JPS61215608A - Painted furniture - Google Patents

Abstract

PURPOSE:Painted furniture being excellent in durability and having a paint film excellent in gloss, transparency, stain proofness and weather resistance, provided with a protective layer based on a functional group-containing vinylidene fluoride copolymer. CONSTITUTION:Wooden, metallic or the like furniture is painted with a coating composition prepared by mixing a fluorine-containing copolymer obtained by polymerizing 50-99mol% vinylidene fluoride with 1-50mol% functional group- containing vinyl monomer of any one of formula I-IV [wherein X is OH, COOH or glycidyl, k is 0 or 1, m is 0-10, n is 0-4 (n=1-4 when X is OH), Y is H or CH3 and p is 1-4] and, optionally, at most 30mol% fluoroolefin other than vinylidene fluoride at -20-150 deg.C and a pressure of 0-30kg/cm<2>G in the presence of a polymerization catalyst in a solvent with, optionally, 10-1,900wt% acrylic resin, 0.5-2 equivalent per equivalent of the total functional groups in said polymer of a crosslinking agent and a curing agent and dissolving the obtained mixture in a suitable solvent so as to obtain a solution of 5-70wt% concentration at a film thickness of 5-100mu and crosslinked and cured at room temperature.

Description

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

[Conventional technology]

Traditionally, wooden or plastic furniture has been given a glossy finish.
Painted furniture is manufactured by providing a protective layer to impart stain resistance, or to impart stain resistance or rust prevention to metal furniture. Such a protective layer has not only gloss, stain resistance, and rust resistance, but also weather resistance, transparency, moisture resistance,
It needs to have excellent heat resistance and durability.

As the resin used for the protective layer, acrylic resin, urethane resin, alkyd resin, vinyl chloride resin, thermoplastic vinylidene fluoride resin, vinyl fluoride resin, phenol resin, silicone resin, epoxy resin, nitrocellulose, unsaturated polyester resin, Various paint resins, such as saturated polyester resins and modified resins thereof, have been developed and are used as paints.

[Problem that the invention seeks to solve]

For example, the surface of wardrobes is generally given a transparent finish using urethane resin paint, unsaturated polyester resin paint, acrylic resin paint, alkyd resin paint, NC lacquer, or the like.

However, the protective layers formed from these paints tend to reduce gloss, cause chalking, crack, etc., have poor durability, are sticky, and do not have sufficient stain resistance. or

On the other hand, when trying to form a protective layer using thermoplastic vinylidene fluoride resin or vinyl fluoride resin, which has excellent stain resistance, heat resistance, and moisture resistance, it is difficult to form the desired protective layer if it does not bake at high temperatures. It cannot be used on wooden furniture because it cannot be changed. Further, a protective layer formed by baking on a metal material generally has a drawback of poor gloss and lack of transparency.

The purpose of the present invention is to be able to cure at room temperature, have excellent stain resistance, be hard and scratch resistant, and have transparency.
An object of the present invention is to provide painted furniture having a protective layer formed from a fluororesin paint containing a fluorine-containing copolymer capable of forming a coating film with excellent gloss.

[Means for solving problems]

The present invention relates to painted furniture provided with a protective layer containing as a main component 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 usually 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 crosslinking agent, It is obtained by crosslinking and curing at room temperature and has a film thickness of about 5 to 100 μm.

The fluorine-containing copolymer has properties that conventional fluororesins do not have, namely, it cures at room temperature to form a hard film, and the formed coating film has the corrosion resistance, weather resistance, and antifouling properties of the fluoropolymer. It retains its characteristics such as It also has good adhesion to wood, 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 1.0 to 25 mol%.

Gel permeation chromatography (G
The molecular weight measured by PC (based on polystyrene) is usually 1
It ranges from 10,000 to 500,000.

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

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

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

Further, the fluorine-containing copolymer of the present invention has good compatibility with an acrylic resin and can be used in combination with an 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 Examples of acrylic resins include Hytaloid 3004 Hytaloid 3018, Hytaloid 3046C (all manufactured by Hitachi Chemical), Acridic A31O-45, Acridic A314, Acridic 47-540 (all manufactured by Dainippon Ink and Chemicals), etc. Not limited to these.

