JP3447097B2 - Manufacturing method of patterned marble - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a patterned artificial marble having water resistance and luster and having an excellent depth feeling.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining an artificial marble-like molded article, a casting method in which a radical-polymerizable thermosetting resin compound is cast in a mold at a temperature of about room temperature to 80 ° C.,
A press molding method is known in which a sheet molding compound or a bulk molding compound is compression-molded using a mold having a temperature of 100 to 160 ° C. at a molding pressure of ³ to 150 kgf / cm ² . In the former method, a molded product with relatively good transparency can be obtained, and by applying a pigment to the back surface of the molded product, a patterned artificial marble with an excellent depth feeling can be obtained. Has a long drawback. The latter method has a short molding cycle and is excellent in mass productivity, but it is inferior in transparency because it contains a resin such as a saturated polyester resin, polystyrene, or polymethylmethacrylate as a fiber reinforcing material or a low shrinkage agent in the compound. However, since it is necessary to add a pigment to the compound for patterning, there is a drawback that the compound manufacturing machine needs to be washed every time the pigment is changed.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and efficiently coats the back surface of a molded article obtained by heat compression molding in a mold to efficiently It is intended to provide a method for producing artificial marble which has a sense of depth and is easy to pattern.

[0004]

The present invention provides a dihydric alcohol containing hydrogenated bisphenol A as an essential component and α,
Copolymerization with unsaturated polyester (I), copolymerizable monomer (II), unsaturated polyester (I) and copolymerizable monomer (II) obtained by using β-ethylenically unsaturated dibasic acid Possible unsaturated alcohol (III) and low molecular weight styrene having a number average molecular weight of less than 5000 with a molar ratio of styrene / maleic anhydride in the range of 3/1 to 7/1.
The maleic anhydride copolymer (IV) is contained, and the unsaturated alcohol (III) is used in a weight ratio of unsaturated alcohol (III) / copolymerizable monomer (II) of 1/99 to 50/50. Range, unsaturated polyester (I) / [copolymerizable monomer (I
The weight ratio of (I) + unsaturated alcohol (III)] is 30/70.
The weight ratio of styrene-maleic anhydride copolymer (IV) / [unsaturated polyester (I) + copolymerizable monomer (II) + unsaturated alcohol (III)] is 10 to 70/30.
/ 90 to 40/60, and a resin composition (V) containing glass powder and / or aluminum hydroxide is heat-compressed and molded in a mold, and a patterned artificial marble is applied with a paint on the back surface of the molded product. Manufacturing method.

The unsaturated polyester (I) used in the present invention contains hydrogenated bisphenol A as an essential component.
It is synthesized from a polyhydric alcohol and an α, β-ethylenically unsaturated dibasic acid, and if necessary, a saturated dibasic acid, an alcohol other than hydrogenated bisphenol A, dicyclopentadiene and the like can be used in combination. Examples of the α, β-ethylenically unsaturated dibasic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and their anhydrides, and the synthesis method thereof is not particularly limited. Examples of the saturated dibasic acid which is optionally used in combination include adipic acid, sebacic acid, succinic acid, gluconic acid, phthalic anhydride, o-phthalic acid, isophthalic acid, terephthalic acid and tetrahydrophthalic acid. To be Examples of divalent alcohols other than hydrogenated bisphenol A include alkanediol, oxaalkanediol, and diols obtained by adding ethylene oxide or propylene oxide to bisphenol A. In addition to this, a monovalent or trivalent alcohol may be used. Examples of alkanediols include ethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol,
1,5-pentadiol, 1,6-hexanediol,
Examples include cyclohexanediol. Examples of the oxaalkane diol include diethylene glycol and trioxyethylene glycol. Examples of monohydric or trihydric alcohols used in combination with these dihydric alcohols include octyl alcohol, oleyl alcohol and trimethylolpropane. These acids or alcohols may be used in combination.

