JP2009197145A - Kitchen, washstand and bathroom member coated with fluorocopolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide kitchen members, washstand members and bathroom members coated with a fluorocopolymer, which is excellent in contamination resistance, water repellency, oil repellency, non-adhesiveness, chemical resistance and solvent resistance when the fluorocopolymer is applied and baked once without surface preparation and which exhibits excellent adhesion to various base materials. <P>SOLUTION: Kitchen members such as a sink, a countertop, a door material and drain members are exemplified whose surfaces are coated with the fluorocopolymer containing vinylidene fluoride, tetrafluoroethylene, reactive silicone oil, vinyl ether having a hydroxy group and an unsaturated carboxylic acid as essential polymerization units. Or washstand members such as the countertop, a bowl and a mirror cabinet are exemplified whose surfaces are coated with the fluorocopolymer. Or bathroom members such as a wall material, a ceiling material and drain members are exemplified whose surfaces are coated with the fluorocopolymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has excellent characteristics such as stain resistance, water and oil repellency, non-adhesiveness, chemical resistance and solvent resistance, which are the characteristics of fluororesin, and excellent adhesion to various substrates. The present invention relates to a kitchen, a bathroom, and a bathroom member, the surface of which is coated with a fluorine copolymer.

Various materials such as kitchen sinks, countertops, door materials, drainage outlets, vanity countertops, bowls, mirror cabinets, bathroom wall materials, ceiling materials, drainage outlets, etc. are contaminated. Various materials such as materials that are difficult to adhere and materials that can easily wipe off dirt have been proposed. Various materials with excellent scratch resistance have been proposed. For example, a stainless steel kitchen sink utilizes the inherent characteristics of stainless steel such as toughness and elasticity, and exhibits an advantage that even if tableware such as teacups is dropped carelessly, cracks do not occur. However, the disadvantage is that the surface hardness is low, and it is easy to get wrinkled and dirty. The stainless steel kitchen sink has one of the advantages of the beautiful appearance unique to stainless steel, but wrinkles and dirt can significantly deteriorate the appearance.
For this reason, the number of cases where coating is applied in order to improve the scratch resistance and contamination resistance has recently increased. A variety of inorganic and organic paints are used as coating materials. However, when organic fluororesins are used, there is a problem with adhesion, and primer coating must be applied before applying fluorine coating. (Patent Document 1). Or the method of ensuring adhesiveness by providing a connection particle | grain on a base-material surface layer is proposed (patent document 2).

Recently, artificial marble has been widely used for countertops, but food contaminants may stick to the surface and may be difficult to remove, and may be painted to improve ease of wiping. is there. In this case, inorganic paints such as silica and various organic resins such as fluororesin have been proposed, but as a problem when applying the fluoro paint, there is a problem in adhesion as in the above-described sink, When used for a long time, there was a problem that the coating film was easily peeled off.
Japanese National Patent Publication No. 7-506514 JP 2002-309386 A

According to the inventions of Patent Documents 1 and 2 described above, excellent adhesion can be secured even with a fluororesin having generally poor adhesion. However, in any case, ground treatment is necessary, and complicated work is still required.
The present invention has been devised to solve such problems, and by providing a fluorine copolymer containing a hydroxyl group-containing vinyl ether and an unsaturated carboxylic acid on the substrate surface in order to improve adhesion, Fluorine coexisting with excellent adhesion to various substrates as well as excellent stain resistance, water and oil repellency, non-adhesiveness, chemical resistance, solvent resistance, etc. by one coating and baking without surface treatment Kitchen materials such as sinks, counter tops, door materials, drain outlet members coated on the surface of the polymer, or bathroom vanity parts such as counter tops, bowls, mirror cabinets, wall materials, ceiling materials, drain outlet members, etc. It aims at providing the member for bathrooms.

As a result of intensive studies, the present inventors have determined that as an essential polymerization unit, a fluorine copolymer containing vinylidene fluoride, tetrafluoroethylene, reactive silicone oil, a hydroxyl group-containing vinyl ether, and an unsaturated carboxylic acid is used as a kitchen, a bathroom vanity, It discovered that the said subject was solved by providing in the base-material surface of each member of a bathroom, and completed this invention. That is, the said subject is solved by the following this invention.

