JP2002097810A - Bath room internal surface member with antifouling property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To rather easily remove dirt of internal surface members of a bath room for maintenance-free. SOLUTION: In this bath room internal surface member with antifouling property, a gel coat layer, having a modified silicone oil containing double bonds in molecules mixed in a base resin including double bonds in molecules, is formed on a surface forming at least the inside of the bath room.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for imparting an antifouling function to a bathroom inner surface member.

[0002]

2. Description of the Related Art Waterproof pans and side wall plates constituting the inner surface of a bathroom, and small-sized storage panels (hereinafter referred to as "inside members of the bathroom") incorporated in the side wall plate include FRP molded products, artificial marble, and the like. Various selections are made. Furthermore, in recent years, polypropylene resins (P
Molded articles made of thermoplastic resins such as P) and high-density polyethylene resin (PE) are also widely used. However, the interior member of the conventional bathroom is apt to be stained with water scale, oil, mold and the like, and has a poor appearance, which is not preferable in terms of hygiene.
Therefore, it is necessary to take time-consuming treatment such as cleaning with a detergent or the like as a measure for removing dirt.

[0003] In the interior member of the bathroom as described above, a transparent gel coat layer may be formed on the surface thereof to give a sense of transparency and luxury. That is, the gel coat composition is an unsaturated polyester resin, a vinyl ester resin,
A thermosetting acrylic resin, an epoxy resin, a liquid thermosetting resin composition containing a pigment, a curing accelerator, etc. alone or in a mixture of a phenol resin, etc., and a polymerization initiator added thereto, and spray or After application to the mold surface with a brush, it is used, for example, by FRP molding, or directly applied on the molded product, and it is used with water, hot water and It functions as a protective layer against ultraviolet rays and the like, but does not have an antifouling function.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and aims at maintenance-free operation which makes it possible to relatively easily remove dirt from the inner surface of a bathroom. It is.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a first gist of the present invention resides in a bathroom inner surface member and has a double bond on its surface. It is characterized in that a gel coat layer is formed by mixing a modified silicone oil containing a double bond in a molecule with a base resin contained in the molecule to impart antifouling property.

A second gist of the present invention is a glass fiber reinforced plastic in a bathroom inner surface member, in which a modified silicone oil containing a double bond in a molecule is mixed with a base resin containing a double bond in a molecule. It is characterized by becoming.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies on gel coat compositions, the present inventors have found that base resins containing double bonds in the molecule, such as unsaturated polyester resins, vinyl ester resins, and thermosetting acrylic resins. It has been found that the above problem can be solved by a gel coat composition characterized by blending a modified silicone oil containing a double bond in the molecule to the present invention, and the present invention has been achieved. It forms a special silicone-containing layer, thereby imparting water repellency, and provides an antifouling effect by repelling dirt components. The index of water repellency is indicated by the contact angle of water,
Preferably it is 90 degrees or more.

[0008] The bathroom inner surface member of the present invention is not particularly limited, and is made of a thermosetting resin, and is formed by various molding methods such as RTM (resin transfer molding) molding, SMC molding, BMC molding, and hand lay-up molding. And other various molding methods. Usually, it is generally molded by so-called SMC molding or hand lay-up molding in which an unsaturated polyester resin is dispersed in a glass fiber mat and molded. In recent years, many injection molding (or injection compression) molding methods using a thermoplastic resin such as an ABS resin have appeared.

A water-repellent resin layer is formed on the surface of the inner member in order to impart an antifouling effect, that is, water repellency. The first (first invention) of the forming method is to form a gel coat composition having water repellency. The gel coat composition is applied directly to the inner surface of the inner member, or the gel coat composition is applied to the surface of the mold for molding the inner member, and in this state, the resin for forming the inner member is filled in the mold and the gel coat layer is integrally formed on the inner member surface. Can be formed. Here, as an example of the latter, the outline will be described by a hand lay-up method.A gel coat composition is applied to a mold surface, and after drying this, an unsaturated polyester resin containing an inorganic filler or a pigment is applied. A polyester resin containing glass fibers is laminated while defoaming, and is heated and cured, and then demolded to obtain an inner surface member. In the case of RTM molding, for example, a gel coat composition is formed on the mold surface. And then apply a polyester resin containing inorganic fillers and pigments, and further place a preformed chopped strand glass mat on the inside surface of the bathroom, close the mold here, and put the curing agent in the mold. It is obtained by injecting and heating and curing a polyester resin contained therein. According to the second (second invention) SMC or BMC molding method of the forming method, for example, a filler, a release agent,
A curing agent, a thickener, etc. are compounded, and the modified silicone is further mixed with the mixture, and the resulting mixture is compressed and impregnated into a glass fiber mat to form a sheet. It is placed and cured under heat compression to obtain an inner member made of a glass fiber reinforced resin composition having a water-repellent surface.