The acrylic resin preferably contains 50% by weight or more of methyl methacrylate 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, and uniformly mixing and dissolving it in an appropriate solvent. It is formed by applying it to furniture, crosslinking and curing it at room temperature. Curing progresses quickly at room temperature, usually within 1
- Although the hard coating can be changed in 10 days, the time required for curing can be shortened by raising the temperature and drying to a level that does not adversely affect the substrate.

The crosslinking agent is a compound having two or more groups capable of crosslinking the fluorine-containing copolymer by reacting with a functional ta group (hydroxyl group, carboxyl group, or glycidyl group) usually contained in the fluorine-containing copolymer. It is. When the functional group is a hydroxyl group, the curing 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,
Examples include, but are not limited to, triethylenetetramine, xylenediamine, metaphenylenediamine, benzyldimethylamine, bisaminopropyltetraoxaspiroundecane, and the like. Examples of acid anhydrides include, but are not limited to, phthalic anhydride, pyromellitic anhydride, and mellitic anhydride. Examples of amino resins include, but are not limited to, alkyl etherified methylolmelamine, alkyl etherified methylolurea, 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. ), aromatic triepoxides represented by the formula: % formula % (in the formula, R2 is a trivalent aromatic group, and Z is the same as above), etc. but not limited to.

It is preferable to adjust the amount of the crosslinking agent to be 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic resin.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include esters 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 methylflucol 1, ethyl alcohol, and methylflucol; aromatics such as toluene and xylene One or more types of hydrocarbons may be used.

The concentration of the fluorine-containing copolymer varies depending on the coating method and coating manufacturing method, 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, dyes, pigments, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, light stabilizers, and coating compositions. Anti-foaming agents, dispersants, antifoaming agents, etc. may be added.

The painted furniture of the present invention can be made of wood, plastics, FRP, F
A fluororesin paint containing a polymer whose main component is a fluorine-containing copolymer and a crosslinking agent is applied to furniture made of RTp, L-U, metal, etc. When painting at room temperature to heating, apply directly to the furniture. However, in the case of wooden furniture, it may be applied after preparing the base, or it may be applied after applying a base treatment such as sealing, coloring, and undercoating, and then applying an intermediate coat layer. In the case of metal furniture, the furniture may optionally be coated with another layer, such as one or more commonly used primer coats such as wash primer, anti-corrosion paint, epoxy resin paint, etc. A protective layer used in the invention may also be formed.

Application to furniture can be carried out by conventional methods such as spraying, brushing, dipping, roll coating, and knife coating.

Specific examples of the painted furniture of the present invention include, for example, furniture for storage,
This includes furniture for reception areas, study rooms, bedrooms, offices, schools, kitchens, childcare, hospitals, etc. The materials used include solid wood such as hardwood and softwood, wood such as veneer and plywood, plastics such as melamine resin, polyester resin, and phenolic resin, steel, aluminum, stainless steel, and zinc tie-casting. Examples include metal and tow.

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

Example I 70 mol% VdF, 20 mol% CTFE and M5FP
50 parts (parts by weight,
) 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 was An amount equivalent to 1.1 and 0.05 g of dibutitin dilaure 1 as a curing accelerator were added and mixed uniformly to prepare a coating composition.

On the other hand, a 15 cm x 10 cm x 1 am board was prepared by wiping the surface of the contact material with alcohol, then spraying with water, and polishing with #150 abrasive paper to condition the surface.

The coating composition was applied to this plate by brushing to form a coating film with a thickness of 28 μm, and the coating was cured at 25° C. for 7 days to obtain a test piece.

Example 2 70 mol% VdF, 20% mol CTFE and M5FP
Fluorine-containing copolymer consisting of IG mol% and MMA80
An acrylic resin consisting of mol% EMA10mol% and HEMAIO mol% was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio) to 50% by weight.
Adjust the face of
To the OHHI3 of the fluorine-containing copolymer and acrylic resin, an amount equivalent to Coronate EHONCO value 1.1 and a curing accelerator dibutyltin dilaurate were added to LXIO-'g per 1 g of solid content and mixed uniformly to form a coating composition. It was adjusted.

