KR100445992B1 - Method for preparing acrylic-modified unsaturated polyester resin for producing artificial marble with low cost and resin composition containing the same resin - Google Patents

Abstract

PURPOSE: Provided is a method for preparing an acrylic-modified unsaturated polyester resin for producing artificial marble having excellent appearance with low cost. CONSTITUTION: The method for preparing an acrylic-modified unsaturated polyester resin for producing artificial marble by the copolymerization of an aliphatic or aromatic dihydric acid with polyhydric alcohol comprises the steps of: (a) reacting isophthalic acid with di- or tri-hydric glycol at an alcohol/acid equivalent ratio of 2-2.5 to form a prepolymer having an acid value of 2-3; (b) adding to 10-25 parts by weight of the prepolymer of step (a), 7-15 parts by weight of maleic acid or fumaric acid and 10-20 parts by weight of phthalic anhydride and reacting the mixture to form an unsaturated resin; and (c) adding to 59-70 parts by weight of the unsaturated resin of step (b), 25-35 parts by weight of styrene and 10-30 parts by weight of multifunctional acrylic monomer having 3-6 acrylic functional groups and reacting the mixture.

Description

Method for producing acrylic modified unsaturated polyester resin for artificial marble production and resin composition containing same

The present invention relates to a method for producing an acrylic modified unsaturated polyester resin for artificial marble, and a resin composition containing the same, and more particularly, to prepare a prepolymer by reacting isophthalic acid and glycol, wherein maleic acid or fumaric acid and anhydrous A method of preparing an acrylic modified unsaturated polyester resin for preparing artificial marble by adding a styrene monomer and an acrylic monomer by adding phthalic acid to the unsaturated polyester resin, and adding powdered stone, thickener, curing agent, It relates to a resin composition for artificial marble production made by mixing.

Artificial marble is widely used as a counter top plate, a furniture top plate, a building finishing material, various decorative materials, and the like, and conventionally, as an artificial marble manufacturing resin, unsaturated polyester is used or polymethyl methacrylate resin is used.

However, the artificial marble using a conventional unsaturated polyester resin has a poor appearance and must be made of a coating layer, and abnormalities are generated on the surface, which entails considerable difficulty in correcting or repairing.

In addition, Japanese Patent Application Laid-Open No. 61-141654 discloses a method for producing artificial marble using polymethyl methacrylate resin, which basically has a disadvantage in that the resin manufacturing process of polymethyl methacrylate is complicated and the raw material cost is high. have.

Therefore, the present inventors have made efforts to solve the problems of the conventional resin composition for manufacturing artificial marble, acrylic modified unsaturated poly for producing artificial marble of the present invention by modifying the unsaturated polyester resin to acrylic, beautiful appearance and low price A method for preparing an ester resin has been developed.

An object of the present invention is to provide a method for producing an acrylic modified unsaturated polyester resin for producing artificial marble with excellent appearance and low cost, and a resin composition containing the same.

Hereinafter, the present invention will be described in detail.

The present invention,

(A) reacting isophthalic acid and a bivalent glycol with an alcohol / acid equivalent ratio of 2 to 2.5 in the presence of an esterification catalyst and a reaction stabilizer to prepare a prepolymer having an acid value of 2-3;

(B) adding unsaturated maleic acid or fumaric acid and phthalic anhydride, and a reaction stabilizer to the prepolymer of (a) to react to prepare an unsaturated polyester resin, and

(C) It relates to a method for producing an acrylic modified unsaturated polyester resin for artificial marble production comprising the step of adding and reacting a styrene monomer and a polyfunctional acrylic monomer to the unsaturated ester resin of (b).

The present invention will be described in more detail as follows.

The present invention relates to a method for producing an acrylic modified unsaturated polyester resin for producing artificial marble having excellent appearance and low cost, and a composition for preparing artificial marble using the same, wherein the unsaturated polyester resin which is thermoset as a resin added to the artificial marble composition in the present invention The resin modified with acryl is added.

Unsaturated polyester resin is basically manufactured using isophthalic acid, so excellent in chemical resistance. When this is prepared by modifying it with a polyfunctional acrylic monomer, the acrylic modified unsaturated polyester of the present invention is obtained.

Here, the acrylic modified unsaturated polyester resin is produced by ester reaction of saturated acid, unsaturated acid, and dihydric alcohol, and has an unsaturated bond in the middle of the linear polymer, and this unsaturated bond, polyfunctional acrylic monomer, and styrene monomer By combining, a hardened product having a very dense network can be obtained.

