JPH0655549A - Artificial marble style bathtab - Google Patents

Abstract

PURPOSE:To avoid cracking when molding is performed and to obtain an artificial marble style bathtab with excellent hot water resistance and heat resistance by using a compsn. contg. an unsatd. polyester prepd. by reacting an unsatd. dibasic acid and/or an acid anhydride thereof with a hydrogenated bisphenol A propylene oxide derivative and a polymerizable monomer. CONSTITUTION:A hydrogenated bisphenol A propylene oxide derivative to be used is expressed by formula I. In the formula, m and n are each an integer to make m+n 2.2-4.0 on average. An unsatd. polyester using this is dissolved in a polymerizable monomer to form a gelcoat layer and/or a cast layer. It is possible thereby to suppress discoloration of a cured product, to avoid generation of cracks caused by internal stress during curing and to obtain an artificial marble style bathtab with excellent hot water resistance, heat resistance, weatherability and workability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial marble-like bathtub, and more particularly to an artificial marble-like bathtub which prevents cracks during molding and has excellent hot water resistance, heat resistance and workability.

[0002]

2. Description of the Related Art Conventionally, an isophthalic acid-modified unsaturated polyester resin has been mainly used as a gel coat layer for an artificial marble bath. However, in the case of this isophthalic acid-modified unsaturated polyester resin, cracks and blisters may occur on the surface of the bath due to resin deterioration during long-term use, fading, loss of luster, and easy adhesion of dirt etc. There was a drawback to In order to deal with this drawback, as a gel coat layer, unsaturated polyester resin, epoxy resin, etc. obtained by using a polyhydric alcohol component such as water-added bisphenol A and bisphenol A propylene derivative which are mainly used for anti-corrosion Is used. In the case of these resins, the above-mentioned drawbacks can be solved, but there is a drawback that the coloring and / or gloss on the surface of the molded product is deteriorated due to intense coloring after curing and long-term deterioration such as ultraviolet rays. In order to prevent coloring and / or gloss reduction due to long-term deterioration such as ultraviolet rays, we are trying to deal with it by using an ultraviolet absorber, but the coloring after curing becomes more intense and the coloring prevention effect can not occur much. Therefore, the solution is strongly desired. On the other hand, an isophthalic acid-modified unsaturated polyester resin is mainly used also as a casting layer of an artificial marble bathtub. In the case of this isophthalic acid-modified unsaturated polyester resin, the adhesiveness with the filler may be reduced during long-term use to reduce transparency, or blister may occur on the gel coat surface due to the reduced adhesiveness. There was a flaw. In order to deal with this drawback, as in the gel coat layer, unsaturated polyester resin and epoxy obtained by using a polyhydric alcohol component such as water-added bisphenol A and bisphenol A propylene derivative which are mainly used for anti-corrosion. Resin or the like is used. In the case of these resins, the above-mentioned drawbacks can be solved, but there are drawbacks that the coloring of the cured product becomes severe, and cracks occur due to internal stress during curing. As a method of preventing the occurrence of cracks due to internal stress during curing, the reactivity of the unsaturated polyester resin is lowered, or a part of the acid-glycol component is changed to increase the elongation of the cured product to soften it. However, in this case, the hot water resistance and the heat resistance also decrease, and the solution thereof is strongly desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, suppresses coloring of the cured product, prevents the occurrence of cracks due to internal stress at the time of curing, and is resistant to hot water and heat. Provided is an artificial marble-like bathtub having excellent properties, weather resistance, and workability.

[0004]

The present invention relates to an unsaturated dibasic acid and / or its acid anhydride and a compound represented by the general formula [I].

