JPH07278345A - Resin composition and its production - Google Patents

Abstract

PURPOSE:To provide a resin composition giving an artificial marble having excellent water-resistance and suitable e.g. for bathtub enabling bathing throughout the day by mixing a resin raw material, an inorganic filler, a vinyl-type silane-coupling agent and a specific organic silane compound and curing the mixture. CONSTITUTION:This resin composition is produced by mixing (A) a resin raw material (e.g. unsaturated polyester resin) with (B) an inorganic filler or an inorganic fiber (e.g. glass fiber), (C) a vinyl-type silane coupling agent (e.g. vinyltriethoxysilane) and (D) a non-reactive organic silane compound of formula, Rn-SiX4-n (R is a non-reactive organic group; X is a hydrol-yzable group; (n) is 1-3) (preferably methyltrimethoxysilane or dimethyldimethoxysilane). The amounts of the components B and D are preferably 30-40 pts.wt. and 0.05-2 pts.wt., respectively, and that of the component C is usually 0.1-5 pts.wt. based on 100 pts.wt. of the component A. The amount of the component D is preferably 20-60 pts.wt. based on 100 pts.wt. of the component C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a method for producing the same. More specifically, the present invention relates to a resin composition having excellent water resistance, particularly a resin composition suitable for producing artificial marble and a method for producing the same.

[0002]

2. Description of the Related Art Artificial marble produced from a composition in which a reactive resin such as an unsaturated polyester resin, polymethylmethacrylate, or a vinyl ester resin is filled with an inorganic filler, has a high-grade appearance on its outer surface and a high formability. Because of its superiority, nowadays various bathtubs, system kitchens,
It is becoming widely used for counter tops and the like. These artificial marbles are often used especially around water, which requires a high degree of water resistance. However, in general, since the resin component of the artificial marble and the inorganic filler have poor wettability, when used in a water-immersed state for a long time, water is accumulated at the interface between the raw material resin of the artificial marble and the inorganic filler, and the strength is lowered. However, there is a problem that the appearance changes to white. Therefore, conventionally, for the purpose of improving the wettability of the interface between the resin component of the artificial marble and the inorganic filler, various silane coupling agents having reactivity with the resin raw material, particularly vinyl silane coupling agents have been used. The vinyl-type silane coupling agent improves the wettability of the above-mentioned interface and also improves the water resistance of the artificial marble by coupling the resin and the inorganic filler by a chemical reaction.

[0003]

However, as a tendency in recent years, interest in bathtubs that can be bathed for 24 hours is increasing. In such a case, the water resistance of a conventional vinyl-based silane coupling agent is increased. Is insufficient,
There is a demand for artificial marble with even better water resistance. The present invention has been made in consideration of such a situation,
An object of the present invention is to provide a resin composition capable of producing artificial marble and the like having higher water resistance and a method for producing the resin composition.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the above-mentioned problems of the prior art and have found that they have a hydrolyzable group in addition to the resin raw material, the inorganic filler or the inorganic fiber and the vinyl silane coupling agent. From the resin composition produced by using a non-reactive organic silane compound having a specific structure having no reactive functional group, it was found that an artificial marble having extremely high water resistance can be produced, and further intensive studies have been conducted. Completed the invention.

Therefore, according to the present invention, the resin raw material, the inorganic filler or the inorganic fiber, the vinyl-based silane coupling agent, and the following formula I: R _n -SiX _4-n (I) (wherein R is a non-reactive compound) A non-reactive organic silane compound represented by formula (1), a non-reactive organic silane compound represented by formula (1), a group (X) represents a hydrolyzable group, and n represents an integer of 1, 2 or 3 and cured. Resin composition.

The resin raw material in the present invention means an unsaturated polyester resin, a polymethylmethacrylate resin, a methylmethacrylate monomer, a vinylester resin or the like.