As an essential polymerization unit, a sink, a counter top, and a surface coated with a fluorine copolymer containing vinylidene fluoride, tetrafluoroethylene, a reactive silicone oil of the following general formula (1), a hydroxyl group-containing vinyl ether, and an unsaturated carboxylic acid, Kitchen materials such as door materials and drain outlet members, countertops coated with the fluorine copolymer on the surface, bowls, mirror vane members such as mirror cabinets, and walls coated with the fluorine copolymer on the surface Bathroom materials such as wood, ceiling, and drainage members.
_{R 1 - [Si (CH 3} ) 2 -O] n-Si (CH 3) 2 -R 2 (1)
[In formula (1), R ₁ represents an alkyl group or 1 to 6 carbon atoms - represents a _{(CH 2) m-OOC (} CH 3) C = CH 2 or -CH = CH _2.
R ₂ represents an alkyl group having 1 to 6 carbon atoms, or — (CH ₂ ) m—OOC (CH ₃ ) C═CH ₂ or —CH═CH ₂ . n represents 1-420 and m represents 1-6. ]

According to the present invention, the surface is coated with a fluorocopolymer having excellent adhesion resistance to various substrates while being excellent in stain resistance, water / oil repellency, non-adhesiveness, chemical resistance, solvent resistance, etc. Kitchen components such as sinks, countertops, doors, and drainage outlets, bathroom vanity members such as countertops, bowls, and mirror cabinets, and bathroom materials such as wall materials, ceilings, and drainage outlets can be provided.

1. Kitchen member or bathroom vanity member or bathroom member The kitchen member of the present invention includes a base material such as a sink, a counter top, a door material, a drain port member, and a fluorine copolymer provided on the base material. Including the film. Moreover, the member for vanity tops of this invention contains base materials, such as a countertop, a bowl, a mirror cabinet, and the film | membrane of the fluorine copolymer provided on the said base material. Moreover, the member for bathrooms of this invention contains base materials, such as a wall material, a ceiling material, and a drain port member, and the coating film of the fluorine copolymer provided on the said base material. Each member will be described below.

(1) Base Material The kitchen member of the present invention includes base materials such as a sink, a counter top, a door material, and a drain port member. First, the sink and counter top include a stainless steel plate and FRP resin processed into a sink or counter top shape. The stainless steel plate may be polished or embossed. Examples of the resin for FRP resin include acrylic resin, unsaturated polyester resin, vinyl ester resin, epoxy resin, and diallyl phthalate resin. Examples of such FRP resins include styrene, peroxide-based curing agents, polyisocyanate compounds, glass fibers, aluminum hydroxide, pattern materials, pigments, ultraviolet absorbers, internal release agents, and the like as appropriate. It is done. The door material may be a particle board, MDF, plywood, natural wood, or metal plate that is surface-coated with a resin sheet, paint, or the like and processed into a door material shape. Examples of the drain port member include PP resin and ABS resin processed into a predetermined shape.
The member for a vanity according to the present invention includes base materials such as a counter top, a bowl, and a mirror cabinet. Examples of the counter top include acrylic resin, unsaturated polyester resin, and vinyl ester resin processed into a predetermined shape. The bowl may be the above resin or pottery. Examples of mirror cabinets include polystyrene resin and metal plates with excellent impact resistance.
The bathroom member of this invention contains base materials, such as a wall material, a ceiling material, and a drain port member. Examples of the wall material and the ceiling material include a resin sheet processed into a predetermined shape, a steel plate such as a stainless steel plate or a galvanized steel plate surface-coated with a paint, or a resin such as a polystyrene resin or an unsaturated polyester resin. Examples of the drain port member include PP resin and ABS resin processed into a predetermined shape.

(2) Fluorine copolymer film A film made of a fluorine copolymer containing vinylidene fluoride, tetrafluoroethylene, reactive silicone oil, a hydroxyl group-containing vinyl ether, and an unsaturated carboxylic acid as essential polymer units.

