JPH1029246A - Fiber reinforced plastic molding, bathtub and washing place and manufacture of fiber reinforced plastic molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make stain adhesion difficult, and realize sanitary usage in a member made of fiber reinforced plastic used in the neighborhood of a bathroom by a method wherein a surface layer is made of organic silica compound- containing unsaturated polyester resin-based gelcoat resin. SOLUTION: Uniform dispersion is obtained by agitatingly adding the respective predetermined amounts of organic silicon compound 1 represented by acrylic modified organopolysiloxane, inorganic antibacterial agent 2 represented by silver zeolite and organic antibacterial agent 3 represented by TBZ to gelcoat resin 4 made of isophthalatic acid-based unsaturated polyester resin. Further, after being added with the proper amount of hardener and hardening accelerator, the dispersion is formed into coating film with a spray gun so as to form a gelcoat layer by hardening. After forming a fiber reinforced plastic layer 5 made of glass fibers and unsaturated polyester resin to the gelcoat layer, the resultant assembly is removed from a mold so as to allow to obtain an aimed molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having excellent stain resistance and made of fiber reinforced plastic which can be used as a raw material for water such as a bathtub, a washing place, a counter and a kitchen counter.

[0002]

2. Description of the Related Art Conventionally, fiber-reinforced plastics using unsaturated polyester resin and glass fiber have been used in areas where waterproofness is required, such as bathtubs and washing places, and where light weight and high strength are required. Was. These laminated structures are generally composed of a monochromatic gel coat layer and a fiber reinforced plastic layer from the surface. Gel coat layer is a coating film used to improve hot water resistance and chemical resistance,
Painted by spray-up method. The gel coat resin is used by coloring an unsaturated polyester resin with a single color pigment and adding a fine silicon oxide powder so as to be suitable for coating to obtain a state suitable for coating (called thixotropic). As a general molding method, a gel coat is applied to a mold and cured, followed by laminating a fiber reinforced plastic made of glass fiber and an unsaturated polyester resin, curing and then releasing the mold.

On the other hand, thermoplastic pellets formed by adding an organic silicon compound or an antibacterial agent to pellets have been put to practical use, but there is no example applicable to thermosetting plastics such as unsaturated polyester resins. Therefore, there is no measure against the occurrence of dirt, mold, or slime in a member such as a bathtub or a washing place made of a thermosetting plastic used around a bathroom, and a measure of simply removing the member by cleaning has been taken. Many of the causes of slimming are due to the propagation of bacteria, and fungi and bacteria multiply on attached dirt.

[0004]

SUMMARY OF THE INVENTION In these members made of fiber reinforced plastic used around the bathroom, it is difficult to adhere dirt, and it is necessary to suppress the propagation of mold and bacteria that multiply the dirt on the bait, thereby improving hygiene. The challenge was to be able to use it.

[0005]

The molded article of the present invention is a molded article made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer is an unsaturated polyester containing an organosilicon compound. It is composed of a resin-based gel coat resin.

According to the above invention, the water repellency of the surface layer is improved, and the interaction with the dirt component is reduced, so that the antifouling property is greatly improved. In addition, mold and bacteria also have a small amount of adherent dirt, and their growth is also suppressed.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer is made of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound. It is a molded article of a fiber reinforced plastic.

The surface layer is a bath of a fiber-reinforced plastic made of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound.

The surface layer is a washing place for fiber-reinforced plastics composed of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound.

Since the organosilicon compound is a low surface free energy substance, the gel coat resin surface layer containing the same has a low activity with respect to a dirt component, thereby improving the antifouling property.
Furthermore, since the adhesion of the dirt components is reduced, the growth of mold and bacteria that feed on them is suppressed.