[Chemical 2] An unsaturated polyester and a polymerizable monomer obtained by reacting with a hydrogenated bisphenol A propylene oxide derivative represented by the formula (m and n are integers in which m + n is 2.2 to 4.0 on average) The present invention relates to an artificial marble-like bathtub formed by forming a gel coat layer and / or a casting layer with an unsaturated polyester resin composition containing

Unsaturated dibasic acid and / or used in the present invention
Alternatively, as the acid anhydride thereof, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, etc. are used. These may be used in combination of two or more. Further, if necessary, a saturated dibasic acid and / or its acid anhydride can be used, and examples of these compounds include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid and trimellitic anhydride. , Succinic acid,
Azelaic acid, adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, rosin-maleic anhydride adduct, chlorendic acid, chlorendic anhydride, tetrachlorophthalic acid, tetra Chlorophthalic anhydride, tetrabromophthalic acid, tetrabromophthalic anhydride, etc. are used. The amount of the unsaturated dibasic acid and / or its acid anhydride is preferably 70 mol% or more of the acid component from the viewpoint of reactivity, hot water resistance of the molded article, heat resistance and the like. In the present invention, the hydrogenated bisphenol A propylene oxide derivative represented by the above general formula is used as the polyhydric alcohol component. This hydrogenated bisphenol A propylene oxide derivative is hydrogenated bisphenol A
The average amount of propylene oxide added is 2.2 mol to 4.0 mol per mol. If the amount of propylene oxide added is less than 2.2 mol, cracks will occur in the gel coat layer due to stress during demolding and thermal shock during use, and if it exceeds 4.0 mol, resin will remain on the bath surface during long-term use. Deterioration causes cracks and blisters, fading, loss of luster, and dirt. If the amount of propylene oxide added is less than 2.2 mol, cracks are generated in the casting layer due to stress during curing and / or demolding and thermal shock during use, and exceed 4.0 mol. When,
During long-term use, the unsaturated polyester resin deteriorates and the adhesiveness with the filler decreases, resulting in decreased transparency and blistering on the gel coat surface.

In the present invention, in addition to the above-mentioned derivatives, other polyhydric alcohol components such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexane may be added if necessary. Diol, neopentyl glycol, triethylene glycol, isopentyl glycol, 2,2-diethyl-1,3-propanediol, 2
It is also possible to use -n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, glycerin, trimethylolpropane, dicyclopentadiene, pentaerythritol and the like. . The amount of the bisphenol A propylene oxide derivative is preferably 50 mol% or more of the polyhydric alcohol component from the viewpoint of hot water resistance and heat resistance of the molded product.
The ratio of the acid component and the alcohol component of the unsaturated polyester used in the present invention is preferably 1.0 / 1.0 to 1.3 in terms of total number of carboxyl groups / total number of hydroxy groups.
The unsaturated polyester used in the present invention is obtained by subjecting the acid component and the polyhydric alcohol component to a condensation reaction, and this reaction is carried out by desorbing water generated when both components react to the outside of the system. proceed.

The unsaturated polyester thus obtained is dissolved in a polymerizable monomer and cured with a curing agent to obtain a cured product with high heat resistance and water resistance. Examples of the polymerizable monomer used at this time include styrene, vinyltoluene, divinylbenzene, methyl methacrylate, vinyl acetate and the like.

Examples of the curing agent include azo compounds such as azobisisobutyronitrile, peracids such as t-butyl perbenzoate and t-butyl peroctoate, hydroperoxides, benzoyl peroxide, and peroxides. Lauroyl,
Peroxides such as dicumyl peroxide and methyl ethyl ketone peroxide, and various organic peroxides such as hydroperoxide such as cumene hydroperoxide are used. Further, these curing agents may be used, if necessary, for example, metal soaps such as cobalt naphthenate and cobalt octenoate, and quaternary dimethylbenzyl ammonium chloride and the like.
Primary ammonium salts, β-diketones such as acetylacetone, dimethylaniline, N-ethyl-metatoluidine,
It can also be used in combination with a curing accelerator such as amines such as triethanolamine. If necessary, additives such as a polymerization inhibitor such as hydroquinone may be added to the composition. Further, when coloring the gel coat layer and / or the casting layer, a commercially available organic or inorganic dye or pigment can be added to the composition.

The above composition is applied to a mold (lower mold) with a spray gun or the like and cured to form a gel coat layer. Then, the above composition is blended with a filler such as silicon dioxide and degassed, and the mixture is poured into a mold having a lid with an upper mold and cured to form a casting layer, which is formed into a desired shape. The artificial marble tone bath tub is obtained. still,
The above composition may be used in only one of the gel coat layer and the casting layer to form an artificial marble bath.

