JPS61218610A - Stainproof fan - Google Patents

Abstract

PURPOSE:The titled product having improved stain resistance, hardness, slightly being scratched, having improved durability, obtained by providing a fan with a protecting layer comprising a functional group-containing vinylidene fluoride copolymer or a crosslinked material of it as a main component. CONSTITUTION:Preferably a copolymer comprising a (A) 65-85mol% vinylidene fluoride, (B) 1-10mol% functional group-containing vinyl monomer such as a compound (e.g., CF2=CFCF2CH2OH, etc.) shown by the formula [X is OH, COOH, or glycidyl; k is 0 or 1; m is 0-10 integer; n is 0-4 (with the proviso that n is 1-4 when X is OH) integer], or 65-85mol% component A, 1-10mol% component B, and (C) 10-25mol% fluoroolefin (e.g., CF2=CF2, etc.) except component A is dissolved in a solvent such as methyl isobutyl ketone, etc., blended with a polyisocyanate crosslinking agent and a curing promoter such as dibutyltin laurate, etc., to give a coating composition, which is applied to a fan, to give the aimed product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antifouling fan. More specifically, the present invention relates to an antifouling fan provided with a protective layer that has excellent antifouling properties, is hard and scratch-resistant, and has excellent transparency and gloss.

[Conventional technology]

Conventionally, in order to facilitate the removal of dirt from ventilation fans, for example, it has been proposed to form a coating film of fluororesin baking paint on the blades and frames (Utility Model Publication No. 51-108).
356 and JP-A-53-13540).

[Problem that the invention seeks to solve]

This proposal attempts to take advantage of the corrosion resistance, weather resistance, stain resistance, and other properties of fluororesin, but conventional fluororesin baking paints do not bake at high temperatures.
g, so it cannot be used with blower fans made of plastic. Furthermore, even if the base material of the fan is metal, it is necessary to provide a special layer of brimer because fluororesin does not easily adhere to metal. Furthermore, the baked coating film obtained is relatively soft and easily scratched, and is also poor in transparency, which poses a problem in terms of decorativeness.

The object of the present invention is to provide a fluororesin containing a fluorine-containing copolymer that can be cured at room temperature, has excellent stain resistance, is hard and scratch resistant, and can form a coating film with excellent transparency and gloss. An object of the present invention is to provide an antifouling fan having a protective layer formed from paint.

[Means for solving problems]

The present invention relates to an antifouling fan, which is provided with a protective layer mainly composed of a vinylidene fluoride copolymer having a functional group and/or a crosslinked product of a vinylidene fluoride copolymer having a functional group. .

[Function and Examples]

The protective layer in the present invention is formed by applying a fluororesin paint consisting of a polymer composition mainly composed of a vinylidene fluoride copolymer having a functional group (hereinafter referred to as a fluorine-containing copolymer) and a crosslinked side, Obtained by crosslinking and curing at room temperature.

The fluorine-containing copolymer has properties not found in conventional fluororesins, namely, it cures at room temperature to form a hard film, and the formed coating film has the corrosion resistance, weather resistance, and stain resistance of fluoropolymers. It retains its characteristics such as It also has good adhesion to plastics and metals. The components, composition, etc. of such a fluorine-containing copolymer are explained in detail in Japanese Patent Application No. 175123/1983.

In the present invention, the fluorine-containing copolymer usually contains 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, and 1 to 50 mol% vinyl monomer having a functional group, preferably 1 to 10 mol%. or vinylidene fluoride 50 to 99 mol%, preferably 65 to 85 mol%, vinyl monomer having a functional group 1 to 50 mol%, preferably 1 to 10 mol%, and preferably less than 30 mol% of fluoroolefins other than vinylidene fluoride. is comprised of 10 to 25 mol%.

The molecular weight measured by gel permeation chromatography (GPC, polystyrene standard) of the fluorine-containing copolymer containing vinylidene fluoride as the main component and having a functional group is as follows:
Usually in the range of 10,000 to 500,000.