The surface layer is a molded article made of a fiber-reinforced plastic composed of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound and an antibacterial agent. Molding made of a fiber reinforced plastic composed of an antibacterial agent comprising at least one of an inorganic antibacterial agent as an antibacterial agent, and an unsaturated polyester resin-based gelcoat resin containing an antibacterial agent comprising at least one organic antibacterial agent and an organosilicon compound. Body.

Further, the organic silicon compound is added in an amount of 0.1 to 100 parts by weight of the unsaturated polyester resin-based gel coat resin.
It is a molded article of a fiber-reinforced plastic comprising a surface layer containing 3 to 5 parts by weight. Further, when the organic silicon compound is an unsaturated polyester resin-based gel coat resin 10
0.3 to 5 parts by weight with respect to 0 parts by weight,
Further, it is a molded article of fiber reinforced plastic comprising a surface layer further containing an antibacterial agent.

The surface layer contains 0.1 to 5 parts by weight of an inorganic antimicrobial agent and 0.1 to 5 parts by weight of an organic antimicrobial agent per 100 parts by weight of an organic silicon compound and an unsaturated polyester resin gel coat resin. A molded article of a fiber-reinforced plastic comprising an unsaturated polyester resin-based gel coat resin contained in an amount of 1 to 5 parts by weight.

The surface layer is made of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound and an antimicrobial agent, thereby improving the antifouling property. The growth of bacteria causing slime is suppressed, and the addition of an organic antibacterial agent suppresses the growth of mold. The addition of the organosilicon compound reduces the adhesion of dirt components, which become bait for bacteria and mold, and therefore, a small amount of inorganic antibacterial agent and organic antibacterial agent can be expected to have a sufficient effect.

The surface layer has at least two types of gel coat resins and at most five types of gel coat resins, and a ratio of at least 0.3 parts by weight to at most 5 parts by weight of the organosilicon compound to 100 parts by weight of at least one type of gel coat resin. To form a surface layer by atomization and painting.

Further, the surface layer has two to five types of gel coat resins, and at least one type of the gel coat resin is added with 0.3 parts by weight of an organosilicon compound to 100 parts by weight.
A bath containing not less than 5 parts by weight and not more than 5 parts by weight.

The surface layer has two to five types of gel coat resins, and the organic silicon compound is contained in the range of 0.3 to 5 parts by weight based on 100 parts by weight of at least one type of gel coat resin. It is a washing place.

By using two or more and five or less gel coat resins for the surface layer, a molded article having a pattern can be obtained, and at the same time, a molded article having an antifouling effect can be obtained by adding an organic silicon compound. . Further, by forming the surface layer by atomization and painting, a molded article having a pattern such as a shadow pattern can be obtained, and at the same time, a molded article having an antifouling effect as described above can be obtained.

Further, by applying the molded article to a bathtub or a washing place, it is possible to provide a bathroom member which is provided with a pattern and has excellent stain resistance.

Hereinafter, the present invention will be described in detail with reference to examples. Examples of the organic silicon compound in the present invention include silicone compounds such as dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane. These silicone compounds include, but are not limited to, alkyd-modified, polyester-modified, acryl-modified, and epoxy-modified silicone compounds.

The antibacterial agent in the present invention includes silver nitrate, silver sulfate and silver chloride as inorganic antibacterial agents. Zeolite supporting silver, copper, zinc or tin. And silica gel supporting silver, copper, zinc or tin, but not limited thereto.

As an organic antibacterial agent, a phenyl ether derivative such as 10,10'-oxybisphenoxaarsine, an N-haloalkylthio compound such as cyclofluanide, 2- (4-thiazolyl) benzimidazole (TB)
Z); sulfone derivatives such as 2,3,5,6 tetracholol-4- (methylsulfonyl) pyridine; and quaternary ammonium salts such as cetyldimethylethylammonium bromide. is not.

