KR100396834B1 - Thermosetting unsaturated polyester resin composition - Google Patents

Abstract

PURPOSE: A thermosetting unsaturated polyester resin composition is provided, to improve impact resistance, scratch resistance and bending resistance, to reduce density after molding and to enhance appearance. CONSTITUTION: The thermosetting unsaturated polyester resin composition comprises 100 parts by weight of a thermosetting unsaturated polyester resin having a viscosity of 100-800 cP at a room temperature; 100-800 parts by weight of pulverized natural stone; 10-150 parts by weight of a hollow glass bead; 0.05-3 parts by weight of a high temperature curing catalyst and a cobalt-based curing accelerator; 0.1-5 parts by weight of a silane-based coupling agent; and 5 parts by weight or less of a pigment and an additive such as a color stabilizer, a thermal stabilizer, a photostabilizer, etc. Preferably the hollow glass bead is spherical and hollow and has a diameter of 10-30 micrometers, a real density of 0.6-0.8 g/cc and a volume density of about 0.3-0.4.

Description

Thermosetting Unsaturated Polyester Resin Composition

The present invention relates to a thermosetting unsaturated polyester resin composition, and more particularly, having excellent mechanical strength, such as impact resistance, scratch resistance, bending resistance, and the like as an unsaturated polyester resin, natural stone crushed material, hollow glass beads, etc. The present invention relates to a thermosetting unsaturated polyester resin composition which can be widely applied to buildings and apartments because it is economical as it is lighter than natural stones or other tides due to the small specific gravity after molding, and thus the transportation cost and labor is low.

Generally, natural stone such as granite and marble is mainly used as a wall and floor of a building. However, natural stone is difficult to apply to a thin molded product due to its weak strength, and can not only be used thickly, but also because of its high specific gravity, it is difficult to carry and work during construction.

Therefore, artificial stone with high strength and similar appearance to natural stone is used to replace natural stone. By the way, conventionally developed artificial stone has a specific gravity smaller than natural stone and the mechanical strength is large, so that it can be used by thinning the thickness, but still due to the large specific gravity is difficult as natural stone. Particularly, Korean Patent Publication No. 96-004268 stated that artificial marble made of dolomite becomes lighter.Since the dopite has a specific gravity (2.75-2.90g / cm3), silica (2.65g / cm3) and calcium carbonate are different weight fillers. Considering the fact that it is larger than (2.7-2.9 g / cm 3) and aluminum hydroxide (2.4 g / cm 3), the contents are not valid.

In Japanese Patent Laid-Open No. 4-266916, in order to form artificial marble, artificial marble, which is a thermosetting resin composition, is crushed and used as a marble chip instead of natural stone particles, thereby reducing the specific gravity of the molded product. Considering that the specific gravity of artificial stone produced by crushing natural stone is 2.65 g / cm 3 and about 2.3-2.5 g / cm 3, the specific gravity thereof is about 1.7 g / cm 3. However, this artificial marble has a different pattern and color than natural stone, and has a disadvantage of being traded at a high price in the market due to high manufacturing cost.

On the other hand, the molding material using the natural stone particles should use particles having a large diameter in order to produce a natural texture, it is difficult to mold because of the large fluidity due to the large particles. In addition, cracks or warpage occur in the molded article during molding. Therefore, conventionally, fine powder stone particles or small particle diameters are used, or marble chips crushed with a resin composition are used, or resin and stone particles are mixed in the middle of the mold by molding to flow at room temperature. The surface of the molded article was polished after being made. However, in this case, there is a disadvantage that the molding shrinkage is increased by using a lot of resin.

In addition, the existing artificial stone has a problem that the molding manufacturing process is complicated to obtain a variety of colors and patterns due to the large mold shrinkage rate (Korea Patent Publication No. 71-16, 85-71) This is because the amount of resin is used about 20-30% by weight (Korean Patent Publication No. 96-004267) because the molded article shrinks due to shrinkage of the resin during curing. Therefore, reducing the amount of resin in the manufacturing will not only significantly reduce the shrinkage but also lower the manufacturing cost.

The present invention has been made to solve the above problems, it is light in the manufacture of the molded article, the molding shrinkage rate is low, and excellent thermosetting properties such as impact resistance, scratch resistance, crack resistance, flex resistance, without losing the texture of natural stone It is an object to provide an unsaturated polyester resin composition.

In the present invention, in order to manufacture a light molded article, and to improve moldability and molding shrinkage rate, the resin amount is reduced by using hollow ceramic glass beads instead of silica, aluminum hydroxide, and the like, which are generally used as inorganic fillers. The said objective is achieved by reducing 8 weight%.

