JP2013159680A - Artificial marble, bathtub and method of manufacturing artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To surface-modify the surface of an artificial marble made of an unsaturated polyester resin to be hydrophilic.SOLUTION: An artificial marble is obtained by molding an unsaturated polyester resin, where the unsaturated polyester resin has compounded therewith a hydrophilizing agent, which comprises an unsaturated polyester comprising an unsaturated dibasic acid, a saturated dibasic acid and polyethylene glycol. Thus, the surface of the artificial marble can be modified to be hydrophilic. The artificial marble reduces a cleaning load to enhance cleaning properties, when it is particularly used for a member in a water section such as a bathtub and a wash bowl, to which oily soil originated from the human body adheres.

Description

  The present invention relates to an artificial marble made of unsaturated polyester resin that can be used in a bathtub, a wash bowl, a kitchen sink, and the like, and an artificial marble bathtub.

  Traditionally, thermosetting resins such as unsaturated polyester resin, acrylic resin, and vinyl ester resin are mainly used for so-called “water-based” products such as bathtubs, wash counters / bowls, kitchen counters / sinks, and toilet parts. It is manufactured by curing and molding the composition. In applications such as those described above, dirt may adhere with use, and may stain and be difficult to remove. Therefore, by increasing the hydrophilicity of the surface of the thermosetting resin bathtub such as an unsaturated polyester resin composition, the adhesion of dirt is prevented, and the attached dirt is easily cleaned to ensure easy cleaning as a result. It is demanded.

Patent Document 1 discloses an antifouling method in which polyethylene glycol or an alkyl ether thereof is applied or immersed in a cured unsaturated polyester resin cured product and graft polymerization is performed by flowing a nitrogen gas to make the surface of the resin composition hydrophilic. An unsaturated polyester cured body for structural use is disclosed.
In this case, after the unsaturated polyester resin is cured to obtain a molded product, polyethylene glycol is further graft-polymerized on the surface of the cured product, which requires two steps and is troublesome and requires special equipment. There was a problem.

Patent Document 2 uses a hydrophilizing agent in which a specific amount of ultrafine particulate anhydrous silica, polyethylene glycol having a weight average molecular weight of 1,000 to 5,000,000 or polyethylene oxide is added to unsaturated polyester. A resin body is disclosed.
However, in this case, in order to improve the hydrophilicity, if the amount of the hydrophilizing agent that is incompatible with the unsaturated polyester resin is increased, the curability of the obtained cured product is lowered and the surface of the cured product is not sticky. There have been problems such as the occurrence of such problems and the inability to maintain the hydrophilic function for a long period of time.

Patent Document 3 discloses a technique for producing a plastic by addition polymerization of a non-functional monomer and a functional monomer having a hydrophilic group as an antifouling plastic product, and curing and molding the plastic by molding. Has been.
However, this technique is a technique for adding a hydrophilic group to a thermoplastic acrylic resin, and is difficult to apply to a thermosetting unsaturated polyester resin.

JP 2006-298985 A JP 2005-29586 A Japanese Patent Laid-Open No. 10-87856

  The present invention has been made to solve the above-described problems, and in order to facilitate the cleaning of the surface of the artificial marble, the surface of the unsaturated polyester resin artificial marble is modified to be hydrophilic. The purpose is to do.

In order to achieve the above object, according to the invention described in claim 1, artificial marble obtained by molding an unsaturated polyester resin, wherein the unsaturated polyester resin contains a hydrophilizing agent, The hydrophilizing agent is made of unsaturated polyester containing unsaturated dibasic acid, saturated dibasic acid and polyethylene glycol, so that the surface of the unsaturated polyester resin suitable for easy-cleaning baths is made hydrophilic. It was possible to quality. Since the surface of the artificial marble can be made to have a smaller water contact angle than before, the surface of the artificial marble can be made hydrophilic, so it is easier to remove oil-derived oil stains and oil stains adhering to the surface of the artificial marble. be able to.
Since polyethylene glycol is used as the polyhydric alcohol, it has moderate compatibility with the unsaturated polyester resin, and when the resin is cured, the hydrophilizing agent crosslinks with the resin so that the cured body of the unsaturated polyester resin. The hydrophilicity of the surface of the artificial marble can be maintained for a long time without impairing the physical properties and water resistance. Since it can be manufactured using a general unsaturated polyester-based artificial marble manufacturing facility, an increase in manufacturing cost can be prevented.