Example 1 0.3 parts by weight of an acryl-modified organopolysiloxane, 0.1 parts by weight of silver zeolite and 0.1 parts by weight of TBZ were added to 100 parts by weight of a gel coat resin composed of an isophthalic unsaturated polyester resin. Then, the mixture was uniformly dispersed by stirring. A predetermined curing agent and a curing accelerator were added thereto, and a coating film having a thickness of about 0.5 mm was formed by a spray gun and cured to form a gel coat layer. Subsequently, a fiber-reinforced plastic layer composed of glass fibers and an unsaturated polyester resin was formed by a known method. This was removed from the mold to obtain the desired molded product.

FIG. 1 is a schematic view showing a surface portion of a molded article in Example 1 of the present invention. 1 is an organic silicon compound represented by an acrylic-modified organopolysiloxane. 2
Is an inorganic antibacterial agent represented by silver zeolite. 3 is an organic antibacterial agent represented by TBZ. 1, 2 and 3 are dispersed in the gel coat resin layer 4, respectively.
5 is a fiber reinforced plastic layer made of glass fiber and unsaturated polyester resin.

Example 2 1 part by weight of an acryl-modified organopolysiloxane, 0.5 part by weight of silver zeolite, and 0.5 part by weight of TBZ were added to 100 parts by weight of a gel coat resin composed of an isophthalic unsaturated polyester resin.
The mixture was uniformly dispersed by stirring. A predetermined curing agent and a curing accelerator were added thereto, and a coating film of about 0.5 mm was formed by a spray gun and cured. Subsequently, a target molded product was obtained in the same manner as in Example 1.

Example 3 2 parts by weight of an acryl-modified organopolysiloxane, 1 part by weight of silver zeolite, and 1 part by weight of TBZ were added to 100 parts by weight of a gel coat resin composed of an isophthalic unsaturated polyester resin, followed by stirring. Dispersed uniformly. A predetermined curing agent and a curing accelerator are added thereto, and about 0.5 mm
Was formed and cured. Subsequently, a target molded product was obtained in the same manner as in Example 1.

Example 4 3 parts by weight of an acryl-modified organopolysiloxane, 2 parts by weight of silver zeolite, and 2 parts by weight of TBZ were added to 100 parts by weight of a gel coat resin composed of an isophthalic unsaturated polyester resin, followed by stirring. Dispersed uniformly. A predetermined curing agent and a curing accelerator are added thereto, and about 0.5 mm
Was formed and cured. Subsequently, a fiber-reinforced plastic layer composed of glass fibers and an unsaturated polyester resin was formed by a known method. By demolding this, a desired bathtub was obtained.

(Example 5) By the pressure of three gel coat tanks, three gel coat resins are discharged from a gun after passing through a certain mixing pipe, mixed with a curing agent and atomized at an arbitrary atomizing pressure. Using a multicolor gun device, the coating was performed under an atomizing pressure of 2.0 kg / cm ² . The three types of gel coat resins in the three gel coat tanks of the multicolor gun device and the discharge weight ratio are shown below.

[0029] To 100 parts by weight of the black gel coat resin, 2 parts by weight of an acryl-modified organopolysiloxane was previously added, and a black gel coat resin uniformly dispersed by stirring was used. The gel coat resin applied in this manner was cured at 50 ° C. for 30 minutes. The thickness of the gel coat after curing was 0.4 mm. Subsequently, a fiber-reinforced plastic layer composed of glass fibers and an unsaturated polyester resin was formed by a known method. This was removed from the mold to obtain the desired patterned molded body.

As shown in FIG. 2, the molded article obtained by such a method is a part 6 of a gel coat resin containing an organic silicon compound represented by an acrylic-modified organopolysiloxane.
And a portion 7 of the gel coat resin not containing them. By scattered in this manner, the surface design becomes a spot pattern.

(Example 6) Two gel coat resins are discharged from a gun after passing through a certain mixing pipe by the pressure of two gel coat tanks, mixed with a hardener, and atomized at an arbitrary atomization pressure. Was applied to a mold in a washing room under the conditions of an atomizing pressure of 2.0 kg / cm ² .
The two types of gel coat resins in the two gel coat tanks of the multicolor gun device and the discharge weight ratio are shown below.