The composition of the present invention A) 100 parts by weight of the thermosetting unsaturated polyester resin having a viscosity of 100 to 800 centipoise at room temperature

B) 100 to 800 parts by weight of natural stone crushed

C) 10 to 150 parts by weight of used glass beads

D) 0.05 to 3 parts by weight of a high temperature curing catalyst and a cobalt based curing accelerator

E) 0.1 to 5 parts by weight of silane coupling agent

F) It is characterized by consisting of up to 5 parts by weight of pigments and additives such as color, heat, light stabilizer.

Hereinafter, the present invention will be described in detail.

First, as the A) thermosetting unsaturated polyester resin used in the present invention, an olso type is generally used, but in this case, chemical invasion is easy due to many ester groups in the molecular structure. Therefore, in order to prevent chemical invasion, bisphenol type having relatively few ester groups, iso type having a stereomolecular arrangement, vinyl ester type having a double bond at the end group, and complete homogeneous curing, and novolak type vinyl ester type similar to phenol resin Used. It is economically advantageous to use the Allo type as interior materials used in general buildings that do not handle chemicals.

These may be used alone or in the form of a mixture of two or more depending on the intended use, and it is particularly preferable to use a resin having a viscosity in the range of 100 to 800 centipoise at room temperature and a nonvolatile content of 50 to 70% by weight.

On the other hand, B) natural stone crushed material used in the present invention uses stone waste generated from mining the raw stone in each domestic stone quarries to be processed into building slabs.

It is used by crushing and drying domestic sifting stone (Pocheon Stone, Sinbuk Stone, Il Dong Stone, Geochang Stone, Jinan Stone, Uncheon Stone, Mungyeong Stone, Cheol Won Stone, etc.) and Marble Glass Sculpture. You can choose to. In order to produce a molded article close to natural stone, the average particle diameter of the natural stone crushed product should be selected within 0.5-20 mm, and various sizes of regions may be appropriately combined. These may be used alone or in combination of two or more depending on the desired pattern.

The amount of the natural stone crushed material B) to be used is 100 to 800 parts by weight based on 100 parts by weight of the unsaturated polyester resin A) and is preferably used in the range of 300 to 600 parts by weight depending on the desired pattern.

C) Hollow Ceramic Glass Beads are used as the inorganic filler used in the present invention, which has a specific gravity of 0.6-0.8 g / cc and a bulk specific gravity of about 0.3-0.4 g / cc, compared to other inorganic fillers. It has a very small specific gravity which makes it possible to greatly reduce the weight of the molded part. Considering that the specific gravity of silica, calcium carbonate, aluminum hydroxide, and the like, which are commonly used in the art, is specific gravity of 2.65 g / cm 3 of silica, 2.7 g / cm 3 of calcium carbonate, and 2.4 g / cm 3 of aluminum hydroxide, The proportion is much smaller than these.

Features and advantages of hollow glass beads are as follows. First, the shape is circular and there is an empty space in the beads, so the specific gravity is very low, making a light product. Second, since there is an empty space in the bead and has a spherical shape, the impact amount and impact energy in one direction are dispersed in multiple directions to act as a shock absorber in the molded article. Third, since it is also used as a heat insulating material to block heat due to the empty space in the bead, it can be used as a heat insulation product for flame retardant products. Fourthly, the fluidity of the slurry is improved because the shape is spherical and the surface is smooth to reduce the mixing viscosity. Fifth, there is an advantage that the surface area is small, so that the amount of resin can be used as well as economical, the molding shrinkage is small.

In the present invention, the hollow glass beads may be used alone or in different proportions with other fillers. The amount of hollow glass beads C) used is usually 10 to 150 parts by weight and preferably in the range of 20 to 100 parts by weight with respect to 100 parts by weight of unsaturated polyester resin A).

The diameter of the hollow glass beads is preferably 10 to 30um.

On the other hand, the D) curing catalyst used in the present invention is preferably used for high temperature curing in addition to about 10 kinds other than TBPT (t- butyl peroxy benzoate) and TBHP (t- butyl hydroperoxide). Cobalt-based accelerators, in particular cobalt naphtanate or cobalt octoate, are used as curing accelerators. The amount of the curing catalyst and the curing accelerator D) used is usually 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight based on 100 parts by weight of the unsaturated polyester resin A).

As the coupling agent E) used in the present invention, a silane coupling agent in which an organic functional moiety is a vinyl group or a methacryl group is used. The amount of the coupling agent E) used is usually 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on 100 parts by weight of the unsaturated polyester resin A).