In general, monomers used in the production of unsaturated polyester resins include polyhydric alcohols having 2 to 3 functional groups and aliphatic or substituted aliphatic alcohols having 2 to 6 carbon atoms and alicyclic having 4 to 14 carbon atoms having 2 to 4 carboxyl groups in the molecule. And aromatic carboxylic acids and unsaturated acids.

Here, as the dihydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,5-pentanediol, neopentyl Glycols, 1,6-hexanediol or 1,4-cyclohexanediol, trimethylolpropane, triethylolpropane or glycerol as trihydric alcohol and pentaerythritol as tetrahydric alcohol.

Examples of the carboxylic acid having two or more reactive groups include adipic acid, azeline acid, succinic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, phthalic anhydride, terephthalic acid, isophthalic acid, diethyl terephthalic acid, trimellitic acid, and 4 Hydrogen phthalic anhydride or trimellitic anhydride, and unsaturated carboxylic acids include maleic acid, fumaric acid or maleic anhydride.

In the present invention, isophthalic acid or phthalic anhydride having excellent chemical resistance among the saturated acids, and maleic anhydride or fumaric acid are used as the unsaturated acid, and alcohols are propylene glycol or neopentyl glycol, etc. This short, high strength polyester resin is produced.

The acrylic modified unsaturated polyester resin of the present invention can be prepared by (a) reacting isophthalic acid with a divalent glycol in an alcohol / acid equivalent ratio of 2 to 2.5 in the presence of an esterification catalyst and a reaction stabilizer to prepare a prepolymer having an acid value of 2-3. (B) preparing an unsaturated ester by adding maleic acid or fumaric acid and phthalic anhydride, and a reaction stabilizer to the prepolymer of (a), followed by reaction to prepare an unsaturated ester, and (c) the unsaturated ester of (b). A styrene monomer and a polyfunctional acrylic monomer are added to the resin and reacted.

In more detail, (A) 10-25 parts by weight of isophthalic acid and 2 to trivalent glycol are prepared in the presence of 0.001 to 0.1 parts by weight of an alcohol / acid equivalent ratio of 2 to 2.5. (B) 7 to 15 parts by weight of maleic acid or fumaric acid and 10 to 20 parts by weight of phthalic anhydride are added to 10 to 25 parts by weight of the (a) prepolymer to react with an unsaturated polyester in the presence of 0.001 to 0.1 parts by weight of a stabilizer. A step of preparing a resin, (c) 25 to 35 parts by weight of a styrene monomer and 10 to 30 parts by weight of an acrylic monomer are reacted by 59 to 70 parts by weight of the (b) unsaturated unsaturated resin.

First, (a) preparing the prepolymer, in order to prepare the prepolymer by reacting the alcohol / acid equivalent ratio of 2 to 2.5, first, the alcohol mixture is put into a reactor equipped with a stirrer, a thermometer, nitrogen gas injection, a charge cooler, and the like. . Then, the mixture is heated to 80 to 120 DEG C while injecting nitrogen gas to melt, followed by addition of acid with stirring. At this time, 0.005 to 0.5 parts by weight of the esterification catalyst is added. After adding 0.001 to 0.01 parts by weight of the reaction stabilizer, the condensed water began to flow out of the reaction system at 170-180 ° C while increasing the temperature continuously, and the reaction product became clear when the condensed water was removed while raising the reaction temperature to 210-220 ° C. Done. The reaction is continued while increasing the amount of nitrogen gas injected, and the reaction is terminated at an acid value of 2 or less and then cooled to 120 ° C or less.

Next, (b) while adding maleic acid or fumaric acid and phthalic anhydride to the prepolymer prepared above, adding 0.001 to 0.1 parts by weight of a reaction stabilizer and raising the temperature while injecting nitrogen to increase the temperature of the acid anhydride at 160 to 170 ° C. The ring-opening reaction took place, and dehydration was confirmed, the temperature was raised to 210 ° C. and the nitrogen was added at an acid value of 25 or less while maintaining the reaction at that temperature until the styrene monomer dilution viscosity reached 8 to 18 poise. The unsaturated polyester resin of degree is manufactured.

Then, (C) the unsaturated polyester resin obtained in the above (B) was cooled to 180 to 170 ° C., diluted in a styrene monomer as a reactive monomer, and then an acrylic monomer was added at 40 ° C. or lower to obtain a final acrylic modified unsaturated polyester resin. Manufacture.