In the present invention, the water resistance and other characteristics make it 2
The molar ratio of polyhydric alcohol / α, β-ethylenically unsaturated dibasic acid is preferably 0.90 / 1.00 to 1.20 / 1.
00, more preferably 1.00 / 1.00 to 1.10 /
The molar ratio of saturated dibasic acid / α, β-ethylenically unsaturated dibasic acid is preferably 0 / 1.00.
~ 0.70 / 0.30, more preferably 0 / 1.00
The range is 0.55 / 0.45. The molar ratio of hydrogenated bisphenol A / alcohol other than hydrogenated bisphenol A is preferably 0.10 / from the viewpoint of properties such as water resistance.
0.90 to 0.50 / 0.5, more preferably 0.20 / 0.80 to 0.40 / 0.6 from the viewpoint of gloss and workability.
The range is 0. The molar ratio of (α, β-ethylenically unsaturated dibasic acid and saturated dibasic acid) / dicyclopentadiene is preferably in the range of less than 1.00 / 0.05. The number average molecular weight of the unsaturated polyester (I) is usually in the range of 1000 to 6000 in view of workability and water resistance.
The molar ratio of (α, β-ethylenically unsaturated dibasic acid and saturated dibasic acid) / (monohydric or trihydric alcohol) is usually in the range of less than 1.00 / 0.05.

Copolymerizable monomer (II) used in the present invention
Examples of styrene, p-chlorostyrene, vinyltoluene, divinylbenzene, acrylic acid or methacrylic acid esters with alcohols having 1 to 18 carbon atoms (for example, methyl methacrylate, butyl acrylate, trimethylolpropane). Trimethacrylate) and the like. You may use these in combination of 2 or more types. Examples of unsaturated alcohols (III) include 2-
Hydroxy acrylate such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
Hydroxy methacrylate such as 2-hydroxybutyl methacrylate, methyl maleate (2-hydroxyethyl), ethyl maleate (2-hydroxyethyl), propyl maleate (2-hydroxyethyl), butyl maleate (2-hydroxyethyl), Methyl maleate (2-hydroxypropyl), ethyl maleate (2-
Alkyl (hydroxyalkyl) ester of maleic acid such as hydroxybutyl), methyl itaconate (2-hydroxyethyl), ethyl itaconate (2-hydroxyethyl), propyl itaconate (2-hydroxyethyl), ethyl itaconate (2 -Hydroxypropyl),
Alkyl (2-hydroxyalkyl) itaconic acid esters such as methyl itaconic acid (2-hydroxybutyl), alcohols having an allyl group such as allyl alcohol, amides such as hydroxymethyl acrylamide and hydroxymethyl methacrylamide, hydroxymethyl styrene and hydroxyethyl. Examples thereof include hydroxyalkyl styrenes such as styrene, but 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate are preferable in terms of price and availability. You may use these unsaturated alcohols in combination of 2 or more type.

The styrene-maleic anhydride copolymer (IV) used in the present invention is obtained at a styrene / maleic anhydride molar ratio in the range of 3/1 to 7/1 and has a number average molecular weight of less than 5,000. is there. Preferably, the molar ratio of styrene / maleic anhydride is 4/1 to 5/1 and the number average molecular weight is 1
It is 500 to 3000. When the molar ratio of styrene / maleic anhydride is less than 3/1, the compatibility with the unsaturated polyester resin is poor, and the characteristics of the artificial marble obtained by the phase separation deteriorate, and the molar ratio exceeds 7/1. Therefore, the transparency of the obtained molded article is lowered. Further, when the number average molecular weight is 5,000 or more, the compatibility with the unsaturated polyester (I), the copolymerizable monomer (II) and the unsaturated alcohol (III) is poor, and the artificial marble obtained by phase separation is obtained. The characteristics of are degraded. This copolymer is already known,
For example, product name GSM-503, G manufactured by Gifu Shellac Factory
There are SM-505 and the like. The amount of the unsaturated alcohol (III) used is the unsaturated alcohol (III) / copolymerizable monomer (I
The weight ratio of I) is 50/50 to 1/99, preferably 1 /
The range is 99 to 15/85. Unsaturated alcohol (III) / copolymerizable monomer (II) weight ratio is 50/50
If it exceeds, the water resistance of the obtained artificial marble is lowered. Furthermore, when the amount of unsaturated alcohol (III) used is less than 1/99, the styrene-maleic anhydride copolymer (IV)
Is an unsaturated polyester (I), a copolymerizable monomer (II)
Also, the compatibility with the unsaturated alcohol (III) becomes poor, and the characteristics of the obtained artificial marble deteriorate due to the phase separation.