The vinyl monomer having the above-mentioned functional group usually has the formula: % formula %) (wherein,
is O~4 [However, if X is a hydroxyl group, it is 1~4]
indicates an integer. ), a compound represented by the formula: %formula%) (wherein, an integer of ~4,
X is as defined above, or a compound represented by the formula: %Formula% (wherein, Y is as defined above).

The fluoroolefins other than vinylidene fluoride mentioned above are usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., and preferably tetrafluoroethylene or chlorotrifluoroethylene. be.

As a method for producing the fluorine-containing copolymer used in the present invention, for example, each component is mixed in the presence of a solvent, using a polymerization catalyst, at a temperature of -20 to 150°C, preferably 5 to 95°C, and at a temperature of 0 to 30 kg. /cdG, preferably 10kg/cd
Methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under pressure conditions of G or less may be employed.

Furthermore, the vinylidene fluoride copolymer of the present invention has good compatibility with acrylic resin, and can be used in combination with acrylic resin.

The above-mentioned acrylic resin refers to a single or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, commercially available Acrylic resins include Hyfroid 3004, Hifroid 3018, Hifroid 3046C (all manufactured by Hitachi Chemical), Acrizo Ink A-810-45, Acridic A314, Acridic 47-540 (
All of them are manufactured by Dainippon Ingi Chemical Industry Co., Ltd.) and the like, but are not limited to these.

The acrylic resin preferably contains methyl methacrylate of 50 or more and has a molecular weight (GPC) of 5,000 to 300,000 from the viewpoint of compatibility with the fluorine-containing copolymer.

The blending ratio of the fluorine-containing copolymer and acrylic resin is usually 1 part by weight of the fluorine-containing copolymer to 1 part by weight of the acrylic resin.
The amount is 0 to 1900 parts by weight, preferably 25 to 400 parts by weight. When blended within this range, the weather resistance, translucency, and
Good pigment dispersibility etc.

The protective layer in the present invention is usually prepared by blending a fluorine-containing copolymer with a crosslinking agent as described above, uniformly mixing and dissolving it in a suitable solvent, and applying a coating composition to a substrate such as a fan blade or frame. It is formed by applying it to the surface, crosslinking and curing it at room temperature. Curing progresses quickly at room temperature, and a hard coating film is usually obtained in 1 to 10 days, but the time required for curing can be shortened by drying at a temperature raised to a level that does not adversely affect the substrate.

The crosslinking agent is a functional group (
It is a compound having two or more groups capable of crosslinking a fluorine-containing copolymer by reacting with a hydroxyl group, a carboxyl group, or a greensill group.

When the functional group is a hydroxyl group, the crosslinking agent is usually an isocyanate, an acid anhydride, or the like. When the functional group is a carboxyl group, it is usually an isocyanate, an amine, an amino resin, a compound containing a glycidyl group, etc. When the functional group is a glycidyl group, it is usually an amine. Examples of isocyanates include, but are not limited to, hexamethylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, and block isocyanates thereof. Examples of amines include diethylenetriamine, triethylenetetramine, Examples of acid anhydrides include, but are not limited to, xylene diamine, metaphenylene diamine, benzyldimethylamine, bisaminopropyltetraoxaspirone undecane, etc., and include phthalic anhydride, lomeliftic anhydride, mellitic anhydride, etc. These include, but are not limited to: Examples of amino resins include, but are not limited to, alkyl etherified methylol melamine, alkyl etherified methylol urea, alkyl etherified benzoylguanamine, and the like. An example of a compound containing a glycidyl group is the formula: %Formula% (wherein, Z represents a glycidyl group, and R1 represents an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group having 6 to 10 carbon atoms. ) or aromatic dieboxides, and aromatic triepoxides represented by the formula: % formula % (wherein R2 is a trivalent aromatic group and Z is the same as above). but is not limited to these.

The amount of the crosslinking agent is preferably adjusted to 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic copolymer.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include ester necks such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran; amides such as N-dimethylformamide and N-dimethylacetamide; alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; aromatic carbonization such as toluene and xylene One or more types of hydrogens may be used.

The concentration of the fluorine-containing copolymer varies depending on the coating method, coating manufacturing method, etc., but is usually 5 to 70% by weight, preferably 20 to 60% by weight.