FIG. 1 shows a cross-sectional view of an example of the artificial marble bath according to the present invention. In FIG. 1, 1 is a gel coat layer (thickness 0.3 mm), 2 is a casting layer (thickness 10 mm), and 3 is a reinforcing layer (thickness 1 mm).

[0011]

EXAMPLES The present invention will be described below with reference to examples. In addition, "parts" in the following examples means "parts by weight". Example 1 10 moles of fumaric acid and 11 moles of hydrogenated bisphenol A propylene oxide derivative represented by the above general formula (bisol H-3PN, Toho Chiba brand name m + n is 3 on average) were mixed with a stirrer, a condenser and a temperature. It was charged in a four-necked flask having a meter and an inert gas inlet, and allowed to react for 15 hours at 210 ° C. by a conventional method while passing nitrogen gas to obtain an unsaturated polyester. To 70 parts of this unsaturated polyester, 30 parts of styrene monomer was added, and further 50 ppm of hydroquinone was added to obtain a composition A. Next, 97 parts of this composition A was added to the thixotropic agent (Elogiel 200,
3 parts of Aerosil Co., 0.1 part of cobalt naphthenate (cobalt content 6% by weight) and 1.0 part of a hardening agent (55% solution of methyl ethyl ketone peroxide) were added, and this was added to a cup gun (Wider 60, Iwata). (Manufactured by Mfg. Co., Ltd.) was applied to a molding die by spraying to a thickness of 0.3 mm and cured at 50 ° C. for 1 hour to form a gel coat layer. Composition A
To 100 parts, add 0.1 part cobalt naphthenate (cobalt content 6% by weight), 150 parts filler (silicon dioxide, M10S manufactured by Nippon Fellow Co., Ltd.) and 1.0 part hardener (methyl ethyl ketone peroxide 55% solution). Then, after mixing and defoaming with a stirrer, FRP was previously set as a reinforcing layer in the upper mold and poured into a molding mold and cured at 50 ° C. for 3 hours and then demolded.
I got an artificial marble bathtub. The characteristics are shown in Table 1.

Example 2 8 moles of fumaric acid, 2 moles of isophthalic acid and 11 moles of hydrogenated bisphenol A propylene oxide derivative (bisol H-3PN) were mixed with a stirrer, a condenser, a thermometer and an inert gas inlet. The flask was charged into a neck flask and reacted at 210 ° C. for 15 hours by a conventional method while passing nitrogen gas to obtain an unsaturated polyester. To 70 parts of this unsaturated polyester was added 30 parts of styrene monomer,
Further, 50 ppm of hydroquinone was added to obtain a composition B. The composition B was used, and otherwise the same as in Example 1 to form a gel coat layer, and the same as in Example 1 to form a casting layer to obtain an artificial marble tone bath. The characteristics are shown in Table 1.

Example 3 10 mol of fumaric acid, 7.5 mol of hydrogenated bisphenol A propylene oxide derivative (bisol H-3PN) and 3.5 mol of neopentyl glycol were added to a stirrer, a condenser, a thermometer and an inert gas inlet. Was charged in a four-necked flask having a pressure of 50 ° C. and reacted at 210 ° C. for 15 hours in a conventional manner while passing nitrogen gas to obtain an unsaturated polyester. To 70 parts of this unsaturated polyester, 30 parts of styrene monomer was added, and further 50 ppm of hydroquinone was added to obtain a composition C. The composition C was used, and otherwise the same as in Example 1 to form a gel coat layer, and the same as in Example 1 to form a casting layer to obtain an artificial marble tone bath. The characteristics are shown in Table 1.

Example 4 Composition A was used in the same manner as in Example 1 to form a gel coat layer. Separately, 6 mol of fumaric acid, 4 mol of isophthalic acid, 4.5 mol of propylene glycol, and 6.0 mol of neopentyl glycol were charged into a four-necked flask having a stirrer, a condenser, a thermometer and an inert gas inlet, and charged with nitrogen. An unsaturated polyester was obtained by reacting for 15 hours at 210 ° C. in a conventional manner while passing gas, and 30 parts of styrene monomer was added to 70 parts of the unsaturated polyester, and further 50 ppm of hydroquinone was added to obtain a composition D. Next, the composition D was used and the other treatments were performed in the same manner as in Example 1 to form a casting layer, thereby obtaining an artificial marble-like bath. The characteristics are shown in Table 1.