[0032] A black gel coat resin was used in which 2 parts by weight of an acryl-modified organopolysiloxane was previously added to 100 parts by weight of the black gel coat resin and uniformly dispersed by stirring. The gel coat resin applied in this manner was cured at 50 ° C. for 30 minutes. The thickness of the gel coat after curing was 0.4 mm. Subsequently, a fiber-reinforced plastic layer composed of glass fibers and an unsaturated polyester resin was formed by a known method. By removing the mold, a desired patterned washing place was obtained.

Comparative Example 1 A predetermined curing agent and a curing accelerator were added to a gel coat resin composed of the same isophthalic unsaturated polyester resin as in Example 1, and a coating film of about 0.5 mm was formed with a spray gun. Formed and cured to form a gel coat layer. Subsequently, a fiber-reinforced plastic layer composed of glass fibers and an unsaturated polyester resin was formed by a known method. This was removed from the mold to obtain the desired molded product.

Comparative Example 2 0.2 parts by weight of an acryl-modified organopolysiloxane, 0.05 parts by weight of silver zeolite and 0.05 parts by weight of TBZ were added to 100 parts by weight of a gel coat resin composed of an isophthalic unsaturated polyester resin. Then, the mixture was stirred and dispersed. A predetermined curing agent and a curing accelerator are added to this, and about 0.5 m
m were formed and cured. Subsequently, a target molded body was obtained in the same manner as in Example 1.

The water repellency of the surfaces of the moldings, bathtubs and washing surfaces obtained in the respective Examples and Comparative Examples was measured by Kyowa Interface Science Co., Ltd. It measured with the contact angle measuring device (CA-Z type).
Further, stain resistance was confirmed according to JIS K3370. The stain resistance was compared visually, and the degree of contamination in Comparative Example 1 was defined as (△).
Good cases were evaluated as (（) and relative evaluations were made. The results are shown in (Table 1).

[0036]

[Table 1]

Next, tests were carried out on the antibacterial performance and the mold resistance of each molded product, bathtub and washing place obtained in each of the examples and comparative examples. 50m from the molded body
A sample of mx 50 mm was cut out, and 1 cc of a bacterial solution (general bacteria and Escherichia coli) was added dropwise to each sample, and cultured at 37 ° C for 24 hours. Thereafter, the bacteria were washed out with a sterilized phosphate buffer. The viable cell count in the washed-out liquid was measured by a pour plate method using a cell count medium. The results are shown in (Table 2).

[0038]

[Table 2]

Each sample (50 mm × 5 mm) on an agar medium
0 mm) and sprayed with Aspergillus niger bacteria solution.
C. for 7 days. The results are shown in (Table 3).

[0040]

[Table 3]

As is evident from (Table 1), the first embodiment
The molded articles of Nos. 1 to 6 showed a remarkable improvement in water repellency as compared with Comparative Example 1, and also had improved stain resistance. In contrast,
Compared to Comparative Example 1, the molded article of Comparative Example 2 showed little improvement in water repellency and stain resistance.

In addition to the case where the organic silicon compound is uniformly dispersed on the surface (Examples 1 to 4), the excellent water repellency and the good water repellency can be obtained not only when the organic silicon compound is dispersed as in Examples 5 and 6. It became clear that stain resistance was obtained. The reason is that when water droplets 8 adhere to the surface as shown in FIG. 2, a part 6 of the gel coat resin containing the organosilicon compound comes in contact with a part of the water droplets 8 and good water repellency and stain resistance are obtained. Think you can get it. Further, when a molded article is formed using more than five types of gel coat resins and various colors, a remarkable water repellent effect and an antifouling effect cannot be obtained. Therefore, two to five types of gel coat resins are suitable. The reason for this is that when the number of gel coat resins becomes six or more, the probability that water droplets adhering to the surface do not contact the part 6 of the gel coat resin containing the organosilicon compound increases as shown in FIG.
It is considered that the water repellent effect and the antifouling effect are reduced.