Examples of the inorganic filler or inorganic fiber used in the present invention include glass powder,
Glass frit, glass balloon, aluminum hydroxide, magnesium hydroxide, calcium carbonate, alumina,
Examples thereof include, but are not limited to, magnesia, silica powder, silica frit, silica balloon talc, glass fiber, alumina fiber, carbon fiber, silicon carbide fiber, silicon nitride fiber and the like. In addition, this inorganic filler or inorganic fiber may be used alone, or may be used in combination with several kinds of inorganic fillers or several kinds of inorganic fibers, or may be used in combination with inorganic filler and inorganic fiber. . The amount of the inorganic filler or inorganic fiber used is appropriately determined in consideration of desired physical properties and the like, and is not particularly limited, but is usually 20 to 60 parts by weight, preferably 30 to 50 parts by weight with respect to 100 parts by weight of the resin raw material. Parts, especially 30 to 40 parts by weight.

The vinyl silane coupling agent used in the present invention is an organic functional group containing an ethylenically unsaturated double bond such as a vinyl group, an acryloxyalkyl group or a methacryloxyalkyl group and a methoxy group or an ethoxy group. Silanes having an alkoxy group or a hydrolyzable group such as a halogen atom such as a chlorine atom. Specific compounds include vinyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ- (acryloxypropyl) trimethoxysilane, γ- (methacryloxy). Propyl) methyldimethoxysilane and the like. These compounds are usually used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the resin raw material. The above compounds may be used as they are, or may be hydrolyzed to form a partial condensate, or two or more kinds may be used simultaneously.

The non-reactive organosilane compound in the present invention is represented by the above formula I. R in the formula I is a non-reactive organic group, for example, one having 1 to 20 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group and a hexyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl such as a phenyl group. Group, benzyl group, aralkyl group such as phenethyl group, aralkyl group such as tolyl group, and the like. The group X is a hydrolyzable group, for example, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group or an ethoxy group,
Alternatively, it is a halogen atom such as a bromine atom, a chlorine atom, or an iodine atom. Further, n is an integer of 1, 2 or 3.

Specific examples of the non-reactive organic silane compound represented by the formula I include methyltrichlorosilane, methyltrimethoxysilane, methyltris (β-methoxyethoxy) silane, dimethyldichlorosilane, dimethyldimethoxysilane and dimethyltris (β. -Methoxyethoxy)
Silane, octyltriethoxysilane, cyclohexyltrichlorosilane, phenyltrimethoxysilane, phenyltris (β-methoxyethoxy) silane, diphenyldichlorosilane, diphenyldimethoxysilane, phenyltris (β-methoxyethoxy) silane, benzyltriethoxysilane, phenethyl Trichlorosilane, p
-Tolyltrichlorosilane and the like can be mentioned, and among these, methyltrimethoxysilane and dimethyldimethoxysilane are particularly preferable. Further, these compounds may be used as they are, or may be hydrolyzed to form a partial condensate, or two or more kinds may be used simultaneously.

In the present invention, the non-reactive organosilane compound is added in an amount of 0.01 to 3.
It is preferably used in an amount of 0 part by weight, and particularly preferably used in an amount of 0.05 to 2.0 per 100 parts by weight of the resin raw material.
Parts by weight. This is because when the amount of the non-reactive organic silane compound used is less than the above range, the strength and water resistance of the resin composition itself are insufficient, and even when it is more than the above range, the strength of the resin composition itself is insufficient. Further, the water resistance is not further improved, which is not preferable from the economical point of view, and a problem such as coloring due to heating may occur. The non-reactive organic silane compound is preferably used in an amount of 10 to 150 parts by weight, particularly preferably 20 to 60 parts by weight, based on 100 parts by weight of the vinyl silane coupling agent. this is,
When the amount of the non-reactive organosilane compound used is less than the above range, the strength and water resistance of the resin composition itself are insufficiently improved, and even when it is more than the above range, the strength and water resistance are improved. Is gradually decreased.

The present invention also provides an inorganic filler or inorganic fiber as a resin raw material, a vinyl-based silane coupling agent, and the following formula I: R _n -SiX _4-n (I) (wherein R is a non-reactive organic compound). Group, X represents a hydrolyzable group, and n represents an integer of 1, 2 or 3, and is added and cured. The present invention relates to a method of manufacturing a product.