  In addition, according to the invention of claim 2, the mixing ratio of the hydrophilizing agent to the unsaturated polyester resin is 95: 5 to 50:50 by mass ratio. The surface of the unsaturated polyester resin suitable for a cleanable bathtub can be modified to be hydrophilic. The surface of the artificial marble is modified by making the surface ratio of the unsaturated polyester resin artificial marble by adjusting the blending ratio of the hydrophilic agent to the unsaturated polyester resin to 95: 5 to 50:50 by mass ratio. It is possible to easily remove the oily and fat stains and oil stains derived from the human body adhering to.

  Moreover, according to the invention of Claim 3, the blending ratio of the unsaturated polyester resin and the hydrophilizing agent is 90:10 to 60:40 in terms of mass ratio, which is more suitable for an easily cleanable bathtub. The surface of the unsaturated polyester resin can be modified to be hydrophilic. By making the blending ratio of the unsaturated polyester resin and the hydrophilizing agent 90:10 to 60:40 by mass ratio, the surface of the unsaturated polyester resin artificial marble was modified to be hydrophilic and adhered to the surface of the artificial marble. It makes it easier to remove oil-based dirt and oil stains from the human body than before, and it is relatively expensive compared to unsaturated polyester resins without sacrificing water resistance and hot water resistance for a long time as an artificial marble bathtub. The blending ratio of the hydrophilizing agent can be optimized, and a significant increase in manufacturing cost can be prevented.

  According to a fourth aspect of the present invention, the artificial marble includes a base made of an unsaturated polyester resin not containing the hydrophilic agent and an unsaturated polyester resin containing the hydrophilic agent, and the surface of the base. Since the hydrophilizing agent is blended only on the surface of the artificial marble, the cost can be suppressed.

  Moreover, according to invention of Claim 5, since a bathtub is formed with the artificial marble in any one of Claims 1-4, the fat-and-oil stain derived from the human body which remains on the surface of a bathtub whenever it bathes is conventionally Can be easily removed, improving the cleaning performance.

  According to the invention described in claim 6, a hydrophilizing agent containing unsaturated dibasic acid, saturated dibasic acid and polyethylene glycol is blended in the unsaturated polyester resin, and the unsaturated polyester resin is cast-molded. By using a general unsaturated polyester-based artificial marble manufacturing facility, artificial marble with higher hydrophilicity and higher antifouling properties can be produced. can do.

According to the invention of claim 7, an unsaturated polyester resin containing a hydrophilizing agent containing unsaturated dibasic acid, saturated dibasic acid and polyethylene glycol is applied to the surface of the mold (gel coat layer), A method for producing artificial marble, characterized by forming an artificial marble by injecting an unsaturated polyester resin not containing a hydrophilizing agent into a mold coated with an unsaturated polyester resin containing a hydrophilizing agent. By doing so, it is possible to produce artificial marble having higher hydrophilicity and higher antifouling properties than conventional ones, using a general unsaturated polyester-based artificial marble production facility.
Furthermore, since the hydrophilizing agent is blended only on the surface of the artificial marble, the cost can be reduced.

  According to the present invention, an unsaturated polyester resin to which a hydrophilic agent for unsaturated polyester resin is added is added to the surface of the artificial marble by modifying the surface of the unsaturated polyester resin artificial marble to be hydrophilic. The oil and fat stains and oil stains can be removed more easily than before, and the user's cleaning load can be reduced.

It is a figure which shows the structure of the unsaturated polyester resin bathtub which is 1 aspect of this invention. It is a figure which shows the structure of the unsaturated polyester resin bathtub which is 1 aspect of this invention.

First, the component which comprises the artificial marble (unsaturated polyester resin composition) concerning this invention is demonstrated.
Artificial marble is molded from an unsaturated polyester resin containing a hydrophilizing agent. A hydrophilizing agent consists of unsaturated polyester containing unsaturated dibasic acid, saturated dibasic acid, and polyethyleneglycol.