Example 5 The composition D of Example 4 was used, and otherwise the same treatment as in Example 1 was carried out to form a gel coat layer, and the composition A was further used and treated in the same manner as in Example 1 and poured. A mold layer was formed to obtain an artificial marble bathtub. The characteristics are shown in Table 1.

Comparative Example 1 10 mol of fumaric acid and 11 mol of hydrogenated bisphenol A propylene oxide derivative (bisol H-2PN) were placed in a four-necked flask having a stirrer, a condenser, a thermometer and an inert gas inlet, An unsaturated polyester was obtained by reacting at 210 ° C. for 15 hours in a conventional manner while passing nitrogen gas. To 70 parts of this unsaturated polyester, 30 parts of styrene monomer was added, and further 50 ppm of hydroquinone was added to obtain a composition E. The composition E was used and the same treatment as in Example 1 was carried out otherwise to form a gel coat layer, and the same treatment as in Example 1 was carried out to form a casting layer to obtain an artificial marble-like bath. The characteristics are shown in Table 1.

Comparative Example 2 10 mol of fumaric acid and 11 mol of hydrogenated bisphenol A propylene oxide derivative (bisol H-5PN) were charged into a four-necked flask having a stirrer, a condenser, a thermometer and an inert gas inlet. An unsaturated polyester was obtained by reacting for 15 hours at 210 ° C. in a conventional manner while passing nitrogen gas, and 30 parts of styrene monomer was added to 70 parts of this unsaturated polyester.
Composition F was obtained by adding 0 ppm. Then composition F
Was used to form a gel coat layer by the same procedure as in Example 1 and the same procedure as in Example 1 to form a casting layer to obtain an artificial marble tone bath. The characteristics are shown in Table 1.

Comparative Example 3 10 mol of fumaric acid and 11 mol of bisphenol A propylene oxide derivative (bisol H-2PN) were charged into a four-necked flask having a stirrer, a condenser, a thermometer and an inert gas inlet, and nitrogen gas was introduced. Passing through 21
An unsaturated polyester was obtained by reacting at 0 ° C. for 15 hours by a conventional method. To 70 parts of this unsaturated polyester, 30 parts of styrene monomer was added, and further 50 pp of hydroquinone
m was added to obtain a composition G. The composition G was used and treated in the same manner as in Example 1 to form a gel coat layer, and the composition D was used and treated in the same manner as in Example 1 to form a casting layer, thereby producing an artificial marble-like bath. Obtained. The characteristics are shown in Table 1.

Tensile strength and elongation are JIS K71
13. Weather resistance conforms to JIS K7200 (using sunshine weatherometer), and its appearance change is based on color difference (JIS
(According to Z8730), and the hot water resistance of the bath was determined according to JIS A5704. For the gel coat resin and the casting layer resin, a 300 mm × 300 mm × 3 mm (thickness) casting plate was prepared, and its tensile strength, tensile elongation and hot water resistance were examined according to JIS A5704. The hot water resistance was determined by immersing the casting plate in hot water at 98 ° C., taking it out and observing it every 100 hours, and examining the time of occurrence of blisters and cracks.

[0020]

[Table 1]

[0021]

EFFECTS OF THE INVENTION The artificial marble bath according to the present invention is free from heat shrinkage and cracking due to stress during demolding, and is excellent in hot water resistance, heat resistance and weather resistance.

[Brief description of drawings]

FIG. 1 is a sectional view of an example of a bath according to the present invention.

Claims (1)

[Claims] 1. An unsaturated dibasic acid and / or its acid anhydride and a compound represented by the general formula [I]: An unsaturated polyester and a polymerizable monomer obtained by reacting with a hydrogenated bisphenol A propylene oxide derivative represented by the formula (m and n are integers in which m + n is 2.2 to 4.0 on average) An artificial marble-like bath formed by forming a gel coat layer and / or a casting layer with an unsaturated polyester resin composition containing.