1) Fluorine monomer As the fluorine monomer, vinylidene fluoride and tetrafluoroethylene are essential components. In addition, chlorotrifluoroethylene, hexafluoroethylene, etc. may be added as appropriate.

2) Reactive silicone oil The following general formula (1) is used as the reactive silicone oil.
_{R 1 - [Si (CH 3} ) 2 -O] n-Si
(CH ₃ ) ₂ -R ₂ (1)
[In formula (1), R ₁ represents an alkyl group or 1 to 6 carbon atoms - represents a _{(CH 2) m-OOC (} CH 3) C = CH 2 or -CH = CH _2.
R ₂ represents an alkyl group having 1 to 6 carbon atoms, or — (CH ₂ ) m—OOC (CH ₃ ) C═CH ₂ or —CH═CH ₂ . n represents 1-420 and m represents 1-6. ]
The reactive silicone oil represented by the general formula (1) is preferably polydimethylsiloxane with one end being methacryl-modified, polydimethylsiloxane with one end being acrylic-modified, polydimethylsiloxane having both ends methacryl-modified. These reactive silicone oils may be used alone or in combination of two or more.

3) Hydroxyl group-containing vinyl ether Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and the like, and 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether are particularly preferable.

4) Unsaturated carboxylic acid Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, 3-butenoic acid, 4-pentenoic acid, and acrylic acid and methacrylic acid are particularly preferable.

5) Blending amount The blending amount of each component in the present invention is 30 to 80 mol% of a fluorine-based monomer, 0.005 to 25 mol% of a reactive silicone oil represented by the general formula (1), and 10 to 40 mol of a hydroxyl group-containing vinyl ether. % And unsaturated carboxylic acid is preferably 0.5 to 20 mol%.

The fluorine copolymer film in the present invention has excellent adhesion to various substrates as described above. That is, various methods generally used for improving the adhesion are not required. That is, it is not necessary to pre-apply primer paint, mechanically roughen the surface, or activate the surface by corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, or the like. As long as the surface is clean, the fluorocopolymer film of the present invention adheres firmly to the substrate. In particular, room temperature water is used daily in kitchens, bathroom vanities, and bathrooms, but adhesion does not deteriorate even when exposed to warm water for a long time. The reason is considered as follows.

In the present invention, a hydroxyl group-containing vinyl ether and an unsaturated carboxylic acid are included as polymerization components, but a hydroxyl group is included as a polar group in the hydroxyl group-containing vinyl ether, and a carboxyl group is included as a polar group in the unsaturated carboxylic acid. On the other hand, it is considered that polar groups such as hydroxyl groups are also present on the surfaces of various steel sheets and various resins on the substrate side, and since these polar groups can be chemically bonded to each other, a strong bond between the film and the substrate is obtained. It is considered that the adhesiveness is expressed.

In order to cure the fluorine copolymer in the present invention, an isocyanate curing agent may be used as the curing agent. Examples of the isocyanate curing agent include aromatic diisocyanates such as aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate and xylylene diisocyanate, And these blocked isocyanates are preferred.

Although the fluorine copolymer in the present invention is transparent, for example, a coloring pigment may be added for coloring. Moreover, in order to express metallic or pearly feeling, aluminum powder or pearl pigment may be added. In addition, matting agents can be added to create a more calm texture. For sinks, lubricating powders such as PTFE (polytetrafluoroethylene) widely used in the world as a lubricant may be added. Furthermore, an antibacterial agent and an antifungal agent may be added for the drain port member.

(Preparation of fluorocopolymer A)
After degassing into a stainless steel autoclave with a stirrer (withstand pressure of 100 kg / cm ² ), 96 g of vinylidene fluoride, 81 g of tetrafluoroethylene, 69.6 g of hydroxybutyl vinyl ether, 2.2 g of acrylic acid, the following structural formula CH ₂ = C ( _{CH 3) -COO-C 3 H} 6 - Si (CH 3) 2 - [O-Si (CH 3) 2] 44 -OSi (CH 3) 3
Were added 10.5 g of methacryl-modified silicone oil, 200 ml of butyl acetate, 200 ml of n-butanol and 1.3 g of t-butyl peroxypivalate, and the internal temperature was raised to 60 ° C. while stirring. Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction.

