency, oil repellency, stain resistance, and immersion in warm water. This is presumably because the polymer forming the antifouling coating layer was not applied.

[0048]

According to the composite material having the antifouling surface of the present invention, since the fluoroalkyl group of the fluorine-containing compound is exposed on the surface of the composite material, the water repellency and the oil repellency are increased, thereby increasing the surface of the molded article. When used for bathtubs, washrooms, wall materials, etc. in bathrooms, it becomes difficult for dirt such as water stains to adhere to the surface of the molded article. Dirt can be easily removed. Further, since the composite material having the antifouling surface of the present invention is formed by chemically bonding the antifouling coating material and the composite material surface, the composite material is rubbed and washed with a sponge or the like, or soaked in warm water. However, peeling of the paint hardly occurs, and the durability is high. Furthermore, in the composite material provided with the antifouling surface of the present invention, since the fluoroalkyl group of the fluorine-containing compound is exposed on the surface of the composite material, the friction coefficient of the composite material surface is reduced, and the scratch resistance is improved. As described above, the composite material having the antifouling surface of the present invention not only has excellent antifouling properties, but also has excellent toughness, and these have a synergistic effect on the durability of the material. Therefore, according to the present invention, an antifouling surface is provided which is hardly adhered with dirt, is easily cleaned and removed even if it is adhered, has strong adhesion to a substrate, and has long-term durability. A composite material is obtained which is very advantageously used in household equipment such as bathroom products and plumbing products.

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[Procedure amendment]

[Submission date] November 21, 2000 (200.11.
21)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

Synthesis Example 2 (Synthesis of Polymer 2) Using the same apparatus as in Synthesis Example 1, 196.1 g of ethyl acetate was charged into a flask. Next, 53.2 g of 3- (perfluorooctyl) ethyl methacrylate (10 mol
%) 2-methacryloyloxyethyl isocyanate 46.5 g ( 30 mol%), n-butyl methacrylate 56.8 g (40 mol%), 2-ethylhexyl methacrylate 39.6 g (20 mol%), diacyl as a polymerization initiator A peroxide-based peroxide catalyst: 3.92 g of Perloyl IB (manufactured by NOF Corporation) was mixed, uniformly dissolved, and charged into a dropping funnel. The flask was set in a 60 ° C. oil bath, stirring was started while flowing nitrogen gas, and after the internal temperature of the flask reached 60 ° C., the dropping of the monomer from the dropping funnel into the flask was started and completed in one hour. did. After maintaining the temperature at 60 ° C. to 63 ° C. for an additional hour, 261.5 g of ethyl acetate was added thereto, and the mixture was made uniform and cooled. Gel permeation chromatography (hereinafter abbreviated as GPC) of this polymer 2 GPC
The average molecular weight (Mw) in terms of polystyrene is 10,3.
00.

Continued on the front page F term (reference) 4J038 CC021 CC071 CC081 CC101 CD091 CF021 CG031 CG061 CG071 CG141 CH151 CH191 CH201 CH251 CJ131 GA06 GA07 GA09 GA11 GA12 KA06 NA05 PA17 PC03 PC04 PC08 PC10

Claims (9)

[Claims] (A) a radically polymerizable unsaturated compound having one or more fluorine atoms in a molecule: 1 to 99 mol%,
(B) a radically polymerizable unsaturated compound having at least one functional group selected from a carboxyl group, an isocyanate group, an epoxy group and an amino group in the molecule: 1 to 99 mol%;
And (C) other radically polymerizable unsaturated compounds: 0 to 98
A resin composition for antifouling coating comprising a mole% of a copolymer. 2. The method according to claim 1, wherein (A) the radically polymerizable unsaturated compound having at least one fluorine atom in the molecule is an ethylenically unsaturated compound having a fluoroalkyl group having 1 to 10 carbon atoms. Resin composition for antifouling coating. 3. A composite material having an antifouling surface, wherein the resin composition for antifouling coating according to claim 1 or 2 is coated on the surface of the composite material. 4. The composite material comprises a resin component, a fiber reinforcement and / or
4. The composite material having an antifouling surface according to claim 3, which is a resin composite material comprising a filler. 5. The composite material having an antifouling surface according to claim 3, wherein the composite material constitutes a constituent member of a house facility. 6. The resin composition for antifouling coating according to claim 1, wherein the resin composition is diluted with a solvent, applied to the surface of a composite material, and heat-treated. A method for producing a composite material provided with an antifouling surface according to item 1. 7. A method for applying a resin composition for antifouling coating according to claim 1 or 2 to a surface of a mold for molding a composite material, and molding the composite material using the mold. Item 3-
A method for producing a composite material having an antifouling surface according to any one of claims 5 to 13. 8. A sheet having a surface layer comprising the antifouling coating resin composition according to claim 1 or 2 is bonded to the surface of the composite material. A method for producing a composite material having the antifouling surface according to the above. 9. A sheet having a surface layer comprising the resin composition for antifouling coating according to claim 1 or 2 so that the surface of the antifouling surface layer becomes the surface of the molded article on the surface of a mold for molding a composite material. The method for producing a composite material having an antifouling surface according to any one of claims 3 to 5, wherein the composite material is integrally formed with the sheet using the mold.