KR980009380A - Thermosetting resin composition - Google Patents

Abstract

The present invention relates to a thermosetting resin composition useful for producing a molded article for building materials, which has a low mold shrinkage ratio, excellent mechanical properties such as crack resistance, and has a variety of hues and patterns, And to provide an improved epoxy resin composition.

The composition of the present invention is a composition comprising A) 100 parts by weight of an epoxy resin, B) 30 to 100 parts by weight of a polyfunctional carboxylic acid compound, C) 0.01 to 10.0 parts by weight of a curing accelerator, D) 100 to 400 parts by weight of an inorganic filler, E) From 0 to 50 parts by weight of a radical polymerizable monomer; and H) from 0 to 30 parts by weight of a thermoplastic resin. It is possible to make light, complicated shapes such as sink, bathtub, washbasin, urinal, and toilet bowl.

Description

Thermosetting resin composition

Since this is a trivial issue, I did not include the contents of the text.

TECHNICAL FIELD The present invention relates to a thermosetting resin composition which is excellent in mechanical strength, particularly crack resistance, and is useful for producing molded articles for building materials.

Generally, complex shapes such as sinks, washbasins, kneaders, urinals, and urinals are required to be manufactured by the molding method in terms of strength, stain resistance and heat resistance, and these products have conventionally been made of inorganic materials such as stainless steel and ceramics Or made of a plastic material such as unsaturated polyester or acrylic resin.

However, in the case of pottery, it is excellent in stain resistance and heat resistance, but it has a high specific gravity and no elasticity, which is inconvenient for transportation and construction, and is easily broken even after construction. Also, since the coefficient of thermal expansion is very small, There is a risk of breakage, and there is a disadvantage in that it is difficult to expect the accuracy of dimensions since it is fired after molding.

Also, in the case of stainless steel, there is a problem that condensation water is generated on the back side of the sink due to the difference from the outside temperature in the winter, and the sink and the furniture are corroded.

Molds such as unsaturated polyester or acrylic resin, which are widely used next, are lighter in weight and higher in strength than ceramics. However, in order to have sufficient crack resistance, the thickness of the product must be increased. Particularly, There is a problem that the molding process becomes complicated. (Korean Patent Publication No. 92-3, No. 94-10217, No. 71-16, No. 85-71, No. 73-55, No. 73-232), or a pottery product, And it is easily scratched by other hard materials, resulting in a poor appearance condition in a short time. For example, Schock & Co. GmbH of the Schradorf 7060, Federal Republic of Germany, is a registered trademark of Silacrol (a registered trademark of Shock Company), austemite of ICI (Sinks, wash basins, bathtubs, etc.) made of resin mixed materials such as polyurethane resin, polyurethane resin, polyurethane resin, There is a need for the manufacture of improved products.

Disclosure of the Invention The present invention has been made to solve the above problems and it is an object of the present invention to provide an epoxy resin composition which is excellent in mechanical properties such as mold shrinkage and crack resistance and exhibits various colors and patterns and is improved in appearance degradation by a scratching effect And curing it in advance in a preheated fillet to prepare a desired molded article.

FIG. 1 is a state diagram of a surface of a test piece for visual deterioration judgment of visual appearance used in Examples and Comparative Examples of the present invention. FIG.

The composition of the present invention is a composition comprising A) 100 parts by weight of an epoxy resin, B) 30 to 100 parts by weight of a polyfunctional carboxylic acid compound, C) 0.01 to 10.0 parts by weight of a curing accelerator, D) 100 to 400 parts by weight of an inorganic filler, E) , 0 to 50 parts by weight of a radical polymerizable monomer, and H) 0 to 30 parts by weight of a thermoplastic resin dispersible as a polymer of a monomer G) Wherein the viscosity of the final composition is from 5,000 to 30,000 poise at room temperature (25 DEG C) and a pot life of at least 5 hours.