Further, the obtained polymerization solution was concentrated to obtain a 50% butyl acetate / n-butanol mixed solution. Further, Coronate HX [manufactured by Nippon Polyurethane Industry Co., Ltd.] was added to this solution so that the hydroxyl group / NCO group of the polymer was 1/1, to prepare a fluorinated copolymer A.

(Coating for stainless steel mirror kitchen sink)
A SUS304 stainless steel plate BA material having a thickness of 0.7 mm was used as a coating original plate and drawn into a sink shape. Then, buffing was performed to finish the surface to a mirror surface. The base material was subjected to alkali degreasing treatment, water washing treatment, and drying treatment, and then the fluorine copolymer A was spray-coated. Thereafter, the coating film was dried at an ultimate plate temperature of 180 ° C. for 20 minutes to obtain a mirror kitchen sink on which a transparent film having a thickness of 10 μm was formed.

A test piece was cut out from the bottom of the stainless steel kitchen sink thus obtained, and subjected to a hot water adhesion test, an appearance test, and an antifouling test (oil-based magic repeatability). The results are shown in Table 1.
1) Warm water-resistant adhesion test After immersing the test piece continuously in warm water at 80 ° C for 168 hours, the specimen was dried, peeled off, and evaluated by coating film adhesion. The evaluation criteria were as follows.
◎: No peeling ○: The ratio of the area of the peeling portion to the area where the tape is applied is 10% or less. Δ: The ratio exceeds 10% and is 50% or less. X: The ratio exceeds 50%.

2) Appearance evaluation Visually evaluated whether there was no abnormality in the appearance, such as whether the finish after painting was smooth or not, and whether there was no skin.
○: Good, ×: Bad

3) Antifouling test The antifouling property was evaluated by the removability of oily magic (black, red, magic ink trade name). The coating surface is painted with oil-based magic, left at room temperature for 1 hour, and then removed by dry wiping. The removability of the coating film surface after repeating this 20 times is evaluated.

◎: No trace at all ◯: Very slight trace △: Significant trace ×: Full trace remains

(Coating on artificial marble kitchen countertops)
As FRP resin for artificial marble, using unsaturated polyester resin, other styrene, peroxide curing agent, polyisocyanate compound, glass fiber, aluminum hydroxide, pattern material, pigment, ultraviolet absorber, internal release agent, etc. Was added into a countertop shape. Thereafter, the surface of the substrate was cleaned with alcohol, and the fluorine copolymer A was spray-coated, and then the coating film was dried at a reaching plate temperature of 120 ° C. for 20 minutes, and then left at room temperature for 1 day to cure. When finished, a kitchen countertop on which a transparent film having a film thickness of 7 μm was formed was obtained. A hot water resistant adhesion test, appearance test, and antifouling test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Coating on decorative steel plate for bathroom wall)
As a decorative steel sheet for bathroom wall material, a galvanized steel sheet having a thickness of 0.45 mm was used as a coating original sheet. As a pre-coating treatment, first, the surface was adjusted, followed by a coating type chromate treatment.
Next, the base paint was applied and baked after the primer paint was applied and baked. Further, the pattern printing layer was applied by screen printing and then dried. Then, as a top layer, the fluorocopolymer A was applied by screen printing, and then the coated film was dried at an ultimate plate temperature of 180 ° C. for 20 minutes to form a transparent film having a film thickness of 10 μm on the outermost layer. A decorative steel sheet for wall material was obtained. A hot water resistant adhesion test, appearance test, and antifouling test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Covering on bathroom drain outlet)
As a drain outlet member of the bathroom, a water-sealed cylinder made of ABS resin was used. First, the entire surface was cleaned with alcohol, and the fluorine copolymer A was spray-coated, and then the coated film was dried at an ultimate plate temperature of 80 ° C. for 20 minutes, and then allowed to stand at room temperature for 1 day to complete the curing. A sealed water bottle having a transparent film having a thickness of 5 μm was obtained. A hot water resistant adhesion test, appearance test, and antifouling test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