In the present invention, the inorganic filler or the inorganic fiber, the vinyl-based silane coupling agent, and the non-reactive organic silane compound represented by the above formula I are added to the resin raw material, respectively, Inorganic fiber
It may be added to the resin raw material after being pretreated with either or both of the vinyl-based silane coupling agent and the non-reactive organosilane compound represented by the formula I. When the inorganic filler or the inorganic fiber is pretreated, it can be carried out by a conventional method for treating these silane coupling agents. For example, in the case of an inorganic filler, a mixture of a vinyl-based silane coupling agent and a non-reactive organic silane compound is added directly or dissolved in a solvent and added, and then mixed with a mixer such as a Henschel mixer, and then heat treated. The vinyl silane coupling agent and the non-reactive organic silane compound may be reacted with the inorganic filler. The curing is preferably carried out at 80 to 150 ° C. for 1 hour or longer.
In the case of inorganic fibers, for example, if the inorganic fibers are immersed in a solution prepared by dissolving a vinyl-based silane coupling agent and a non-reactive organic silane compound in a suitable solvent, heat treatment may be performed under the same conditions as above. Good. In addition, here, the inorganic filler or the inorganic fiber has been shown an example of being pretreated with both the vinyl-based silane coupling agent and the non-reactive organic silane compound, but is treated with either one, the other component is simply It goes without saying that they may be added.

In the present invention, a resin curing agent, for example, a known azo compound such as azobisisobutyronitrile or benzoyl peroxide, or a peroxide can be used for curing the resin composition. Also for this purpose,
Curing at room temperature by using a redox catalyst system consisting of transition metal salts such as cobalt naphthenate and cobalt octenoate and organic peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cumene hydroperoxide, etc. You can also let it.

The present invention further relates to articles manufactured from the above resin composition of the present invention, such as artificial marble. This artificial marble has higher water resistance than conventional ones and is suitably used as various bathtubs, system kitchens, countertops, and the like.

[0016]

The present invention will now be described based on examples of the present invention, but the present invention is not limited thereto. Examples 1 to 4, Comparative Examples 1 to 4 100 parts by weight of unsaturated polyester resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: G-227), methyl ethyl ketone peroxide (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.,
Trade name: CAT-M) 1.5 parts by weight, cobalt naphthenate (Showa Polymer Co., Ltd., trade name: accelerator cobalt N) 1.5 parts by weight and glass powder (Fellow Co., Ltd., trade name: Frit) # 3134) 40 parts by weight of vinyl-based silane coupling and non-reactive organic silane compound are mixed in proportions shown in Table 1. Each formulation was thoroughly mixed, degassed under reduced pressure, poured into a mold, and cured at room temperature for 12 hours, then further cured at 60 ° C. for 8 hours, removed from the mold and removed from a 5 cm × 5 cm It was cut into test pieces of a size. Using the test piece, JIS A
-5704 The boiling test according to the boiling test method of 7-3 was conducted for 12 cycles, and the light transmittance of the test piece before and after the test was measured (in accordance with JIS A-5705 6-4, measuring instrument: direct reading). Haze Computer, manufactured by Suga Test Instruments Co., Ltd.). The results are summarized in Table 1.

[0017]

[Table 1]

As shown in Table 1, in each of the examples of the present invention, the light transmittance before and after the test was compared with the comparative example in which the non-reactive organosilane compound and the vinyl silane coupling agent were not used together. High survival rate. That is, the decrease rate of the light transmittance after the boiling test is low. This indicates that the resin composition of the present invention is superior in water resistance to the conventional one.