The weight ratio of unsaturated polyester (I) / [copolymerizable monomer (II) + unsaturated alcohol (III)] is
The range is 30/70 to 70/30, preferably 4
The range is 5/55 to 65/35. Weight ratio is 30 /
When it is less than 70, the curing shrinkage ratio becomes large, and the artificial marble is cracked, and when it exceeds 70/30, the properties of the obtained artificial marble deteriorate. The weight ratio of styrene-maleic anhydride copolymer (IV) / [unsaturated polyester (I) + copolymerizable monomer (II) + unsaturated alcohol (III)] is from 10/90 to 40/60. It is set to the range, preferably 15/85 to 30/70. If this weight ratio is less than 10/90, the artificial marble is cracked,
When it exceeds 60, the characteristics of the obtained artificial marble deteriorate.
In addition, unsaturated polyester (I), copolymerizable monomer (I
If the compatibility with I) and unsaturated alcohol (III) is good, the above-mentioned copolymerizable monomer (II) is contained in addition to styrene and maleic anhydride, and [styrene + copolymerizable monomer (II)] / maleic anhydride molar ratio is 3/1 to 7 /
A copolymer having a range of 1 and a number average molecular weight of less than 5,000 can also be used. A tin compound (VI) soluble in the copolymerizable monomer (II), for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin malate, dilauryltin diacetate, dioctyltin diacetate and the like can be used. The tin compound (VI) is used in an amount of 0. 0 with respect to 100 parts by weight of the artificial marble resin composition.
The range of 1 to 1.0 parts by weight is preferable.

As the glass powder and / or aluminum hydroxide, those generally used for artificial marble are used, and the usage amount, particle size and particle size distribution are selected according to the characteristics of the patterned artificial marble to be obtained, and particularly, There is no limit. Further, glass powder and aluminum hydroxide may be used in combination. The paint to be applied to the back surface is selected according to the characteristics of the patterned artificial marble from which commercially available floor paints, wall paints, etc. can be obtained, and there is no particular limitation. The paint is applied by brush coating, roll coating, spray coating, or the like.
In the resin composition (V) of the present invention, the glass fiber, the polymerization catalyst, the thickener, the release agent and the polymerization inhibitor, which are generally used for the bulk molding compound and the sheet molding compound, and further the silane coupling agent as necessary. , UV absorbers, accelerators and chain transfer agents are used. The amount of these used is selected according to the characteristics of the obtained patterned artificial marble and is not particularly limited. Furthermore, the resin composition (V) may be used in combination with polystyrene, polymethylmethacrylate, polyvinyl acetate, a copolymer thereof, or the like, if necessary. These polystyrenes and the like are preferably used in an amount of 30 parts by weight or less with respect to 70 parts by weight of the styrene-maleic anhydride copolymer because of the transparency of artificial marble.

Usually, a composition containing an unsaturated polyester (I), a copolymerizable monomer (II), an unsaturated alcohol (III) and a styrene-maleic anhydride copolymer (IV) is used as a polymerization catalyst, if necessary. After adding the above tin compound (VI) accordingly, glass powder and / or aluminum hydroxide,
Preferably, the above components such as glass fiber having a length of about 0.5 to 6 mm are added, and the mixture is kneaded well, preferably while being deaerated, and left to stand in an atmosphere of room temperature to 60 ° C. for 1 to 5 days for aging. A bulk molding compound having an increased viscosity and good workability can be obtained. This bulk molding compound is heated and compression molded in a mold and cured by radical polymerization. The temperature is preferably 100 to 150 ° C., and the pressure is preferably 20 to 150 kg / cm ² . Thereby, a molded product having excellent water resistance, transparency and luster is obtained. By applying a paint to the back surface of this molded product, a patterned artificial marble having a deep feeling can be obtained. Furthermore, different patterned artificial marbles can be obtained by using the same bulk molding compound by changing the paint.

Further, usually, unsaturated polyester (I),
After adding a polymerization catalyst and, if necessary, a tin compound (VI) to a composition containing a copolymerizable monomer (II), an unsaturated alcohol (III) and a styrene-maleic anhydride copolymer (IV), Glass powder and / or aluminum hydroxide,
Good workability is obtained by adding the above-mentioned components other than glass fiber such as a polymerization catalyst, stirring well, and preferably impregnating the glass fiber having a length of about 25 mm and leaving it in an atmosphere at room temperature to 60 ° C for 1 to 5 days. A sheet molding compound having This sheet molding compound is heat compression molded in a mold and cured by radical polymerization. Temperature is 100-150 ° C, pressure is 20-150
It is preferably about kg / cm ² . Thereby, a molded product having excellent water resistance, transparency and luster is obtained. By applying a paint to the back surface of this molded product, a patterned artificial marble having a deep feeling can be obtained. Moreover, different patterned artificial marbles can be obtained by using the same sheet molding compound by changing the paint.