(Preparation of fluorocopolymer B)
After deaeration in a stainless steel autoclave with a stirrer (withstand pressure of 100 kg / cm ² ), 96 g of vinylidene fluoride, 81 g of tetrafluoroethylene, 2.2 g of acrylic acid, the following structural formula CH ₂ ═C (CH ₃ ) —COO—C _{3 H 6 -Si (CH 3)} 2 - [O-Si (CH 3) 2] 44 -OSi (CH 3) 3
Were added 10.5 g of methacryl-modified silicone oil, 200 ml of butyl acetate, 200 ml of n-butanol and 1.3 g of t-butyl peroxypivalate, and the internal temperature was raised to 60 ° C. while stirring. Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction.

Further, the obtained polymerization solution was concentrated to obtain a 50% butyl acetate / n-butanol mixed solution. Further, Coronate HX [manufactured by Nippon Polyurethane Industry Co., Ltd.] was added to this solution so that the hydroxyl group / NCO group of the polymer was 1/1, thereby preparing a fluorinated copolymer B. Further, the coating film characteristics of the cured coating film of the copolymer B were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2

(Preparation of fluorocopolymer C)
After deaeration in a stainless steel autoclave with a stirrer (withstand pressure of 100 kg / cm ² ), 96 g of vinylidene fluoride, 81 g of tetrafluoroethylene, 69.6 g of hydroxybutyl vinyl ether, the following structural formula CH ₂ ═C (CH ₃ ) —COO— _{C 3 H 6 -Si (CH 3} ) 2 - [O-Si (CH 3) 2] 44 -OSi (CH 3) 3
Were added 10.5 g of methacryl-modified silicone oil, 200 ml of butyl acetate, 200 ml of n-butanol and 1.3 g of t-butyl peroxypivalate, and the internal temperature was raised to 60 ° C. while stirring. Thereafter, the reaction was continued with stirring, and stirring was stopped after 20 hours to complete the reaction.

Further, the obtained polymerization solution was concentrated to obtain a 50% butyl acetate / n-butanol mixed solution. Further, Coronate HX [manufactured by Nippon Polyurethane Industry Co., Ltd.] was added to this solution so that the hydroxyl group / NCO group of the polymer was 1/1, to prepare a fluorinated copolymer C. Further, the coating film characteristics of the cured coating film of the copolymer C were examined in the same manner as in Example 1. The results are shown in Table 1.

From the results in Table 1, it is clear that the kitchen member, the bathroom vanity member, and the bathroom member coated with the fluorine copolymer of the present invention are excellent in hot water adhesion, appearance, and antifouling properties.

The kitchen, vanity table, and bathroom components of the present invention are excellent in productivity, hot water adhesion, appearance, and antifouling properties, so they can be used in system kitchens, vanity tables, and system baths in private or apartment buildings. Is preferred.

Claims (1)

As an essential polymerization unit, a sink, a counter top, and a surface coated with a fluorine copolymer containing vinylidene fluoride, tetrafluoroethylene, a reactive silicone oil of the following general formula (1), a hydroxyl group-containing vinyl ether, and an unsaturated carboxylic acid, Kitchen materials such as door materials and drain outlet members, countertops coated with the fluorine copolymer on the surface, bowls, mirror vane members such as mirror cabinets, and walls coated with the fluorine copolymer on the surface Bathroom materials such as wood, ceiling, and drainage members.
_{R 1 - [Si (CH 3} ) 2 -O] n-Si (CH 3) 2 -R 2 (1)
[In formula (1), R ₁ represents an alkyl group or 1 to 6 carbon atoms - represents a _{(CH 2) m-OOC (} CH 3) C = CH 2 or -CH = CH _2.
R ₂ represents an alkyl group having 1 to 6 carbon atoms, or — (CH ₂ ) m—OOC (CH ₃ ) C═CH ₂ or —CH═CH ₂ . n represents 1-420 and m represents 1-6. ]