A gel coat layer is formed to impart an antifouling effect, that is, water repellency. The gel coat layer is formed by directly applying the gel coat composition to the surface of the molded bathroom interior member, or by forming the bathroom interior member on the interior surface. The gel coat composition is applied to the mold surface to be molded, and in this state, a resin for molding the bathroom inner surface member is filled in the mold to form a gel coat layer integrally with the bathroom inner surface member. Here, as an example of the latter, the outline will be described by a hand lay-up method.A gel coat composition is applied to a mold surface, and after drying this, an unsaturated polyester resin containing an inorganic filler or a pigment is applied. A polyester resin containing glass fibers is laminated while defoaming. This is heated and cured, and then removed from the mold to obtain a bathroom inner surface member. Apply the composition, then apply a polyester resin containing inorganic fillers and pigments, and further place a preformed chopped strand glass mat in the approximate shape of the bathroom interior member, close the mold here, and put it in the mold It is obtained by injecting a polyester resin containing a curing agent and curing by heating. Of course, the gel coat composition can be applied to the SMC molding die surface using a thermosetting resin, and further can be applied to the injection compression molding die surface using a thermoplastic resin.

The gel coat composition or the glass fiber reinforced resin composition of the present invention contains 0.05 to 20 parts by weight of a modified silicone oil containing a double bond per 100 parts by weight of a base resin containing a double bond in a molecule. Parts, preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and the modified silicone oil contains an acryl group and / or a methacryl group, or one end has an acryl group. A silicone oil having a main chain of polydimethylsiloxane, or a silicone oil having an acrylic group and / or a methacryl group in a side chain and having a main chain of polydimethylsiloxane.

Although the amount of the modified silicone oil to be blended is appropriately selected, the base resin 100 having a double bond in the molecule may be used.
The silicone oil is blended in an amount of 0.1 to 10 parts by weight with respect to parts by weight. In addition, an organic peroxide or the like can be compounded in an amount as a polymerization initiator, and an antibacterial agent, a fungicide, and various third agents such as pigments and dyes for high design.
Components can be blended.

In the prior art, when silicone oil is blended, the silicone oil bleeds during use because there is no functional group in the molecule, and the antifouling performance lacks sustainability. In the present invention, the double bond in the base resin and the modified silicone oil react,
Or, since it is in a state close to a molecular compatibility, the antifouling effect has a lasting effect.

Hereinafter, the present invention will be described in more detail. As the base resin, any resin containing a double bond in the molecule may be used. In particular, unsaturated polyester resins, vinyl ester resins, and thermosetting acrylic resins are used. preferable. In this case, as the unsaturated polyester resin, vinyl ester resin, and thermosetting acrylic resin, those known as gel coat compositions can be used, and the following are particularly preferable.

As the unsaturated polyester resin, there are ortho-type, iso-type, tele-type, bis-type and the like. In the ortho-type, orthophthalic acid is used as a saturated dibasic acid component, and maleic anhydride and fumaric acid are used as an unsaturated dibasic acid component. The glycol component forms an ester bond with the saturated dibasic acid component and the unsaturated dibasic acid component using propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol or the like as a glycol component as a raw material. Isophthalic acid and terephthalic acid use isophthalic acid and terephthalic acid as saturated dibasic acid components, respectively, and bis-based unsaturated dibasic acid such as fumaric acid or maleic anhydride, and dihydroxypropylbisphenol A or hydrogenation as glycol component. Bisphenol A and propylene glycol, ethylene glycol, diethylene glycol or the like form an ester bond. As the vinyl ester-based resin, an addition reaction product of an epoxy resin and an unsaturated monobasic acid such as acrylic acid is used as a main chain compound, and bisphenol A type vinyl ester, brominated bisphenol A type vinyl ester, novolak type vinyl ester There are types such as esters. The unsaturated polyester resin and the vinyl ester resin are reacted with styrene in the presence of methyl ethyl kent peroxide or the like to form a three-dimensional structure. There are also various types of thermosetting acrylic resin.The type that introduces hydroxyl groups into the acrylic resin and makes it three-dimensional by the reaction between hydroxyl groups and amino resin or the reaction between hydroxyl groups and isocyanate. A type in which a main chain compound such as polyether to which an unsaturated monobasic acid such as is added is cured with a polyfunctional acrylate, and further, glycidyl acrylate or the like is copolymerized into an acrylic resin having a glycidyl group, and a carboxyl group or an acid anhydride group. Acrylic resin copolymerized with maleic anhydride, itaconic anhydride, etc. is cured with a compound having hydroxyl group, silanol group, etc. Type, 2-isopropenyl-2-oxazoline or 2- An acrylic resin copolymerized with niloxazoline is cured with a compound having a carboxyl group, an acid anhydride group, a phenol group, a thiol group, an epoxy group, an amide group, or an amino group. And a type in which an acrylic resin having a siloxy group, an active methylene group, a methoxy group, a carboxyl group, or the like is reacted with the functional group and cured with a compound having a functional group that cures.