  Unsaturated dibasic acid refers to unsaturated dicarboxylic acid and its derivatives, specifically maleic acid, fumaric acid, itaconic acid, citraconic acid, halomaleic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, anhydrous Examples thereof include maleic acid, fumaric acid, and maleic anhydride. These unsaturated dibasic acids can be used alone or in combination of two or more.

  Saturated dibasic acid refers to saturated dicarboxylic acid and its derivatives, specifically isophthalic acid, terephthalic acid, orthophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sodium 5-sulfoisophthalate Phthalic anhydride, succinic anhydride and the like, preferably phthalic anhydride and isophthalic acid. These saturated dibasic acids can be used alone or in combination of two or more.

Polyethylene glycol is represented by a general formula of “HO— (CH ₂ —CH ₂ —O) _n —H”, where n represents an integer of 2 or more. The average molecular weight of polyethylene glycol is preferably 200 to 4000, more preferably 300 to 1000. If the average molecular weight of polyethylene glycol is 200, sufficient hydrophilicity can be expressed and the polycondensation reaction proceeds reliably.

Here, the average molecular weight of the polyethylene glycol is measured by titration of terminal functional groups. Specifically, the hydroxyl value was measured according to the Japan Oil Chemists' Society method (standard oil and fat analysis test method 2003 version 2.3.6.2), and the average molecular weight was calculated by the following formula.
Average molecular weight of polyethylene glycol = 56100 × 2 / hydroxyl value

  The hydrophilizing agent for unsaturated polyester resin (hereinafter referred to as “hydrophilizing agent”) is an unsaturated polyester obtained by polycondensation of an unsaturated dibasic acid, a saturated dibasic acid and polyethylene glycol.

  The blending molar ratio of unsaturated dibasic acid and saturated dibasic acid constituting the hydrophilizing agent (unsaturated dibasic acid component: saturated dibasic acid component) is preferably about 2: 8 to 8: 2, and more Preferably it is about 3: 7-7: 3. Within the above range, the cured property of the unsaturated polyester resin composition cured by adding a hydrophilic agent to the unsaturated polyester resin can be maintained, and further sufficient hydrophilicity can be exhibited.

  The molar ratio of unsaturated dibasic acid and saturated dibasic acid constituting the hydrophilizing agent and polyethylene glycol (unsaturated dibasic acid component + saturated dibasic acid component: polyethylene glycol component) is preferably about 9:11. ~ 11: 9, more preferably about 1: 1. Within the above range, the polycondensation reaction during the preparation of the hydrophilizing agent proceeds reliably. .

Other raw materials can be polycondensed with the hydrophilizing agent as long as the effects of the present invention are not impaired. Examples thereof include polyhydric alcohols other than polyethylene glycol used in the present invention.
Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6 -Dihydric alcohols such as hexanediol, triethylene glycol and neopentyl glycol; trihydric alcohols such as glycerin and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol.

Other raw materials can be blended with the hydrophilizing agent obtained by polycondensation as long as the effects of the present invention are not impaired. For example, a hydrophilic monomer etc. are mentioned.
Examples of the hydrophilic monomer include sodium styrene sulfonate, sodium isoprene sulfonate, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, vinyl sulfonic acid, acrylamidomethylpropane sulfonic acid, acrylic acid, methacrylic acid, 2 -Acryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, higher alkoxy polyethylene glycol (meth) acrylate, nonylphenyl Polyethylene glycol (meth) acrylate, bis (polyethylene glycol) malate, bis (methoxypoly) Tylene glycol) malate, bis (butoxypolyethyleneglycol) malate, bis (higher alkoxypolyethyleneglycol) malate, bis (nonylphenylpolyethyleneglycol) malate, bis (polyethyleneglycol) fumarate, bis (methoxypolyethyleneglycol) fumarate, bis (butoxypolyethylene) Glycol) fumarate, bis (higher alkoxy polyethylene glycol) fumarate, bis (nonylphenyl polyethylene glycol) fumarate, polyoxyethylene allyl ether and its ester, polyoxyethylene pentenyl ether and its ester, polyoxyethylene undecylenyl ether and its ester Etc.

  The hydrophilizing agent can be produced by polycondensation of an unsaturated dibasic acid, a saturated dibasic acid and polyethylene glycol by a known method. For example, it can be obtained by heating the unsaturated dibasic acid, saturated dibasic acid and polyethylene glycol to about 120 to 210 ° C. with stirring and dehydrating polycondensation under a nitrogen stream.