Hereinafter, the present invention will be described in detail.

The epoxy resin A) used in the present invention is a compound having two or more epoxy groups in its molecular unit and having a molecular weight of 150 or more. Examples of the epoxy resin satisfying this condition include bisphenol A epoxy resin, bisphenol F epoxy resin, beta-methyl epichloro epoxy resin, novolac epoxy resin and cyclic oxyl silicone series, glycidyl ether series, And aliphatic cyclic epoxy resins such as diester ester epoxy resins.

These epoxy resins may be used singly or in the form of a mixture of two or more thereof.

The epoxy equivalent of 70 to 250, preferably 150 to 220, and the average molecular weight of 150 to 220 in order to have the prepared resin composition completely cured and the product prepared by curing have excellent mechanical properties and scratching effect, It is particularly preferable to use an epoxy resin in the range of 1, 000, preferably 180 to 700.

Meanwhile, as the polyfunctional carboxylic acid compound (B) used in the present invention and serving as a curing agent for the epoxy resin, a compound having two or more carboxylic acid groups in the molecular unit and / or its acid anhydride may be mentioned. Examples of such multifunctional carboxylic acid compounds include maleic acid, fumaric acid, succinic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylmethahydrophthalic acid, Methylhexahydrophthalic acid and anhydrides of such acids, and polymers containing polyfunctional carboxyl groups such as poly (meth) acrylic acid may also be used.

These curing agents may be used singly or in the form of a mixture of two or more thereof. The amount of the carboxylic acid compound B) used ranges from 30 to 100 parts by weight per 100 parts by weight of the epoxy resin. If the amount of the polyfunctional carboxylic acid compound (B) to be used is less than 30 parts by weight, breakage and cracking of the final product tends to occur. On the other hand, if the amount is more than 100 parts by weight, do.

As the curing accelerator C) used in the present invention for promoting the reaction between the epoxy resin A) and the polyfunctional carboxylic acid compound B), a compound of a tertiary amine, a tertiary amine alcohol, a tertiary amine phenol, a compound of amidazoles, An ester, a Lewis acid, or an organometallic compound, can be used.

Examples of tertiary amines, tertiary amine alcohols and tertiary amine phenols include triethylamine, trimethylamine,? -Methylbenzyldimethylamine, benzyldimethylamine (BDMA), trisdimethylaminomethylphenol (DMP 30) Aminomethylphenol (DMP 10), dimethylaminoethanol, diethylaminoethanol, benzyltrimethylamine chloride salt (BTMAC) and the like. Examples of imidazoles include 2-methylimidazole, 2-pentadecylimidazole Sol, 2-4-diphenylimidazole, 2-ethyl-4-methylimidazole (EMI-24), and the like. Examples of the Lewis acid include boron trifluoride diethyl ether, titanium chloride, tin chloride, and examples of the organometallic compound include dibutyltin dilaurate, zinc caprylate, potassium acetylacetone, tetrabutyl titanate, ferrocene, Lithium benzoate, and the like. The content of the accelerator is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin A, and if it is less than 0.01 part by weight, the curing of the resin composition is delayed, If the amount exceeds 10 parts by weight, the physical properties of the cured product may deteriorate.

When the curing accelerator is used in the present invention, the final resin composition has a pot life of at least 2 hours at 60 ° C.

The inorganic filler D) used in the present invention is generally selected from among inorganic powders commonly used in the art. Suitable inorganic fillers include hydrates of metal oxides such as silica, titanium dioxide, aluniima, aluminum silicates, magnesium silicate, calcium carbonate, talc, clay and aluminum hydroxide, magnesium hydroxide and calcium hydroxide. Among them, the hydrate of the metal oxide, particularly aluminum hydroxide, is preferable because the resulting resin composition can be produced as a flame-retardant cured product having a transparent and beautiful marble-like appearance, but a filler such as aluminum silicate or silica There is a problem in that the mechanical properties are inferior when compared with the products obtained by using them.