The above coating composition was applied to the same plate as in Example 1 and cured in the same manner as in Example 1 to obtain a test piece.

Examples 3 to 4 A board prepared in the same manner as in Example 1 was undercoated with a woodworking urethane resin paint (Kuru PLJR #100 Clear, manufactured by Dainippon Paint Co., Ltd.) to a film thickness of 30 μm. A test piece was obtained by applying the coating composition prepared in Example 2 with a brush to form a coating film having a thickness of about 30 μm, and curing it at 25° C. for 7 days.

Comparative Example 1 A urethane resin paint for woodworking (Dainippon Paint Co., Ltd. Riluppu P'UR #100 Clear) was directly applied to a board prepared in the same manner as in Example 1 to a film thickness of 40 μm, and the temperature was heated at 25°C.
A test piece was obtained which was cured for 3 days.

Comparative Example 2 An amino alkyd resin paint for woodworking (Rutsu SH#100 Clear manufactured by Dainippon Paint Co., Ltd.) was directly applied to a board prepared in the same manner as in Example 1 to a film thickness of 40 μm.
A test piece was obtained by curing at ℃ for 3 days.

The following tests were conducted on the test pieces obtained in Examples 1 to 4 and Comparative Examples 1 to 2, respectively.

The results are shown in Table 1.

[Gloss]

Measured using Nippon Denshoku Kogyo's VC-2PD (gloss meter).

〔Weatherability〕

Using a Sunshine Weather-O-meter manufactured by Suga Test Instruments ■, an accelerated weather resistance test was conducted for 4000 hours under continuous irradiation, rainfall cycle of 18 minutes/120 minutes, humidity of 60%, and blank panel temperature of 63°C. In addition to measuring the gloss retention rate,
Observe the appearance. In Table 1, ◯ indicates no abnormality, and × indicates occurrence of chiller king.

[Stain resistance]

After filling the LCD on the surface of the test piece with Sakura Bentouch (red) (manufactured by MJ Sakura Crepas) and leaving it for 24 hours, wipe it off with Teisocie paper impregnated with ethanol/methyl ethyl ketone (weight ratio 9/1) to judge the appearance. . In Table 1, ○ indicates no abnormality, and × indicates residual or whitening.

Table 1 Examples 5 to 21 Fluorine-containing copolymers or fluorine-containing copolymers and acrylic resins having the compositions shown in Table 2 (the proportions are shown in Table 2).

) was dissolved in methyl isobutyfloketone, and the solid content concentration was adjusted to 30% by weight. - NC0 value of Coronate EH is 1.0 compared to OHHI3 of the solid content of the solution.
1 equivalent amount and dibutyltin dilaurate at a solid content of 1 g
After adding 1xlO-'g to the mixture and mixing thoroughly, the same branch material prepared in Example 1 was brushed and cured at room temperature for 7 days. The cured coatings obtained were all glossy hard coatings with a thickness of 23 to 28 μm.

Each sample was tested for weather resistance and antifouling properties. The results are shown in Table 2.

In addition, each abbreviation indicating a monomer indicates the following compound.

VdF: vinylidene fluoride CTFE: chlorotrifluoroethylene TFE
: Tetrafluoroethylene M 5 FP :
CF z ”” CF CF z CHt OH3F
HA: CF2=CF CHz CHtO
HHBVE: Hydroxybutyl vinyl ether G
VE: Glycidyl vinyl ether 7 F HA
: CF t = CF CF z CF t C
HtCH,OH MMA: Methyl methacrylate EMA:
Ethyl methacrylate HEMA: Hydroxyethyl methacrylate BMA: Butyl methacrylate MA: Methacrylic acid GMA: Glycidyl methacrylate 5FBA
: CF2=CFCF2COO'H (continued on next page) [Effects of the invention] As described above, the polymer composition containing the vinylidene fluoride copolymer having the above-mentioned functional group as a main component can be cured at room temperature. The coating of the present invention, in which the coating film is provided as a protective layer, can form a coating film with excellent gloss, transparency, stain resistance, and weather resistance regardless of the type of furniture. The furniture has excellent gloss, transparency, stain resistance, weather resistance, and excellent durability.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Or painted furniture provided with a protective layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group.