  The hydrophilizing agent preferably has an average molecular weight of about 1500 to 10000, more preferably about 2000 to 5000. Within the above range, the viscosity of the unsaturated polyester resin composition obtained by blending the unsaturated polyester resin with a hydrophilizing agent becomes appropriate and good workability is obtained, and when the composition is cured and molded. The mechanical strength of the unsaturated polyester resin composition cured product becomes appropriate.

  The hydrophilizing agent is used by being added to the unsaturated polyester resin, and the hydrophilic property of the surface of the cured product obtained by curing by adding a curing agent to the unsaturated polyester resin composition containing the hydrophilizing agent is improved. Can do. Specifically, since the hydrophilizing agent of the present invention uses polyethylene glycol as a polyhydric alcohol, it has moderate compatibility with the target unsaturated polyethylene resin, and when the resin is cured, The hydrophilic function can be maintained over a long period of time without impairing the physical properties and water resistance, which are the characteristics of the cured body of the unsaturated polyester resin, as the agent is crosslinked with the resin.

  The unsaturated polyester resin composition is obtained by dissolving a hydrophilizing agent and an unsaturated polyester in a polymerizable monomer. The blending amount of the hydrophilizing agent in the unsaturated polyester resin composition is preferably about 5 to 50% by mass, more preferably about 10 to 40% by mass.

  The unsaturated polyester used in the unsaturated polyester resin composition is obtained by polycondensation reaction of an unsaturated dibasic acid, an acid component containing other polybasic acid if desired, and an alcohol component by a known method. is there.

  Examples of the unsaturated dibasic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and fumaric anhydride, and these can be used alone or in combination of two or more. Other polybasic acids used as desired are phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, succinic acid, azelain hexahydrophthalic acid, acid, adipic acid, tetrahydrophthalic acid Chlorination of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, anthracene-maleic anhydride adduct, rosin-maleic anhydride adduct, het acid, het anhydride, tetrachlorophthalic anhydride, etc. Halogenated polybasic acids such as polybasic acid, tetrabromophthalic acid, and tetrabumorophthalic anhydride are listed. These can be used alone or in combination of two or more.

  Examples of the alcohol component include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1, Dihydric alcohols such as 6-hexanediol, triethylene glycol and neopentyl glycol, trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric alcohols such as pentaerythritol are used. These can be used alone or in combination of two or more.

  Examples of the polymerizable monomer used in the unsaturated polyester resin composition include (meth) acrylic acid esters such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, divinylbenzene, and methyl methacrylate, and vinyl acetate. Etc. These can be used alone or in combination of two or more. The compounding quantity of a polymerizable monomer is about 50-120 mass parts with respect to 100 mass parts of unsaturated polyester, Preferably it is the range of about 60-100 mass parts.

  The unsaturated polyester resin composition can be blended with other raw materials as long as the effects of the present invention are not impaired. For example, polymerization inhibitors (such as hydroquinone, pyrocatechol, 2,6-di-tert-butylparacresol), dyes, plasticizers, ultraviolet absorbers, thixotropic agents (such as silica powder, asbestos powder, hydrogenated castor oil) , Fatty acid amides, etc.), fillers, stabilizers, antifoaming agents, leveling agents and the like.

  Examples of the curing agent for curing the unsaturated polyester resin composition include organic peroxides. Specifically, it is a curing catalyst such as methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide. The organic peroxide is preferably blended at a ratio of about 0.5 to 3.0% by mass with respect to the unsaturated polyester resin composition.

  In addition to a curing agent such as an organic peroxide, a curing accelerator can be used as desired. Examples of the curing accelerator include metal soaps such as cobalt naphthenate and cobalt octenoate, quaternary ammonium salts such as dimethylbenzylammonium chloride, β-diketones such as acetylacetone, dimethylaniline, N-ethyl-metatoluidine, tri Examples include amines such as ethanolamine. There is no restriction | limiting in particular in the mixture ratio of this hardening accelerator, According to the required sclerosis | hardenability, it determines suitably.

Next, a method for forming an artificial marble according to the present invention will be described.
Examples of the method for molding the artificial marble include a BMC press molding method and an injection molding method.