At this time, the acrylic monomer used is three or more functional groups, and specific examples thereof include trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, and pentaeryth. There are lititol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate or pentaerythritol trimethacrylate, and the tetrafunctional acrylic monomer is pentaerythritol tetraacrylate or pentaerythritol Tetramethacrylate, and the 6 functional acryl monomer are dipentaerythritol hexaacrylate or dipentaerythritol hexamethacrylate.

In the present invention, the artificial marble resin composition is prepared by containing the above resin, and the specific composition thereof is 15 to 40 parts by weight of the acrylic-modified unsaturated polyester resin prepared above, 60 to 80 parts by weight of the filler, and 100 parts by weight of the resin. It prepares by mixing 1.4-3.0 weight part of hardening | curing agents, 0.7-1.5 weight part of thickeners, and 0.7-1.5 weight part of internal mold release agents.

At this time, the filler added is alumina hydroxide, and the thickener is magnesium oxide.

If the content of the acrylic modified unsaturated polyester resin added here is less than 15 parts by weight, there is a problem that the appearance of the manufactured artificial marble is poor, and if it exceeds 40 parts by weight, there is a problem that the filler distribution of the manufactured artificial marble is uneven.

The above composition may be aged for 1 to 10 days to compression molding under a pressure of 50 to 150 Psi, a mold temperature of 50 to 150 ° C., and a pressure stop condition of 2 to 7 minutes to prepare artificial marble.

Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.

Example 1

(A); 10.0 parts by weight of propylene glycol and 19.1 parts by weight of neopentyl glycol were introduced into a reactor equipped with a stirrer, a thermometer, a nitrogen gas injection tube, a charge cooler, etc., heated at 100 ° C. while injecting nitrogen gas, melted, and stirred. 0.042 parts by weight of Fescat 4101 (manufactured by M & T) as an esterification catalyst and 0.003 parts by weight of naphthobin KX 405 (manufactured by Metelgegel Shaft AG, Germany) as a reaction stabilizer were added. The condensed water then begins to flow out of the reaction system at 170 to 180 ° C. while continuously raising the temperature, and the reactant becomes transparent when the condensed water is removed while increasing the reaction temperature to 210 to 220 ° C. The reaction was continued while increasing the amount of nitrogen gas injected, the reaction was terminated at an acid value of 2 to 3, and then cooled to 120 ° C. or less to prepare a prepolymer.

(B); 10.4 parts by weight of phthalic anhydride, 7.8 parts by weight of maleic anhydride, and 0.002 parts by weight of naphthobin KX 405 (manufactured by Metelgegelshaft AG, Germany) were added to the prepolymer, and the temperature was raised while injecting nitrogen while stirring. The ring-opening reaction of the acid anhydride occurs at ~ 170 ℃, dehydration is confirmed and the temperature is raised to 210 ℃, the nitrogen is added to the water while maintaining the reaction at that temperature until the styrene monomer dilution viscosity is 8-18 poise at an acid value of 25 or less 67 parts by weight of unsaturated polyester resin having an average molecular weight of 4300 was prepared.

(All) ; Then, 0.006 parts by weight of hydroquinone was added thereto to stop further reaction, and the resin was cooled to 180 to 170 ° C, diluted in the total amount of the styrene monomer, and then cooled to a temperature of 40 ° C or less to pentaerythr. 15.4 parts by weight of lititol triacrylate was added to prepare 114 parts by weight of resin.

Examples 2 to 3

Next, an acrylic modified unsaturated polyester resin was prepared in a composition and content ratio as shown in Table 1, and the preparation method thereof was the same as in Example 1.

Comparative Example 1

The reaction was carried out in the same order as in Example 1, (A) 18.5 parts by weight of isophthalic acid, 27.4 parts by weight of propylene glycol, and 22.2 parts by weight of maleic anhydride were added to the prepared prepolymer ( B) After preparing an unsaturated polyester resin, an unsaturated polyester resin was prepared by adding 0.004 parts by weight of hydroquinone and 40.0 parts by weight of styrene monomer.

Comparative Example 2

In this case, a phthalic anhydride resin, which does not require the preparation of a prepolymer, was prepared. The ring-opening reaction was performed by adding 24.1 parts by weight of phthalic anhydride, 15.96 parts by weight of maleic anhydride, 13.0 parts by weight of propylene glycol, and 17.8 parts by weight of neopentylglycol. Preparation reaction of the unsaturated polyester resin of Example 1 was carried out.