If the upper limit of the amount of the organosilicon compound is more than 5 parts by weight with respect to 100 parts by weight of the gel coat resin, the basic physical properties such as hot water resistance and chemical resistance of the gel coat resin are unfavorably deteriorated. From the above results, 0.3 parts by weight or more and 5 parts by weight with respect to 100 parts by weight of gel coat resin
It has been found that the effect of the present invention can be obtained by adding the organic silicon compound in an amount of not more than part by weight.

In the above description, only the method of adding an organosilicon compound to at least one kind of gel coat resin among two to five kinds of gel coat resins has been described. It goes without saying that a compound may be added.

As is clear from (Table 2), the first embodiment
The molded articles Nos. To 4 were able to obtain a remarkable antibacterial effect on general bacteria and Escherichia coli as compared with Comparative Example 1. On the other hand, the antibacterial property of the molded article of Comparative Example 2 is not clear as compared with Comparative Example 1.

Regarding the upper limit of the amount of the inorganic antibacterial agent,
If the amount exceeds 5 parts by weight with respect to 100 parts by weight of the gel coat resin, the basic physical properties such as the chemical resistance of the gel coat resin are deteriorated, which is not preferable. From the above results, the gel coat resin 1
It was found that the action and effect of the present invention can be obtained by adding 0.1 to 5 parts by weight of an inorganic antibacterial agent to 00 parts by weight.

As is clear from (Table 3), the first embodiment
The molded articles Nos. To 4 were able to obtain remarkable antifungal performance as compared with Comparative Example 1. On the other hand, the molded article of Comparative Example 2 has a remarkable antifungal effect as compared with Comparative Example 1.

Regarding the upper limit of the amount of the organic antibacterial agent,
If the amount exceeds 5 parts by weight with respect to 100 parts by weight of the gel coat resin, the basic physical properties such as hot water resistance of the gel coat resin are deteriorated, which is not preferable. From the above results, the gel coat resin 1
It was found that the action and effect of the present invention can be obtained by adding 0.1 to 5 parts by weight of an organic antibacterial agent to 00 parts by weight.

[0049]

As described above, according to the molded article of the fiber-reinforced plastic and the bathtub or washing place of the present invention, the following effects can be obtained.

In a molded article made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, the surface layer contains an organic silicon compound, and the gel coat resin is formed by a low surface energy effect of the organic silicon compound. The surface layer has a low activity with respect to dirt components, and the antifouling property is improved. Furthermore, since the adhesion of the dirt component is reduced, the advantageous effect that the growth of the mold and the bacterium which feed on them is suppressed is also provided.

Further, the surface layer is made of a fiber-reinforced plastic bath made of an unsaturated polyester resin-based gel coat resin containing an organosilicon compound, so that a clean and clean bathroom member to which dirt does not easily adhere can be obtained. Can be.

Further, the surface layer is provided as a washing place for a fiber-reinforced plastic made of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound.
A clean and clean bathroom member to which dirt does not easily adhere can be obtained.

The surface layer is made of a fiber-reinforced plastic formed of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound and an antibacterial agent. More positively, a hygienic and clean molded article can be obtained.

Further, as an antibacterial agent, at least one kind of inorganic antibacterial agent, and a fiber reinforced plastic composed of an antibacterial agent comprising at least one kind of organic antibacterial agent and an unsaturated polyester resin-based gel coat resin containing an organic silicon compound. By using a molded body made of the above, a molded body with little adhesion of dirt and actively suppressing the growth of Escherichia coli, general bacteria, and mold can be obtained.