BMC is a block molding material obtained by blending a radical curing molding material. As a BMC manufacturing method, for example, a resin composition is mixed with a resin (including a hydrophilizing agent), a filler (calcium carbonate, aluminum hydroxide, etc.), glass fiber, a curing agent, a pigment, etc. using a mixing device such as a kneader. Can be obtained. The order of mixing, the method of mixing, etc. are not particularly limited.
The resin composition can be obtained by heating and pressure-molding BMC with a press machine. Examples of the molding method include methods such as heat compression molding, transfer molding, and injection molding.
The press molding conditions are the same as the general BMC press molding conditions. The molding temperature is preferably 40 to 180 ° C., the molding pressure is preferably 1 to 20 MPa, and the pressing time is preferably 1 to 60 minutes. is there. Within this range, it may be appropriately selected depending on the composition content of the BMC used, the shape and size of the resin composition, and the like. By this press molding operation, a resin composition of artificial marble having a high commercial value can be molded easily and stably, not only in a flat plate shape but also in a three-dimensional integrated shape.

The injection molding methods include FRP molds and electric molds, and the cost of the molds is lower than that of the BMC press molding method. A BMC press molding method (die: mold) is usually used for a large quantity and a member that requires mass production, and an injection molding method with a low die cost is usually used for a member that does not have a large quantity.
There are two types of injection molding methods, one with and without a gel coat. In the type having a gel coat, first, a gel coat agent is applied to the mold by spraying or the like and dried. The gel coating agent is a mixture of an unsaturated polyester resin (including a hydrophilizing agent) and a curing agent, but a thixotropic agent is also added. The resin composition base material is a resin, filler (calcium carbonate, aluminum hydroxide, etc.), glass fiber, curing agent, pigment, etc., stirred and mixed, poured into a mold, and dried at about 50 ° C. After that, the mold is removed, but at this point, it has not yet been cured sufficiently, and after-curing at about 90 ° C. is almost completely cured.
As for the type with a gel coat, as shown in FIG. 1, the gel coat layer 3 forms the surface of the base 1 made of unsaturated polyester resin. That is, since the gel coat layer 3 comes out on the outermost surface of the resin composition, the hydrophilizing agent is mixed only with the gel coat agent. An FRP backup layer 2 is provided on the back surface of the base 1.
In the type without gel coat, a hydrophilizing agent is mixed with an unsaturated polyester resin composition base material to be molded. In a molding method without a gel coat, a resin composition is injected into a mold and dried at about 50 ° C. A resin composition (including a hydrophilizing agent) stirs and mixes a resin, a filler (such as calcium carbonate and aluminum hydroxide), glass fiber, a curing agent, and a pigment. At this point of time after demolding, the film is not yet fully cured, and is aftercured at about 90 ° C. to be almost completely cured.
In the type without the gel coat layer, the base 1 comes out on the outermost surface of the resin composition as shown in FIG.

By the molding method described above, artificial marble bathtubs, wash counters, wash bowls, kitchen counters, kitchen sinks, toilet members, and the like can be manufactured. In particular, every time it is used, that is, every time it takes a bath, the surface of the bathtub can be more easily removed by manufacturing the bathtub to which the oil and fat stain derived from the human body adheres with the artificial marble according to the present invention. Therefore, since it is necessary to bend and clean the bathtub, a large load can be easily cleaned in a short time, and the cleanability is improved.
Also, even in a wash bowl for hand washing or a kitchen sink for washing things, oil stains derived from the human body adhere, so by manufacturing with artificial marble according to the present invention, dirt on the surface can be removed more easily than before. , Cleaning can be performed easily in a short time, and the cleaning property is improved.

  Examples The unsaturated polyester resin composition relating to the artificial marble according to the present invention will be described below by way of examples. However, this is merely an example of the present invention and does not limit the present invention.

<Production of hydrophilizing agent for unsaturated polyester resin>
(1) Raw materials Maleic anhydride (trade name: maleic anhydride; manufactured by Wako Pure Chemical Industries, Ltd.)
Phthalic anhydride (trade name: phthalic anhydride; manufactured by Wako Pure Chemical Industries, Ltd.)
Succinic anhydride (trade name: Ricacid SA: manufactured by Shin Nippon Chemical Co., Ltd.)
Polyethylene glycol (trade name: polyethylene glycol 400; average molecular weight 400, manufactured by Toho Chemical Co., Ltd.)
Propylene glycol (trade name: propylene glycol; manufactured by ADEKA)

(2) Composition of raw materials Table 1 shows the composition of the hydrophilizing agent prepared using the above raw materials.