Examples 4-6 and Comparative Examples 3-4

Each resin prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 was mixed with a composition as shown in Table 2 to prepare a composition for preparing artificial marble in a conventional manner.

(1) Example 4-Acrylic modified unsaturated polyester resin prepared according to Example 1

Example 5 Acrylic Modified Unsaturated Polyester Resin Prepared According to Example 2

Example 6 Acrylic Modified Unsaturated Polyester Resin Prepared According to Example 3

Comparative Example 3-Unsaturated Polyester Resin Prepared According to Comparative Example 1

Comparative Example 4-Unsaturated Polyester Resin Prepared According to Comparative Example 2

(2) Alumina Hydroxide (DGE FILLER, manufactured by Aljay Marshall, USA)

(3) t-butyl peroxy benzoate (TBPB, Gagwak, Japan)

(4) Bis (4-t-butylcyclohexyl) peroxy dicarbonate (Pergadox-16, Gagwak, Japan)

(5) PS-125, Axl Products, USA

Experimental Example 1

The hardness, tensile strength, tensile modulus, flexural strength, flexural modulus and elongation of the acrylic modified unsaturated polyester resin prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 3 below. As shown.

Here, the bark hardness was measured by ASTM 2583, tensile strength was measured by ISO R3286, tensile modulus by ISO R3268, flexural strength was measured by ISO R3286, flexural modulus by ISO R3268, and elongation was measured by using ISO R527. .

Experimental Example 2

The appearance, the tack hardness, the heat deformation temperature, the flame resistance, the scratch resistance and the pencil hardness were measured for the compositions for preparing artificial marble prepared according to Examples 4 to 6 and Comparative Examples 3 to 4, and the results are shown in Table 4 below. As shown.

Here, the heat deflection temperature was measured by KSM 3305, flame retardancy was measured by KSM 3015, scratch resistance by CS-221-66, and the appearance was visually determined, but determined according to the need of subsequent coating. In addition, the pencil hardness was measured using a pencil hardness tester (manufactured by Mitsubishi Corporation).

From the results of Tables 3 and 4, Examples 1 to 6 of the present invention have good physical properties, but in the comparative example, the resin alone has excellent strength but poor appearance and poor scratch resistance. In addition, it shows that the pencil hardness, the hardness of the bark, the heat deformation temperature, etc. are significantly superior to the physical properties of the comparative example.

Therefore, the acrylic modified unsaturated polyester resin of the present invention is excellent in moldability than conventional unsaturated polyester resin, and when the artificial marble is manufactured using the same, it is possible to produce an artificial marble having excellent physical properties of artificial marble itself.

Claims (6)

In the method for producing an unsaturated polyester resin by ester copolymerization of an aliphatic or aromatic divalent acid and a polyhydric alcohol, (A) reacting isophthalic acid and 2-3 trivalent glycols with an alcohol / acid equivalent ratio of 2 to 2.5 to prepare a prepolymer having an acid value of 2-3; (B) adding 10 to 25 parts by weight of maleic acid or fumaric acid and 10 to 20 parts by weight of phthalic anhydride to 10 to 25 parts by weight of the prepolymer of (a) to react to prepare an unsaturated ester resin, and (C) reacting 59 to 70 parts by weight of the unsaturated ester resin (B) with 25 to 35 parts by weight of styrene monomer and 10 to 30 parts by weight of the polyfunctional acrylic monomer having 3 to 6 acrylic functional groups to react; Method for producing acrylic modified unsaturated polyester resin for artificial marble production, characterized in that consisting of. The method of claim 1, wherein the polyfunctional acrylic monomer is trimethylol ethane triacrylate, trimethylol ethane trimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol propane triacrylate At least one selected from pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate A method for producing an acrylic modified unsaturated polyester resin for producing artificial marble, characterized by using a compound. 15 to 40 parts by weight of the acrylic modified unsaturated ester resin prepared according to claim 1, 60 to 85 parts by weight of filler and 100 parts by weight of the resin, curing agent 1.4 to 3.0 and internal mold release agent 0.7 to 1.5 parts by weight and thickener 0.7 ~ 1.5 parts by weight of artificial marble, characterized in that the composition for producing. 4. The composition of claim 3, wherein the filler is alumina hydroxide. The composition of claim 3, wherein the curing agent is t-butyl peroxy benzoate or bis (4-t-butylcyclohexyl) peroxy dicarbonate. 4. The composition of claim 3, wherein the thickener is magnesium oxide.