KR100596935B1 - Composition for Artificial Marble Having Excellent Mechanical Properties and Method for Preparing the Same - Google Patents

Abstract

The artificial marble having excellent mechanical properties of the present invention includes (A) 100 parts by weight of an acrylic resin syrup, (B) 0.3 to 10 parts by weight of a crosslinking agent, 100 to 300 parts by weight of an inorganic filler, 0.1 to 10 parts by weight of a polymerization initiator, and 0 to Marble Chips. 150 parts by weight and a mixture of (iii) a silane coupling agent and (ii) a phosphate-based coupling agent having an acid or an alcohol as a functional group.

Artificial marble, silane coupling agent, mechanical strength, phosphate coupling agent

Description

Composition for Artificial Marble Having Excellent Mechanical Properties and Method for Preparing the Same}

Field of invention

The present invention relates to an artificial marble composition having excellent mechanical strength. More specifically, the present invention uses a mixture of different types of coupling agents that can complement each other in the composition for artificial marble in an appropriate ratio, so that even a small amount of coupling agent is used without a complicated pretreatment process of the coupling agent. The present invention relates to an artificial marble having excellent mechanical strength.

Background of the Invention

Artificial marble is widely used as a building interior material in recent years, and largely divided into two types, acrylic and unsaturated polyester, depending on the base resin used. Among them, acrylic artificial marble is used for various purposes due to its soft transparency, luxurious texture, and excellent weather resistance, and its demand is continuously increasing.

For example, it is used worldwide as sink tops, vanity tops, counter tops such as banks and general shops, interior walls of commodity stores, bathtubs, sink bowls and various interior sculptures. This is expanding.

Such artificial marble is characterized by being easily damaged by external impact during transportation or processing.

In order to solve the problem of being easily damaged by impact, various types of coupling agents are used to improve mechanical strength. In general, a coupling agent composed of a silane (Si) or a phosphate (PO ₄ ) is used as the coupling agent. In addition, the coupling agent contains an acid (-COOH) or alcohol (-OH), which is a functional group capable of coupling, and the functional group portion is -OR form (R: Methyl, Ethyl, Amono-alkyl, etc.) It may consist of. In the former case, the coupling agent can be used efficiently because no separate pretreatment is required. However, in the latter case, a sufficient amount cannot be added by acting as a scavenger to the radical that serves as a reaction initiation. Through the pretreatment process, the coupling agent may be changed into a form that facilitates the coupling action, or the coupling agent may be excessively added.

Many manufacturers have a high initial capital investment in using coupling agents to improve mechanical strength, do not require additional processes than pretreatment methods that require additional processes, and have a relatively low impact on the reaction. The method of adding an excessive amount of coupling agents is used. However, the excessive use of a relatively expensive coupling agent has the disadvantage of causing an increase in the manufacturing cost, there is a disadvantage that a quality deviation depending on the process conditions such as temperature or humidity.

In order to make up for the above disadvantages, the pretreatment method of the coupling agent to be changed into a form in which the coupling agent can function sufficiently should be simplified as much as possible.

Therefore, the present inventors, in order to overcome the above problems, by using a silane coupling agent as a coupling agent in a proper ratio of a phosphate-based coupling agent having an acid or an alcohol (alcohol) as a functional group, one of the other couple It improves the efficiency of the coupling agent by simultaneously performing the catalyst role required for the pretreatment of the ring agent, thereby minimizing the influence of the coupling agent on the reaction, and having excellent mechanical properties without additional pretreatment or excessive input. It is early to develop the marble composition.

An object of the present invention is to provide an artificial marble composition excellent in mechanical properties.

Another object of the present invention is to provide a method for producing artificial marble having excellent mechanical properties without additional pretreatment or excessive input.

The above and other objects of the present invention can be achieved by the present invention described below.                         

Hereinafter, the content of the present invention will be described in detail below.

The artificial marble composition having excellent mechanical properties of the present invention comprises (A) 100 parts by weight of an acrylic resin syrup, (B) 0.3 to 10 parts by weight of a crosslinking agent, (C) 100 to 300 parts by weight of an inorganic filler, and (D) 0.1 to 10 polymerization initiators. It consists of 0.5-1.5 weight part of mixtures of a weight part, (E) 0-150 weight part of marble chips, and (F) (iii) a silane coupling agent, and (ii) a phosphate type coupling agent which has an acid or an alcohol as a functional group. Hereinafter, each component of this invention is demonstrated in detail below.

(A) acrylic resin syrup

The acrylic resin syrup used in the present invention is a resin syrup in which an acrylic monomer and a polyacrylate which is a polymer thereof are dissolved.

The acrylic monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like.

The acrylic resin syrup of the present invention preferably has an acrylic monomer content of 65% by weight or more and an acrylic polymer content of 35% by weight or less.

(B) crosslinking agent

As the crosslinking agent of the present invention, polyfunctional methacrylate is used, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycerol trimethacrylate, trimethyl propane trimethacrylate and bisphenol A dimethacrylate. The rate is mentioned.

The polyfunctional monomer is added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic resin syrup, preferably 0.3 to 10 parts by weight.