(3) Preparation of hydrophilizing agent [Example 1]
A 1-fold amount of the raw materials shown in Table 1 was put into a 1 liter four-necked flask and heated to 210 ° C. over 1 hour with a mantle heater while slowly stirring. While removing the condensed water, the temperature was maintained at 210 ° C. for 8 hours and cooled to room temperature to obtain 492 g of a hydrophilizing agent (Example product 1). It was 2580 when the average molecular weight was measured by the following method.

[Measurement method of average molecular weight of hydrophilizing agent]
The acid value of the hydrophilizing agent is determined by the Japan Oil Chemists 'Society method (standard oil analysis test method 2003 version 2.3.1), and the hydroxyl value is determined by the Japan Oil Chemists' Society method (reference oil analysis method 2003 version 2.3.6.2). ) And the average molecular weight of the hydrophilizing agent was calculated by the following formula.
Average molecular weight of hydrophilizing agent = 56100 × 2 / (hydroxyl value + acid value)

[Examples 2 and 3]
In preparation of the hydrophilizing agent of Example 1, operation was performed similarly except having changed the raw material into the mixing | blending of Table 1, and 470g and 488g of hydrophilizing agents (Example goods 2 and 3) were obtained. When the average molecular weight was measured, they were 3320 and 2810.

[Example 4]
A 1-fold amount of raw materials other than propylene glycol listed in Table 1 was charged into a 1-liter four-necked flask and heated to 210 ° C. over 1 hour with a mantle heater while stirring slowly. Maintaining 210 ° C. for 3 hours while removing condensed water, cooling to 160 ° C., adding propylene glycol (76 g), heating to 210 ° C. over 1 hour, and adjusting the temperature to 210 ° C. while removing condensed water. The mixture was maintained for 5 hours and cooled to room temperature to obtain 630 g of a hydrophilizing agent (Example Product 4). The average molecular weight was measured and found to be 4650.

[Comparative Examples 1 and 2]
In preparation of the hydrophilizing agent of Example 1, it operated similarly except having changed the raw material into the mixing | blending of Table 1, and obtained 493g and 455g of hydrophilizing agents (comparative example goods 1 and 2). It was 3030 and 2880 when the average molecular weight was measured.

<Preparation of cured body of unsaturated polyester resin composition>
In order to evaluate the hydrophilicity of the obtained hydrophilizing agents (Example products 1 to 4, Comparative product 1 and 2), a cured body of an unsaturated polyester resin composition was prepared by the following method.
(1) Raw material Unsaturated polyester resin (trade name: Rigolac 158BQTN; manufactured by Showa High Polymer Co., Ltd., nonvolatile content 60%, cobalt naphthenate 0.1%, polymerizable monomer (styrene) content is about 67 mass Part)
Curing agent (trade name: Permec N; manufactured by NOF Corporation)
Hydrophilizing agents (Example products 1 to 4, Comparative products 1 and 2)

(2) Blending of Unsaturated Polyester Resin Composition Cured Unsaturated polyester resin composition prepared using the above raw materials is shown in Table 2.

(3) Preparation of cured body of unsaturated polyester resin composition [Prototypes 1-8]
1 times the amount of raw materials listed in Table 2 was added and stirred, and 10 g was applied with a brush on a PET film (width 100 mm × depth 100 mm × thickness 25 μm) and cured at room temperature for 24 hours, then 70 ° C. 30 It dried on the conditions for minutes, isolated PET film, and obtained the unsaturated polyester resin composition hardening body (prototypes 1-5, 7, 8).
Prototype 6 containing no unsaturated dibasic acid did not sufficiently cure and could not obtain a cured product.