Therefore, it is preferable to mix the inorganic fillers D) alone or in combination of two or more kinds depending on the required properties and appearance of the final product, and it is particularly preferable to use silica in an amount of 90% or more of the filler.

The amount of the inorganic filler to be used is 100 to 400 parts by weight, preferably 150 to 350 parts by weight, based on 100 parts by weight of the epoxy resin A). If the amount of the inorganic filler D) used is less than 100 parts by weight, the heat resistance of the cured product is insufficient and it is difficult to obtain a good marble-like feel. On the other hand, when the amount exceeds 400 parts by weight, the viscosity of the resin composition is too high and it is difficult to efficiently perform a molding operation of a mold or the like.

When the inorganic filler is used in the present invention, the viscosity of the composition of the final resin is 3,000 to 25,000 centipoise at 60 ° C.

In the present invention, particles E for granite texture are classified into three types. That is, it is possible to use three kinds of particles made by crushing ⓐ natural stone, ⓐ an organic filler that can be purchased as a commodity, ⓑ particles made by crushing artificial stone, and ⓒ particles made by crushing natural stone.

Organic fillers that are commercialized and available for purchase include the following. Natural Fibers include Wood Flour, Shell Fibers, Cotton Fibers and Vegetable Fibers. Regenerated Cellulose, Acrylonitrile Fibers, Aliphatec Polyamide Fibers, Aromatic Polyamide Fibers, Polyester Fibers, Teflon (Poly tetrafluoroethylene) Fibers, Polyvinylalcohol Fibers, Rubber powder (Rubber Dust, Hard). Here, wood flour has a size of usually 5-140 mesh and a cotton fiber has a size of 10-200 mesh (Mesh), and can be appropriately selected according to the application.

The manufacturing method of the particles made by crushing the artificial stone is as follows. 0-250 parts by weight of a filler such as calcium carbonate, aluminum hydroxide, aluminum silicate, silica, or clay is added to 100 parts by weight of a partially crosslinkable polymer resin such as an unsaturated polyester resin, an acrylic resin, a phenol resin or an epoxy resin, Inorganic pigments such as titanium dioxide, carbon black and iron oxide for expression, and 0 to 5 parts by weight of other organic pigments are added and polymerized. The bulk polymer thus prepared is crushed using an impact crusher, a pulverizer and the like, and then washed with a dehydrator to obtain particles having a desired particle size. Particle washing is to obtain a uniform color when the molded product is manufactured by removing fine particles on the surface of the particles used. Solvents such as acetone, styrene monomer, and methyl ethyl ketone, which have low boiling point and are volatile, To facilitate removal from the particles after washing. When the bulk polymer is obtained, it is obtained by a usual polymerization method by adding a curing agent, a polymerization accelerator, etc. which are generally applied to each resin used. As the curing agent and the polymerization accelerator, peroxide, for example, benzoyl peroxide, azoisobutyronitrile (AIBN), lauryl peroxide and the like are added to radical polymers such as acrylic resin and unsaturated polyester resin. In the case of epoxy resin, Amines, acid anhydrides and imidazoles are used as curing agents, and in the case of phenolic resins, urea, melamine and the like can be used for cross-linking.

When granite made of natural stone is used, granite is firstly used as natural stone such as Pocheon stone, Ildong stone, Jinan stone, Moonguk stone, Shinbuk stone, Geochang stone, Unchcheon stone, And the imports include Capao Bonite, Pokkala Red, Pink Rose, Balmor-al Red, New Imperial Red, Eagle Red, Eagle Red, Carmen Red and African Red are used. When natural marble is used, Arabescate, S-erpeggiante, Pink Aurora, Aurora, Tinose Green, Bianco Carara, Botticino Classico, Travertine, Verde Alpi, and so on.