[0013]

Example 1 1410 g of hydrogenated bisphenol A, 250 g of neopentyl glycol, 370 g of propylene glycol and 1490 g of isophthalic acid were charged into a 5-liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube and a thermometer, The temperature was raised from room temperature to 190 ° C in 1 hour, and then raised to 215 ° C in 5 hours to continue the reaction. When the acid value became 5 mgKOH / g or less, the temperature was lowered to 120 ° C, 810 g of neopentyl glycol and 1070 g of maleic anhydride were charged, the temperature was raised to 160 ° C in 1 hour, and then the temperature was raised to 215 ° C in 4 hours. Warm and continue the reaction, acid value 2
2 mg KOH / g of unsaturated polyester (A) was obtained. Unsaturated polyester (A) 600 g, styrene 350 g,
Resin composition (B) dissolved in 50 g of 2-hydroxyethyl methacrylate, GSM-505 (styrene-maleic anhydride copolymer, styrene / maleic anhydride molar ratio = 5/1, number average molecular weight 2500 (stock) Gifu shellac factory trade name) 600 g of styrene dissolved in 400 g of resin composition (C) and dibutyltin dilaurate, resin composition (B) / resin composition (C) / dibutyltin dilaurate weighted to 60 As /40/0.5,
The resin composition (D) was obtained by thoroughly stirring and mixing. 260mmHg using the planetary mixer
After kneading under reduced pressure, the mixture was allowed to stand in an atmosphere of 40 ° C. for 48 hours to obtain a thickened bulk molding compound (E) having good workability. A bulk molding compound (E) was used to obtain a molded product (F) having a thickness of 8 mm and excellent transparency and luster by using a flat plate mold (250 mm × 500 mm). The linear shrinkage of the molded product (F) was 0.3%. The molding conditions are a mold temperature of 140 ° C. and a molding pressure of 100.
kg / cm ² , and molding time was 10 minutes. Molded product (F) at 90 ℃
After being immersed in the hot water for 100 hours, the appearance was visually evaluated. No blister, crack, or remarkable whitening was observed in the molded product (F). Solvent-based acrylic green paint (Hyster HIS-AF3-540G) on the back of the molded product (F).
R, a product name of Hitachi Chemical Co., Ltd.) was applied using a brush and left for 24 hours to obtain a green artificial marble with a deep texture.

Example 2 Solvent-type acrylic white paint (Hister HIS-UF-1036W, trade name of Hitachi Chemical Co., Ltd.) and solvent-type acrylic were applied to the back surface of the molded product (F) obtained in Example 1. A gray paint (Hyster HIS-AF3-359GY, trade name of Hitachi Chemical Co., Ltd.) is partially applied with a brush,
When left for 24 hours, a patterned artificial marble similar to natural marble was obtained.

Example 3 Using the resin composition (D) obtained in Example 1, the compounds shown in Table 1 were kneaded with a planetary mixer under a reduced pressure of 260 mmHg, and then in an atmosphere of 40 ° C. After standing for 48 hours, a thickened bulk molding compound (G) having good workability was obtained. The bulk molding compound (G) was used to obtain a molded product (H) having a thickness of 3 mm and excellent transparency and gloss, using a flat plate mold (250 mm × 500 mm). The linear shrinkage of the molded product (H) was 0.3%. Molding conditions are mold temperature 140 ℃, molding pressure 10
The molding time was 0 kg / cm ² and the molding time was 10 minutes. Molded product (H) 90
After dipping in hot water at ℃ for 100 hours, the appearance was visually evaluated. No blister, crack, or remarkable whitening was observed in the molded product (H). Solvent-based acrylic green paint (Hister HIS-AF3-540 on the back surface of the molded product (H)
GR) was applied and allowed to stand for 24 hours to obtain a green artificial marble with a deep texture.