<Evaluation of cured body of unsaturated polyester resin composition>
(1) Evaluation of curability The surface of the obtained unsaturated polyester resin composition cured body was touched by hand to evaluate the cured state.
Evaluation was performed according to the following evaluation criteria. The results are shown in Table 3.
(Evaluation criteria)
The surface of the cured body has no stickiness and is firmly cured. : ○
The surface of the cured body is very slightly sticky and slightly hardened. : △
The surface of the cured body is sticky and is not sufficiently cured. : ×

(2) Evaluation of hydrophilicity 1: Measurement of contact angle before dipping treatment The contact angle of the surface of the obtained unsaturated polyester resin composition cured body (the surface from which the PET film was peeled) was measured using a contact angle meter (model: FACE contact). Angle CA-X150 type; manufactured by Kyowa Interface Science Co., Ltd.). It shows that hydrophilic property is so good that the numerical value of a contact angle is small. The evaluation results of each unsaturated polyester resin composition cured product are shown in Table 3.

(3) Evaluation of hydrophilicity 2: Measurement of contact angle after immersion treatment In order to confirm that the hydrophilic function of the obtained unsaturated polyester resin composition cured product is maintained for a long period of time, the unsaturated polyester resin composition The cured body was dipped in warm water at 90 ° C. for 24 hours and then dried, and then the contact angle was measured by the same method as in “Hydrophilicity Evaluation 1”. If the numerical value of the contact angle is not significantly different from the contact angle before the immersion treatment in warm water, it can be said that the hydrophilic function is maintained for a long time. The evaluation results of each unsaturated polyester resin composition cured product are shown in Table 3.

From the results, prototypes 1 to 5 using the hydrophilizing agent of the example product have good curability, and the hydrophilicity is improved with a smaller contact angle than prototype 8 with no hydrophilic agent added. It was. Moreover, the contact angle did not change greatly even after the immersion treatment, and the hydrophilic function could be maintained for a long time.
On the other hand, the prototype 6 using the hydrophilizing agent of Comparative Example (Comparative Example Product 1) did not cure and could not obtain a cured product. Moreover, although the prototype 7 has good curability, it is equivalent to the contact angle of the prototype 8 to which no hydrophilizing agent was added, and the hydrophilicity was not improved.
In addition, when only the maleic anhydride in Example 1 was used in place of maleic acid or fumaric acid in the prototype 1, the same results as the prototype 1 shown in Table 3 were obtained. .
Further, in the prototype 1, only the phthalic anhydride in Example 1 was used in place of isophthalic acid, and as a result, the same result as that of the prototype 1 shown in Table 3 was obtained.
Furthermore, in the above-mentioned prototype 1, when polyethylene glycol in Example 1 was used in place of one having an average molecular weight of 300 or 1000, the same result as that of prototype 1 shown in Table 3 was obtained. was gotten.

DESCRIPTION OF SYMBOLS 1 ... Base 2 ... FRP backup layer 3 ... Gel coat layer

Claims (7)

  An artificial marble obtained by molding an unsaturated polyester resin, wherein the unsaturated polyester resin contains a hydrophilizing agent, and the hydrophilizing agent includes an unsaturated dibasic acid, a saturated dibasic acid, and polyethylene. An artificial marble comprising an unsaturated polyester containing glycol.   The artificial marble according to claim 1, wherein the blending ratio of the hydrophilizing agent to the unsaturated polyester resin is 95: 5 to 50:50 by mass ratio.   The artificial marble according to claim 1, wherein a blending ratio of the unsaturated polyester resin and the hydrophilizing agent is 90:10 to 60:40 in mass ratio.   The artificial marble includes a base made of an unsaturated polyester resin not containing the hydrophilizing agent, and a surface layer covering the surface of the base made of an unsaturated polyester resin containing the hydrophilizing agent. The artificial marble according to any one of claims 1 to 3.   The bathtub formed with the artificial marble in any one of Claims 1-4.   A method for producing artificial marble, comprising blending an unsaturated polyester resin with a hydrophilizing agent containing an unsaturated dibasic acid, a saturated dibasic acid and polyethylene glycol, and casting the unsaturated polyester resin.   A type in which an unsaturated polyester resin blended with a hydrophilizing agent containing unsaturated dibasic acid, saturated dibasic acid and polyethylene glycol is applied to the surface of the mold, and an unsaturated polyester resin blended with the hydrophilizing agent is applied A method for producing artificial marble, characterized by molding an artificial marble by injecting an unsaturated polyester resin not containing a hydrophilizing agent therein.

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