(C) inorganic filler

The inorganic filler of the present invention may be any of inorganic powders commonly used in the art, such as calcium carbonate, aluminum hydroxide, silica, alumina, barium lactate, magnesium hydroxide, and preferably has a size of 1 to 100 μm. .

Among the inorganic powders, aluminum hydroxide is particularly preferable in that it can produce artificial marble having a transparent and beautiful marble appearance.

In the case of the artificial marble slurry, the mixing ratio of the inorganic filler of the present invention is preferably 100 to 300 parts by weight, more preferably 120 to 200 parts by weight, based on 100 parts by weight of the acrylic resin syrup. In the case of the marble chip, the inorganic filler is preferably added in an amount of 80 to 200 parts by weight, preferably 100 to 150 parts by weight, based on 100 parts by weight of the acrylic resin syrup.

(D) polymerization initiator

As the polymerization initiator of the present invention, peroxides such as benzoyl peroxide, lauroyl peroxide, butyl hydroperoxide, cumyl hydroperoxide or azo compounds such as azobisisobutylonitrile are used.

An organic metal salt for accelerating the polymerization rate or an accelerator such as an organic amine can be used here.

The content of the polymerization initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic resin syrup.

(E) Marble Chip

Marble chips of the present invention is a particle for expressing the texture of natural stone, 100 to 150 parts by weight of the inorganic filler, 100 to 150 parts by weight of the inorganic filler, 2 to 10 parts by weight of the crosslinking agent and 0.1 to 10 parts by weight of the initiator is cured Next, this was broken using a hammer mill type shredder or cutter type shredder and then classified into 0.1 to 5 mm size using various sizes of shreds.

In the present invention, the mixing ratio of the marble chip is 0 to 150 parts by weight, and more preferably 0 to 70 parts by weight, based on 100 parts by weight of the acrylic resin syrup.

(F) coupling agent

The coupling agent is a substance having both a hydrophobic functional group capable of binding to a resin and a hydrophilic functional group capable of binding to an inorganic filler in a molecule.

Coupling agents of the invention are beta-3,4-epoxycyclohexylethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-aminopropyltrimethoxy A silane coupling agent and a hydroxyethyl methacrylate phosphate, which are made of Si such as silane and are converted into silanol (Si-OH) form through pretreatment such as hydrolysis and combined with an inorganic filler. A phosphate-based coupling agent (ii) having an acid or alcohol as a functional group that can be directly bonded to the inorganic filler without separate pretreatment is used together.

Specific examples of the silane coupling agent (ⅰ) include β-3,4 epoxycyclohexylethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ- Aminopropyltrimethoxysilane and the like. Specific examples of the phosphate coupling agent (ii) having an acid or an alcohol as a functional group include hydroxyethyl methacrylate phosphate, hydroxymethyl methacrylate phosphate, and the like.

In the case of a silane coupling agent, a hydrolysis process using an acid catalyst can be used as a coupling agent in the state of containing an alcohol (-OH) functional group capable of binding to an inorganic filler. Generally, a weak acid such as acetic acid is diluted thinly. Hydrolysis is performed by mixing an aqueous solution with a coupling agent, and then a process of drying the inorganic filler again after dipping the inorganic filler with the spray or the inorganic filler in the mixed solution. Since such a process is too complicated, an excess amount is used when a silane coupling agent is used.

However, in the present invention, it is possible to act as a coupling agent on its own, and by using a phosphate coupling agent having an acid having a strong acid as a functional group, the silane coupling agent plays a catalytic role necessary for hydrolysis. The efficiency of a coupling agent was improved by making it possible to carry out simultaneously.

In the present invention, the mixing ratio of the coupling agent is 0.2 to 1.0 parts by weight, and more preferably 0.3 to 0.6 parts by weight, based on 100 parts by weight of the acrylic resin syrup. The sum of the two coupling agents is preferably 0.5 to 1.5 parts by weight. When the amount of the coupling agent is 0.5 parts by weight or less, sufficient mechanical properties cannot be expected to be improved. When the amount of the coupling agent is added by 1.5 parts by weight or more, the effect of improving the mechanical properties cannot be expected.

Moreover, as for the relative ratio of (iii) and (ii) coupling agent, (ii) coupling agent is 0.5-1.5 times as compared with (iv) coupling agent. (Ii) When the mixing ratio of the coupling agent is (0.5) or less than that of the coupling agent (i) The coupling agent is unable to sufficiently hydrolyze and the mechanical properties are not sufficient, and when the coupling agent is 1.5 times or more (ii) Couple The influence on the reaction by the ring agent is increased, and the reaction rate is greatly reduced.

Artificial marble having excellent mechanical properties of the present invention is prepared by manufacturing the marble chip and artificial marble slurry prepared from the above, sprinkled in a molding cell and then cured in a hot air oven at 45 to 120 ℃.