In addition, silica, barite, diopside, sericite, flourite, calcite and the like can be crushed and used directly or by hot recrystallization if necessary. When natural stone is not commercially available, the desired particle size can be obtained by using the following crushing process of the particles made by crushing the artificial stone.

The granules may be used alone or in combination of two or more of the above a, b, and c to express the texture. The combination may vary depending on the desired pattern and color of the granules after molding, preferably 2-5 Good results can be obtained by using mixed species.

Further, as the particle of the particles, a mixture of various mesh particles of 4 to 400 mesh, preferably 10 to 150 mesh, is used to exhibit a natural texture and is excellent in physical properties.

Particles for imparting the granite texture are used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the epoxy resin.

In the present invention, pigments and color stabilizers F) can be used for coloring, and when an oxidation inhibitor or a color stabilizer is used, it is possible to prevent the change of the surface of the product during the curing process. The amount of the additive is 2.0 parts by weight or less based on 100 parts by weight of the epoxy resin A). When the amount exceeds 2.0 parts by weight, the physical properties of the cured product are deteriorated.

As the radical polymerizable monomer G) used in the present invention, a radically polymerizable monomer of a single functional group or a radically polymerizable monomer of a single functional group, which exhibits a liquid state at room temperature, and a multifunctional (meth) acrylate polymer are used.

The radically polymerizable monomers of monofunctional groups usable in the present invention are < RTI ID = 0.0 > Examples include (meth) acrylic acid esters such as (meth) acrylic acid, methyl (ket) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and styrene, Aromatic vinyl compounds.

The mixing ratio of the radically polymerizable monomer and the polyfunctional (meth) acrylate of the single functional group in the radical polymerizable monomer is preferably in the range of 0 to 400 parts by weight of the multi-functional (meth) acrylate based on 100 parts by weight of the radical polymerizable monomer of the single functional group Do.

As the polymerization initiator to be used for the polymerization of the radical polymerization monomer, one selected from benzoyl peroxide and lauryl peroxide t-butyl peroxypivalate is added in an amount of 0.1-3 parts by weight per 100 parts by weight of the radical polymerizable monomer use.

The radically polymerizable monomer G) is used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the epoxy resin, and if it is used in excess of 50 parts by weight, the impact resistance is deteriorated.

The thermoplastic resin H) used in the present invention is required to be soluble or dispersible in the radical polymerizable monomer. Examples of the thermoplastic resin that satisfies this requirement include polymethyl methacrylate, polystyrene, polycarbonate, saturated polyester and the like. Among the above-mentioned thermoplastic resins, polystyrene and polymethyl methacrylate have high transparency and a fine appearance Which is particularly preferable for use. The thermoplastic resin preferably has a weight average molecular weight of 3,000 to 40,000, preferably 6,000 to 12,000.

The amount of the thermoplastic resin H) should be such that the molded resin composition does not become opaque due to foaming or phase separation during curing, specifically 0-30 parts by weight, preferably 10-20 parts by weight, per 100 parts by weight of the epoxy resin A) The range of wealth is good.

When the thermoplastic resin used in the present invention has a functional group capable of reacting with an epoxy resin or a polyfunctional carboxylic acid compound, the resultant resin composition is not opaque at the time of curing, and the hardened product in the shape of the finally produced marble is highly satisfactory I have a beautiful appearance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Manufacturing Example] Preparation of Granular Texture Particles E)

100 parts by weight of an epoxy resin (25 DEG C, 20 parts), 85 parts by weight of methyltrihexahydrophthalic acid, 200 parts by weight of aluminum hydroxide and 3 parts by weight of a pigment expressing each color were mixed and polymerized to form artificial stones, Ⓑ 1-5 of particles E, by particle size and color, were prepared. Here, titanium dioxide, carbon black, iron oxide sulfur and the like are used singly or as a mixture of pigments expressing each color. (A) and (c) in (A) and (E) are selected and obtained according to the method described above and are shown in the following Table-1. In the following Examples, particles of the following Table 1 were used as the component E).