Comparative Example 1 The resin composition (B) obtained in Example 1 and polystyrene 40
Resin composition (G) prepared by dissolving 0 g in 600 g of styrene
And the resin composition (B) / resin composition (G) in a weight ratio of 70/30, and well stirred and mixed to obtain the resin composition (I).
Got The formulations shown in Table 1 were kneaded using a planetary mixer under a reduced pressure of 260 mmHg, and then left under an atmosphere of 40 ° C. for 48 hours to obtain a thickened bulk molding compound (J). Bulk molding compound (J), flat plate mold (250 mm x 500 mm)
Was used to obtain a white opaque molded product (K) having a thickness of 8 mm.
Molding conditions are mold temperature 140 ℃, molding pressure 100kg / c
m ² and molding time were 10 minutes. The paint was applied to the back surface of the molded product (K) by using a brush as in Example 1, but a patterned artificial marble having a feeling of depth could not be obtained.

Comparative Example 2 Using the resin composition (D) obtained in Example 1, the compound of Comparative Example 2a shown in Table 1 was kneaded using a planetary mixer under a reduced pressure of 260 mmHg, and then 40 The mixture was allowed to stand for 48 hours in an atmosphere of ° C to obtain a thickened white bulk molding compound (L). Moreover, after using the resin composition (D) obtained in Example 1 and kneading the mixture of Comparative Example 2b shown in Table 1 with a planetary mixer under a reduced pressure of 260 mmHg, in an atmosphere of 40 ° C. Gray bulk molding compound (M) thickened after being left at room temperature for 48 hours
Got

The white bulk molding compound (L) obtained above is dispersed with the gray bulk molding compound (M) obtained above and partially applied,
Using a flat plate mold (250 mm × 500 mm), a molded product (N) having a thickness of 8 mm was obtained. The molding conditions were a mold temperature of 140 ° C., a molding pressure of 100 kg / cm ² , and a molding time of 10 minutes. The molded product (N) had a gray flow pattern and a patterned artificial marble similar to natural marble could not be obtained.

[0019]

[Table 1] * 1) Glass powder (trade name of Nitto Boseki Co., Ltd.) * 2) Aluminum hydroxide (trade name of Showa Denko KK)

[0020]

Industrial Applicability According to the manufacturing method of the present invention, artificial marble having a deep pattern can be easily and efficiently obtained, and the obtained artificial marble has a vanity, a kitchen counter, and a bathtub. , Tiles, wall panels, etc.

Claims (4)

(57) [Claims] 1. An unsaturated polyester (I) and a copolymerizable monomer (II) obtained by using a dihydric alcohol containing hydrogenated bisphenol A as an essential component and an α, β-ethylenically unsaturated dibasic acid. The unsaturated polyester (I) and the unsaturated alcohol (III) copolymerizable with the copolymerizable monomer (II), and the styrene / maleic anhydride molar ratio in the range of 3/1 to 7/1, A low molecular weight styrene-maleic anhydride copolymer (IV) having an average molecular weight of less than 5000 is used, and the unsaturated alcohol (III) is used in an amount of unsaturated alcohol (III) / copolymerizable monomer (II). In the range of 1/99 to 50/50, and the weight ratio of unsaturated polyester (I) / [copolymerizable monomer (II) + unsaturated alcohol (III)] is 30/70 to 70/30. Range of
The weight ratio of styrene-maleic anhydride copolymer (IV) / [unsaturated polyester (I) + copolymerizable monomer (II) + unsaturated alcohol (III)] is in the range of 10/90 to 40/60. And a resin composition (V) containing glass powder and / or aluminum hydroxide is heated and compression molded in a mold,
A method for producing a patterned artificial marble, characterized in that a paint is applied to the back surface of the molded product. 2. A resin composition (V) containing a copolymerizable monomer (I
Resin composition (V) containing a tin compound (VI) soluble in I)
The method for producing a patterned artificial marble according to claim 1. 3. The resin composition (V) further comprising glass fiber,
The resin composition (V) comprising a polymerization catalyst, a thickener, a release agent, a polymerization inhibitor and, if necessary, a silane coupling agent, an ultraviolet absorber, an accelerator and a chain transfer agent. The method for producing the artificial marble with the described pattern. 4. A bulk molding compound or a sheet molding compound, the viscosity of which has been increased by aging the resin composition (V) according to claim 3 at room temperature to 60 ° C., and heat compression molding in a mold. Two
The method for producing the artificial marble with the described pattern.