Examples 5-8, Comparative Examples 5-7 100 parts by weight of unsaturated polyester resin (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name: G-227), methyl ethyl ketone peroxide (manufactured by Nippon Shokubai Chemical Co., Ltd.,
Trade name: CAT-M) 1.5 parts by weight, cobalt naphthenate (manufactured by Showa Polymer Co., Ltd., trade name: accelerator cobalt N) 1.5 parts by weight, and aluminum hydroxide (manufactured by Showa Denko KK, trade name) A vinyl silane coupling agent and a non-reactive organic silane compound are mixed in the proportions shown in Table 2 with respect to 40 parts by weight of Hydilite H-32). Each composition was thoroughly mixed, degassed under reduced pressure, poured into a mold, and cured at room temperature for 12 hours, then further cured at 60 ° C. for 8 hours, removed from the mold, and 5 cm × 5 cm.
It was cut into test pieces of the size. Using the test piece, a boiling test was performed in the same manner as above, and the light transmittance was measured.
The results are summarized in Table 2.

[0020]

[Table 2]

As shown in Table 2, each Example of the present invention using the non-reactive organic silane compound has a lower reduction rate of the light transmittance after the boiling test, as compared with the Comparative Example which does not use it. . This indicates that the resin composition of the present invention has excellent water resistance.

Examples 9-12, Comparative Examples 8-11 Crystalline silica (Sumitomo Coal Mining Co., Ltd., trade name: QZ
CRYSTAL SCT-8) For 100 parts by weight,
A mixture of a vinyl-based silane coupling agent and a non-reactive organic silane compound mixed in the proportions shown in Table 3 was dissolved in isopropanol to prepare a solution having a combined concentration of both compounds of 40% by weight. , Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) for 10 minutes, and then dried in an oven at 120 ° C. for 1 hour to perform surface treatment of crystalline silica. 40 parts by weight converted to the amount of crystalline silica of the surface-treated product is polymethylmethacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: BR-85).
60 parts by weight and 40 parts by weight of methyl methacrylate monomer (manufactured by Mitsubishi Rayon Co., Ltd.) were mixed, and 0.025 of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture.
After adding parts by weight, the mixture was poured into a mold, cured at 80 ° C. for 6 hours, removed from the mold, and cut into a test piece having a size of 5 × 5 cm. Using the test piece, a boiling test was performed in the same manner as above, and the light transmittance was measured. The results are summarized in Table 3.

[0023]

[Table 3]

As shown in Table 3, in each of the examples of the present invention, the light transmittance after the boiling test was compared with the comparative example in which the non-reactive organosilane compound and the vinyl silane coupling agent were not used together. The rate of decrease is low. This indicates that the resin composition of the present invention is superior in water resistance to the conventional one.

[0025]

Industrial Applicability As described in detail above, the resin composition of the present invention exhibits high water resistance to the extent never obtained before, and can be used for articles that are used in a long-term waterlogged state. It can also be applied to molding. Further, according to the method for producing a resin composition of the present invention, a resin composition having enhanced water resistance can be produced by a simple operation. Artificial marble produced from the resin composition of the present invention having such excellent water resistance is a bathtub that can be bathed for 24 hours, which has been attracting attention in recent years, a system kitchen in which contact with water continues for a long time, It exerts a particularly excellent effect as an article around water such as a countertop, and its industrial value is extremely high.

Claims (5)

[Claims] 1. A resin raw material, an inorganic filler or inorganic fiber, a vinyl-based silane coupling agent, and the following formula I: R _n -SiX _4-n (I) (wherein R represents a non-reactive organic group). , X represents a hydrolyzable group, and n represents an integer of 1, 2 or 3) and was mixed and cured with a non-reactive organic silane compound. . 2. The resin composition according to claim 1, which contains 10 to 150 parts by weight of the non-reactive organic silane compound represented by the formula I with respect to 100 parts by weight of the vinyl-based silane coupling agent. 3. A resin raw material comprising an inorganic filler or inorganic fiber, a vinyl-based silane coupling agent, and the following formula I: R _n —SiX _4-n (I) (wherein R represents a non-reactive organic group). , X represents a hydrolyzable group, and n represents an integer of 1, 2 or 3), and the resin composition is cured. Method. 4. The inorganic filler or the inorganic fiber is added to the resin raw material after being pretreated with either or both of the vinyl-based silane coupling agent and the non-reactive organic silane compound represented by the formula I. Item 4. A method for producing the resin composition according to Item 3. 5. An article produced from the resin composition according to claim 1 or 2.