On the other hand, as the modified silicone oil containing a double bond in the molecule, one containing an acryl group and / or a methacryl group in the molecule is preferable, and R- (Si (CH (CH
₃ ) ₂ —O) _n —Si (CH ₃ ) ₂ —R ′ (R is a non-reactive alkyl group such as a methyl group or a butyl group, R ′ is a functional group containing a double bond, for example, a methacryl group or Examples of the structure include an acrylic group, and n is a positive number), and one having an acrylic group and / or a methacryl group at one end and a polydimethylsiloxane in the main chain is preferable.

Another example of the modified silicone oil contained in eight double bond molecules is R-Si (CH ₃ ) ₂ -O-
_{(Si (CH 3) 2 -O} ) m - (SiR '(CH 3) -
O) _n -Si (CH ₃ ) ₂ -R (R is a non-reactive alkyl group such as a methyl group or a butyl group, R ′ is a functional group containing a double bond, and a group containing a methacryl group or an acrylic group. Further, those having an acrylic group and / or a methacrylic group in the side chain and having a main chain of polydimethylsiloxane, such as the structure of (m and n are positive numbers), are also preferably used.

The modified silicone oil having a double bond is a gel coat composition mainly composed of a base resin containing a double bond in a molecule such as an unsaturated polyester resin, a vinyl ester resin, a thermosetting acrylic resin and the like. Or, when mixed with a glass fiber reinforced resin composition and cured, a portion having a double bond such as a methacryl group reacts with a double bond of the base resin, and selectively does not react on the outermost surface of the coated layer. The concentration of the active polydimethylsiloxane molecule increases. Since the polydimethylsiloxane molecule has high water repellency, it is hardly stained and easily removed. Therefore, even if a straight silicone oil comprising only a non-reactive polydimethylsiloxane having no double bond is blended in the gel coat composition, water repellency does not appear unless the number of blended parts is considerably increased. Although there are silicone resins and silicone rubbers in a solid state at room temperature having a structure similar to that of the modified silicone oil, an oily substance at room temperature is excellent as an easy transfer to the outermost surface.

In this case, the modified silicone oil containing the double bond in the molecule becomes too viscous if the molecular weight is excessively large and cannot be selectively collected on the surface. If the molecular weight is too small, it becomes volatile and becomes hard to cure. It is preferable that the number average molecular weight is about 500 to 50,000 because components that volatilize appear.

[0020]

The present invention will be described below in detail with reference to examples and comparative examples. In the following examples, numerical values indicate parts by weight.

Example 1 A one-terminal reactive silicone oil having a methacrylic group at the terminal (a number average molecular weight of 4,6) was used as a modified silicone oil having a double bond with respect to 100 parts by weight of an unsaturated polyester resin-based gel coat resin.
00) was added in an amount of 0.5 part. To the gel coat composition, 1.0 part of methyl ethyl ketone peroxide was added and mixed as a polymerization initiator. Then, the gel coat composition was spray-coated to a thickness of 0.3 mm on the predetermined surface side of the RTM mold, cured at 60 ° C. for 15 minutes, and then removed from the mold to form a gel coat film by so-called hand lay-up molding. Was obtained.

Example 2 An acrylic modified silicone oil having an acrylic group in a side chain and a main chain of polydimethylsiloxane is used as a modified silicone oil having a double bond with respect to 100 parts of an unsaturated polyester resin-based gel coat resin. (Number average molecular weight: 6,000) was added in an amount of 0.5 part. After adding 1.0 part of methyl ethyl ketone peroxide as a polymerization initiator to the gel coat composition and mixing, an inner surface member having a gel coat film formed thereon was obtained in the same manner as in Example 1.

Example 3 100 parts of a gel coat resin based on a vinyl ester resin have the same acrylic group in the side chain as the modified silicone oil having a double bond in the side chain, and the main chain is polydimethylsiloxane. Acrylic modified silicone oil (number average molecular weight 6,000)
Was blended in an amount of 0.5 part. After adding and mixing 1.0 part of methyl ethyl ketone peroxide as a polymerization initiator to the gel coat composition, an inner surface member having a gel coat film formed in the same manner as in Example 1 was obtained.