The fluorine-containing copolymer coating composition may optionally contain other polymers, curing accelerators, pigments, viscosity modifiers, leveling agents, gelling A'l, ultraviolet absorbers, and anti-scald agents. , a dispersant, an antifoaming agent, etc. may be added.

If necessary, the base material may be provided with another layer, such as one or more layers of commonly used undercoat paint such as wash primer, anti-rust paint, or epoxy resin paint, and the protective layer of the present invention may be formed thereon. Good too.

For application to the base material of the blower fan, a conventional method such as a spray method, a brush coating method, a dipping method, a roll coating method, or a knife coating method is applied.

Examples of ventilation fans include home and factory ventilation fans, blowers, dryers, electric fans, and other devices that use blades to blow air, and materials include polypropylene, polyvinyl chloride,
It can be applied to plastics such as polyester, and metals such as steel, iron, aluminum, or alloys thereof.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 70 mol% vdF, 072820 mol% and M5FP
50 parts (parts by weight,
The same applies below) was added to 50 parts of methyl isobutyl ketone and mixed uniformly, and Coronate EH (a polyisocyanate crosslinking agent manufactured by Nippon Polyurethane Industries, Ltd.) was added as a crosslinking agent to the OHHI3 of the fluorine-containing copolymer and the NC0 of Coronate EH. An amount equivalent to 1,1 and 0.05 g of dibutyl tin dilaure as a curing accelerator were added and mixed uniformly to prepare a coating composition.

A steel plate having a length of 150 mm, a width of 70 fi, and a thickness of 1 m was roughened by sandblasting and then degreased with acetone to prepare a substrate.

The coating composition was applied to this substrate by a brush coating method to form a coating film having a thickness of 30 μl, and was cured at 25° C. for 7 days to form a protective film.

Example 2 70 mol% VdF, 072820 mol% and M5FP
Fluorine-containing copolymer consisting of IO mol% and MMA80
An acrylic resin consisting of mol%, EMAIO mol% and HEMAIO mol% was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio) to prepare a 50% by weight face, and Coronate EH was further added as a crosslinking agent to form a fluorine-containing resin. To the OHHI 3 of the copolymer and acrylic resin, an amount equivalent to Coronate EH value NC0 value 1.1 and a curing accelerator dibutyltin dilaurate were added at 1xlO-3g per 1g solid content and mixed uniformly to prepare a coating composition. .

A steel plate having a length of 150 fi, a width of 70 mm, and a thickness of 1 mm was roughened by sandblasting and then degreased with acetone to prepare a substrate.

The above-mentioned coating composition was applied to this substrate by a brush coating method to form a coating film having a thickness of 32 μm, and the coating was cured at 25° C. for 7 days to form a protective film.

Comparative Example 1 A conventional fluororesin baking paint, Polyflon Enamel B5-5109 (top coat manufactured by Daikin Industries, Ltd.), was applied to a substrate prepared in the same manner as in Example 1 by spray painting to a film thickness of 32 μm. A film was formed and baked at 380° C. for 15 minutes to form a protective film.

Comparative Example 2 Polyflon Enamel EK-19, a conventional fluororesin primer paint, was applied to a substrate prepared in the same manner as in Example 1.
00 (manufactured by Daikin Industries, Ltd.) to a film thickness of 8 μm, and then overcoat Polyflon Enamel ES-5109 to a film thickness of 25 μm, and then baked at 380°C for 15 minutes to form a protective film. was formed.

The following tests were conducted on the samples obtained in Examples 1 and 2 and Comparative Examples 1 and 2, respectively. The results are shown in Table 1.

[Hardness test]

According to JIS K5400 6.14, the pencil hardness at which the paint film was broken was measured using (■ Toyo Seiki rupture paint film pencil scratch tester). The pencil used was a Mitsubishi Uni Pencil (manufactured by Mitsubishi Pencil ■).