Further, the amount of the organic silicon compound is 0.1 to 100 parts by weight of the unsaturated polyester resin gel coat resin.
3 parts by weight to 3 parts by weight;
5 parts by weight to 5 parts by weight, and further, 0.1 to 5 parts by weight of an organic antibacterial agent is used to form a molded article of a fiber-reinforced plastic made of an unsaturated polyester resin-based gel coat resin to provide mechanical strength. Alternatively, a molded article having antifouling property, antibacterial property and antifungal property while maintaining basic properties such as hot water resistance can be obtained.

The surface layer has two to five types of gel coat resins, and contains at least 0.3 part by weight and no more than 5 parts by weight of an organosilicon compound per 100 parts by weight of at least one type of gel coat resin. By using the molded article, a molded article having a pattern can be obtained, and at the same time, a molded article having water repellency and stain resistance can be obtained. Further, by using a bathtub or a washing place, it is possible to obtain a clean and clean water surrounding component having a water repellency and an antifouling property at the same time that a pattern is provided.

By spraying and atomizing, a molded article having a pattern such as a shadow pattern can be obtained.
A molded article having water repellency and stain resistance can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a surface portion of a molded body according to a first embodiment of the present invention.

FIG. 2 is a schematic view showing a surface portion of a molded body according to a fifth embodiment of the present invention.

[Explanation of symbols]

Reference Signs List 1 organic silicon compound 2 inorganic antibacterial agent 3 organic antibacterial agent 4 gel coat resin 5 fiber reinforced plastic 6 part of gel coat resin containing organic silicon compound 7 part of gel coat resin not containing organic silicon compound 8 water droplet

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication // B29K 67:00 B29L 31:10

Claims (10)

[Claims] 1. A molded article made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer is made of an unsaturated polyester resin-based gel coat resin containing an organic silicon compound. Molded body of fiber reinforced plastic. 2. A bathtub made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer is made of a fiber-reinforced plastic bath made of an unsaturated polyester resin containing an organic silicon compound. . 3. A washing place made of a fiber reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer is made of a fiber reinforced plastic made of an unsaturated polyester resin containing an organosilicon compound. . 4. The fiber-reinforced plastic molded article according to claim 1, wherein the unsaturated polyester resin-based gel coat resin contains an organic silicon compound and an antibacterial agent. 5. The molded article of fiber-reinforced plastic according to claim 4, wherein the antibacterial agent comprises at least one of an inorganic antibacterial agent and at least one of an organic antibacterial agent. 6. The fiber reinforced plastic according to claim 1, wherein the organic silicon compound is contained in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the unsaturated polyester gel coat resin. Molded body. 7. An antibacterial agent as an antibacterial agent is added in an amount of 0.1 to 100 parts by weight of the unsaturated polyester gelcoat resin.
5 parts by weight to 5 parts by weight, and 0.1 parts by weight of the organic antibacterial agent to 100 parts by weight of the unsaturated polyester-based gel coat resin.
The fiber-reinforced plastic molding according to claim 5, wherein the content is from 5 parts by weight to 5 parts by weight. 8. A molded article made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer has two to five types of gel coat resins, and at least one of the gel coat resins is used. The organosilicon compound was added to the gel coat resin in an amount of 100 parts by weight.
A method for producing a molded article of a fiber-reinforced plastic which forms a surface layer by adding at a ratio of 3 parts by weight or more and 5 parts by weight or less, atomizing and coating. 9. A bath made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer has two to five types of gel coat resins, and at least one type of gel coat resin is used. 0.3 parts of organosilicon compound per 100 parts by weight of resin
A bath of fiber reinforced plastic containing not less than 5 parts by weight and not more than 5 parts by weight. 10. A washing place made of a fiber-reinforced plastic having a surface layer made of an unsaturated polyester resin-based gel coat resin, wherein the surface layer has two to five kinds of gel coat resins, and at least one kind of gel coat resin is used. A washing place for fiber-reinforced plastics containing 0.3 to 5 parts by weight of an organic silicon compound per 100 parts by weight of a resin.