Artificial marble having excellent mechanical properties of the present invention can solve the problem of adding a separate process for the pretreatment of the coupling agent by using a small amount of the coupling agent to improve the mechanical properties without a separate pretreatment process, as well as expensive It can solve the problem of increasing the manufacturing cost due to the excessive use of the phosphorus coupling agent

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

100 parts by weight of methylmethacrylate acrylate syrup (hereinafter referred to as resin syrup) consisting of a mixture of 30% polymethyl methacrylate and 70% methylmethacrylate, 100 parts by weight of aluminum hydroxide, trimethyl propane trimethacrylate 2 Parts by weight, 2 parts by weight of lauroyl peroxide, γ-methacryloxypropyltrimethoxysilane as the silane coupling agent, and hydroxyethyl methacrylate acid phosphate as the phosphate coupling agent as shown in Table 1 The slurry was prepared, sprinkled in a glass forming cell of 300 × 600 × 15 mm, put in a 45 ° C. hot air oven, and the oven temperature was raised to 100 to cure stepwise. After curing was completed, the mixture was cooled to room temperature to obtain a plate-like artificial marble plate. Flexural strength and impact strength of each manufactured artificial marble specimen were measured and the results are shown in Table 2.

Example Comparative Example One 2 One 2 3 4 5 (A) Coupling agent (parts by weight) 0.6 0.5 0.2 0.6 1.0 2.0 0.0 (B) coupling agent (parts by weight) 0.5 0.6 0.2 0.1 1.0 0.0 0.0

Example Comparative Example One 2 One 2 3 4 5 Flexural Strength (㎏f / ㎠) 732 716 597 630 733 695 532 IZOD impact strength (㎏㎝ / ㎝) 1.5 1.4 1.1 1.2 1.5 1.4 0.8

As shown in Table 2, when the total amount of the coupling agent is used at 0.5 parts by weight or less, and when the content of the phosphate-based coupling agent is excessively small relative to the content of the silane coupling agent, the effect of improving the mechanical properties by the coupling agent is greatly increased. In comparison with the case where only one type is used, even when a small amount is used, a greater physical property improvement effect can be expected, and even when the sum of the two coupling agents is mixed by 1.5 parts by weight or more, the additional improvement effect is small.

The artificial marble of the present invention having excellent mechanical properties is mixed with different types of coupling agents in an appropriate ratio, thereby providing an artificial marble having excellent mechanical properties without undergoing a separate coupling agent pretreatment process or mixing excess coupling agent. It has the effect of the invention.                     

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (9)

(A) 100 parts by weight of acrylic resin syrup; (B) 0.3 to 10 parts by weight of the crosslinking agent; (C) 100 to 300 parts by weight of the inorganic filler; (D) 0.1 to 10 parts by weight of the polymerization initiator; (E) 0 to 150 parts by weight of the marble chip; And 0.5 to 1.5 parts by weight of a mixture of (F) a silane coupling agent and (ii) a phosphate coupling agent having an acid or an alcohol as a functional group; The phosphate-based coupling agent having an acid or an alcohol as a functional group is selected from the group consisting of hydroxyethyl methacrylate phosphate and hydroxymethyl methacrylate phosphate, and the coupling agent (F) (I) 0.2 to 1.0 parts by weight of the silane coupling agent and (ii) the phosphate-based coupling agent having an acid or an alcohol as a functional group, respectively, and the relative ratio of the (i) coupling agent and (ii) the coupling agent is ( Iii) a composition for artificial marble, characterized in that (ii) the coupling agent is 0.5 to 1.5 times that of the coupling agent. The group of claim 1, wherein the acrylic resin syrup (A) is made of methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and 2-ethyl hexyl methacrylate. A resin syrup in which an acrylic polymer of these polymers is dissolved in an acrylic monomer selected from the group, wherein the acrylic monomer content is 65% by weight or more, and the acrylic polymer content is 35% by weight or less. The method of claim 1, wherein the crosslinking agent (B) is selected from the group consisting of ethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycerol trimethacrylate, trimethyl propane trimethacrylate and bisphenol A dimethacrylate. Composition for artificial marble characterized in that it is. The composition for artificial marble according to claim 1, wherein the inorganic filler (C) is selected from the group consisting of calcium carbonate, aluminum hydroxide, silica, alumina, barium lactate and magnesium hydroxide. According to claim 1, The marble chip (E) is mixed with 100 parts by weight of the acrylic resin syrup, 100 to 150 parts by weight of the inorganic filler, 2 to 10 parts by weight of the crosslinking agent and 0.1 to 10 parts by weight of the initiator, and then cured. A composition for artificial marble, which is crushed to a size of 0.1 to 5 mm using a hammer mill crusher or a cutter crusher. delete The silane coupling agent according to claim 1, wherein the silane coupling agent is β-3,4 epoxycyclohexylethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ- A composition for artificial marble, characterized in that it is selected from the group consisting of aminopropyltrimethoxysilane. delete 100 parts by weight of the acrylic resin syrup, 0.3 to 10 parts by weight of the crosslinking agent, 120 to 200 parts by weight of the inorganic filler, 0.1 to 10 parts by weight of the polymerization initiator, 0 to 150 parts by weight of the marble chip and the silane coupling agent and the acid or alcohol 0.5 to 1.5 parts by weight of a mixture of a phosphate-based coupling agent having a functional group is mixed and sprinkled in a molding cell, and then cured in a hot air oven at 45 to 120 ℃.