Example 4 A thermosetting acrylic resin-based gel coat resin having 100 parts of a modified silicone oil having a double bond in the side chain having the same acrylic group as in Example 2 and having a main chain of polydimethylsiloxane Acrylic modified silicone oil which is siloxane (number average molecular weight 6,000)
Was blended in an amount of 0.5 part. After adding and mixing 1.0 part of methyl ethyl ketone peroxide as a polymerization initiator to the gel coat composition, an inner surface member having a gel coat film formed in the same manner as in Example 1 was obtained.

Example 5 Unsaturated polyester resin 10
Two parts of a modified silicone oil having a double bond and one end-reactive silicone oil having a methacryl group at the terminal (number average molecular weight of 4,600) was added to 0 parts. 6 parts of polyethylene, 1 part of t-butyl peroxybenzoate, 4 parts of zinc stearate, 100 parts of calcium carbonate
Part of the mixture, and further mixed with 1 part of magnesium oxide, impregnated into a glass fiber chopped strand mat to obtain SMC (glass fiber content: 25% by weight), and cured at a curing temperature of 140 ° C. for 3 minutes to obtain glass fiber. An inner member made of reinforced plastic was obtained.

Comparative Example An inner member having a gel coat film formed thereon was manufactured in the same manner as in Example 1. No silicone oil having a double bond was added.

[Test 1] The contact angle of water was measured for the bathroom inner surface member obtained by applying the above gel coat film. The contact angle of water was measured by a Kyowa Kagaku contact angle meter, and the average of three measurements was recorded. As a result of the measurement, the contact angle was 101 degrees in Example 1, and 103 degrees in the following order.
Degrees, 95 degrees and 97 degrees, all of which showed good results. On the other hand, it was 85 degrees in the comparative example, and the antifouling function could not be expected.

[Test 2] Magic Ink (registered trademark) was applied to the storage panel coated with the above gel coat film.
A wiping test was performed. That is, an oil-based magic ink was applied to the surface, dried, and wiped off. Although wiping was possible in each example, wiping was not possible in the comparative example.

[0029]

According to the present invention, a bathroom inner surface member which is relatively inexpensive and exhibits high antifouling properties can be provided, and its practical value is high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 167/06 167/06 183/07 183/07 C08L 101: 00 C08L 101 : 00 F term (reference) 2D032 GA00 2E025 BA01 BC01 BC02 4F006 AA22 AA34 AA35 AA42 AA53 AB42 AB43 BA11 CA00 DA04 EA05 4F072 AB09 AB29 AD09 AD34 AD38 AD47 AG03 AG04 AH04 AH31 AJ04 AK05 AK14 DB061121 DG14 GA06 GA08 GA15 KA03 MA14 NA05 NA07 PA19 PB04 PB05 PC08

Claims (8)

[Claims] A gel coat comprising a base resin containing a double bond in a molecule and a modified silicone oil containing a double bond in a molecule, at least on a surface constituting the interior of the bathroom in a bathroom inner surface member. A bathroom inner surface member having an antifouling property, wherein a layer is formed. 2. A bathroom interior surface member comprising a glass fiber reinforced plastic in which a modified silicone oil containing a double bond in a molecule is mixed with a base resin containing a double bond in a molecule. Bathroom interior surface member provided with antifouling property. 3. RTM molding, SMC molding, BMC molding,
The bathroom interior member having antifouling properties according to claim 1 or 2, obtained by hand lay-up molding. 4. The base resin of the gel coat composition or the glass fiber reinforced plastic composition containing a double bond in a molecule is selected from unsaturated polyester resins, vinyl ester resins and thermosetting acrylic resins. A bathroom interior member having the antifouling property according to claim 1 or 2. 5. The gel coat composition or the glass fiber reinforced plastic composition contains 0.05 to 20 parts by weight of a modified silicone oil containing a double bond based on 100 parts by weight of a base resin containing a double bond in a molecule. The bathroom interior member provided with the antifouling property according to claim 1 or 2 which is blended. 6. The antifouling bathroom interior member according to claim 1, wherein the modified silicone oil containing a double bond contains an acryl group and / or a methacryl group. 7. The antifouling property according to claim 1, wherein the modified silicone oil containing a double bond has an acrylic group and / or a methacrylic group at one end and a polydimethylsiloxane in the main chain. Bathroom interior components. 8. The bathroom provided with antifouling properties according to claim 1, wherein the modified silicone oil containing a double bond has an acryl group and / or a methacryl group in a side chain, and the main chain is made of polydimethylsiloxane. Inner surface member.