In addition, the present invention uses the additives such as F) pigments, color, heat, light stabilizers, etc. to produce the background color of the product, and if the sulfur change of the surface of the product during the curing process is a problem using an antioxidant, color stabilizer It is recommended to avoid. The amount of the additive is preferably not more than 5 parts by weight based on 100 parts by weight of the unsaturated polyester resin A).

In order to prepare the above-mentioned thermosetting unsaturated polyester resin in the artificial stone similar to natural stone in the present invention, the liquid and solid phase of the above components are mixed separately for about 5 to 10 minutes, the liquid raw material is poured on the solid mixture, and mixed for 3 to 10 minutes. . The mixture was put into a specially produced mold (mould), vibrated at 1000 to 4000 Pa, and then placed in a mold for flat plates heated to 60-100 ° C. Then, a pressure of 150-200 kgf / cm 2 was applied in a hydraulic press to cure for 30 minutes to 2 hours, and then to be hardened for 1 to 2 hours in an oven. If there is only one background color, the above process is followed, but in the case of the double pattern, the desired color is mixed, and then the two mixtures are mixed for 10 to 20 seconds to be molded.

The cured moldings are ground to 50 mesh to match the thickness, then polished to a final product.

Hereinafter, the present invention will be described through Examples and Comparative Examples, but these Examples and Comparative Examples do not limit the protection scope of the present invention.

The specific gravity of the specimen measured in the present invention was evaluated according to ASTM C 97, the American standard, and the specimen size was 10 ^W × 10 ^L × 10 ^T. Mold shrinkage was evaluated according to JIS 6911. Flexural strength was evaluated according to ASTM D 790, specimen size was 50 ^W × 160 ^L × 20 ^T. Compressive strength was evaluated according to ASTM C 170. Dropping impact strength was evaluated according to ASTM D 5628, specimen size was 150 ^W × 150 ^L × 20 ^T.

Example 1-6

Next, specimens were prepared according to the components and the formulations shown in [Table 1].

First, the liquid and solid phases of the components of [Table 1] were separately mixed for about 10 minutes, and the two were mixed again for 5 minutes. The mixture was placed in a mold (mold), vacuum was applied at a frequency of 3000 Hz for 1 minute, and then put into a mold for flat plates heated to 80 ° C. Then, the pressure of 180kgf / ㎠ in a hydraulic press was cured for 30 minutes, and then hardened in the oven for 1 hour. The cured molded article was ground to 50 mesh, polished and polished, and the specimens were prepared to the desired size.

Excess resin generated by using hollow glass beads flowed out when pressed into the press. As a result of comparative evaluation with the case of Comparative Example 1-3, the same amount of resin was used, but considering the amount of resin flowed out, it was found that a small amount of resin is used when using the hollow glass beads.

Physical properties and mechanical strength were evaluated and the results are shown in the following [Table 2].

Comparative Example 1-3

Table 1 shows the components and blending ratios used, except that the composition was changed with only the inorganic fillers silica, calcium carbonate and aluminum hydroxide used in comparison to the case of using hollow glass beads. Specimens were prepared in the same manner and in the same manner as in Example 1. Physical properties and mechanical strength were evaluated and the results are shown in the following [Table 2].

[Comparative Example 4]

The physical properties and mechanical strength of Imperial Red in natural stone were measured and evaluated, and the results are shown in the following [Table 2].

TABLE 1 Composition and Composition of Composition

[Table 2] Property Measurement Results

The thermosetting unsaturated polyester resin composition prepared by the present invention has excellent mechanical strength, such as impact resistance, scratch resistance, and flex resistance, and is lighter than natural stone or other tide due to the small specific gravity after molding, so that the transportation cost and labor when constructing a building It is not only economical but also beautiful in appearance, so it can be widely applied to buildings and apartments.

Claims (3)

A) 100 parts by weight of a thermosetting unsaturated polyester resin having a viscosity of 100 to 800 centipoise at room temperature B) 100 to 800 parts by weight of natural stone crushed C) 10 to 150 parts by weight of used glass beads D) 0.05 to 3 parts by weight of a high temperature curing catalyst and a cobalt based curing accelerator E) 0.1 to 5 parts by weight of silane coupling agent F) A thermosetting unsaturated polyester resin composition comprising: 5 parts by weight or less of a pigment and additives such as color, heat, and light stabilizer. The thermosetting unsaturated polyester resin composition according to claim 1, wherein the unsaturated polyester resin has a viscosity in the range of 100 to 800 centipoise and a nonvolatile content of 50 to 70 wt%. 2. The hollow glass bead according to claim 1, wherein the hollow glass beads are spherical, hollow, and have a specific gravity of 0.6-0.8 g / cc, a specific gravity of about 0.3-0.4., And a diameter of 10 to 30 um. Thermosetting unsaturated polyester resin composition.