Table 1 Examples 3 to 4 and Comparative Examples 3 to 4 Example i was applied to a polypropylene molded plate (10 am x 5 cs x 2 n) whose surface was degreased with ethyl alcohol.
Examples 3 and 4 were obtained by applying a coating composition having the same composition as those in Example 2 and Example 2 with a brush to form a 20μ thick coating film, and curing at 25°C for 7 days to form a protective film. ,
Only the polypropylene molded plate was used as Comparative Example 3. Comparative example 4
The same molded plate as above was used, in which 1% of low molecular weight polytetrafluoroethylene (Lublon L-2, manufactured by Daikin Industries, Ltd.) was added to polypropylene.

The following tests were conducted on this sample. The results are shown in Table 2.

C Hardness Test] Same as above [Gloss Test] Measured using a glossy needle (VC-2PD manufactured by Nippon Denshoku Kogyo ■).

[Transparency test]

Measurement was made by visual judgment of appearance.

@ in Table 2 indicates that the color and pattern of the substrate could be completely determined.

[Antifouling test]

10g of salad oil and 1g of carbon black on the surface of the sample
The mixture with 0 g was applied to an area of approximately the size of the LED and wiped off with tissue paper.

Each symbol in Table 2 indicates the following results.

It was completely removed by wiping 023 times.

Δ: Almost all particles could be removed by wiping 10 times.

×: Could not be removed even after wiping 10 times.

Table 2 Examples 5 to 23 A fluorine-containing copolymer or a fluorine-containing copolymer and an acrylic resin (the proportions are shown in Table 3) having the compositions shown in Table 3 were dissolved in methyl isobutyl ketone, and a solid Min concentration is 30
OH of the solid content of the solution adjusted to be % by weight
Coronate EH in an amount equivalent to NC0 value 1.1 for HI3 and dibutyltin dilaurate per 1 g of solid content.
After adding Xl0-"g and mixing thoroughly, a 0.5-thick steel plate treated with zinc phosphate (Japan Test Panel Industry Co., Ltd.)
was spray coated and cured at room temperature for 7 days.

The cured coatings obtained were all glossy, hard coatings with a thickness of about 25 to 30 μm.

The following tests were conducted for each sample.

The results are shown in Table 3.

〔chemical resistance〕

Put 10% by weight sulfuric acid and 10% by weight potassium hydroxide aqueous solution into two glass containers, and heat each sample at 25°C.
It was soaked in these for 12 days. Thereafter, the appearance of each sample was visually observed to determine the chemical resistance of the coating film. ◎ in Table 3
indicates that there was no abnormality at all, and O indicates that there was no abnormality other than slight discoloration.

[Stain Resistance] 1c11 on the surface of the sample was filled with oil-based ink (■ Sakura Penta Sochi red, manufactured by Sakura Crepas Co., Ltd.), left for 24 hours, and then wiped off with tissue paper soaked with ethanol. O in Table 3 can be completely removed, but some traces remain.
This shows that it was possible to distinguish it from the untested part.

In addition, compounds with respective abbreviations indicating monomers in Examples are shown.

VdF: vinylidene fluoride CTFE: chlorotrifluoroethylene TFE
: Tetrafluoroethylene M 5 FP :
CF t = CF CF z CHt OH3FHA
: CF! Lightning CF CHt CHz OHHBVE
: Hydroxybutyl vinyl ether GVF, :
Glycidyl vinyl ether 7 F HA: C
F z = CF CF t CFtCHtCHlOH MMA: Methyl methacrylate EMA:
Ethyl methacrylate HEMA: Hydroxyethyl methacrylate BMA: Butyl methacrylate MA = Methacrylic acid GMA: Glycidyl methacrylate 5F8A:
CFZ=CFCFgCOOH [Effects of the Invention] As described above, a polymer composition containing a functional group-containing vinylidene fluoride copolymer as a main component can be cured at room temperature, and has excellent hardness, gloss, transparency, and stain resistance. Since a coating film with excellent properties and chemical resistance can be formed on any type of substrate, the antifouling fan of the present invention, which is provided with the coating film as a protective layer, has extremely excellent antifouling properties. , durability, etc.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Alternatively, an antifouling fan is provided with a protective layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group.