[Table 1]

The type of particles E) used in the examples

[Example 1]

A composition composed of the components shown in the following Table 2 at 60 ° C was cast in a preheated metal mold and cured at 80 ° C for 4 hours and at 150 ° C for 2 hours to prepare specimens. The properties were measured and the results are shown in Table 4 below.

[Table 2]

[Example 2]

The same procedure as in Example 1 was carried out except that a composition composed of the components shown in the following Table 3 was used. The properties were measured and the results are shown in Tables 4 and 5 below.

[Table 3]

[Comparative Example 1]

100 parts by weight of orthophthalic acid unsaturated poly ester for molding, 1 part by weight of methyl ethyl ketone peroxide and 200 parts by weight of silica was cast in a preheated metal mold and cured at 90 DEG C for 2 hours and at 110 DEG C for 4 hours To prepare specimens. The properties were measured and the results are shown in Table 4 below.

[Comparative Example 2]

Synthesized waterproofing sheet (white), which is a molded product of an acrylic resin using an external silica filler, was obtained and its physical properties were measured. The results are shown in Tables 4 and 5.

[Comparative Example 3]

A beige aspiration band, a molding product of an unsaturated polyester resin using a calcium carbonate filler of the domestic type, was obtained and its physical properties were measured. The results are shown in the following Table-4.

[Comparative Example 4]

A sink (granite texture) water quenching product, which is a molding product of an unsaturated polyester resin using a domestic aluminum hydroxide filler, was obtained and its physical properties were measured. The results are shown in Tables 4 and 5 below.

Table 4 below shows the measurement results of the mechanical strength, heat resistance, pencil hardness and scratching effects of the examples and comparative examples. The degradation of the appearance due to the scratching effect was measured by measuring the pencil hardness of the surface, The surface of the specimen was scratched with a metal pin as shown in Fig.

[Table 4]

* 1: Specimen thickness 10mm, 1mm height drop steel ball to break the specimen

* 2: Good: Fair: Fair: Bad:

Table 5 below shows the results of measuring the stain resistance of Example 2, Comparative Example 2 and Comparative Example 4 according to JIS K 6902.

Results of contamination measurement

[Table 5]

* ○: Complete removal of contamination △: A little residual of contamination ×: No decontamination

As described above, the epoxy resin composition prepared according to the method of the present invention has excellent workability in a liquid state at 60 ° C and has a very low shrinkage rate during molding, so that there is no problem of cracks and internal deformation due to shrinkage even in a complicated shaped article. In addition, a molded article excellent in crack resistance, mechanical strength, stain resistance, and heat resistance can be produced.

In addition, since the thickness of the resin is thinner than that of the conventional product, the temperature of all the negatives of the resin to be filled when the resin is filled into the preheated metal mold can reach a sufficient temperature for curing and no shrinkage or the like occurs in the post- Can be made into short, light and complicated shapes such as sinks, bathtubs, washbasins, urinals, and toilet flasks.

Claims (8)

A) 100 parts by weight of an epoxy resin, B) 30 to 100 parts by weight of a polyfunctional carboxylic acid compound, C) 0.01 to 10.0 parts by weight of a curing accelerator, D) 100 to 400 parts by weight of an inorganic filler, E) (G) 0 to 50 parts by weight of a radical polymerizable monomer, and H) 0 to 30 parts by weight of a thermoplastic resin, wherein the viscosity of the final resin composition is in the range of room temperature (25 ° C.) To 5,000 to 30,000 poises and a pot life of at least 5 hours. The thermosetting resin composition according to claim 1, wherein the epoxy resin (A) is at least one compound selected from the group consisting of an epoxy resin having an average epoxy equivalent of 70 to 250. The thermosetting resin composition according to claim 1, wherein the polyfunctional carboxylic acid compound (B) is a compound having two or more carboxylic acid groups in a molecular unit and / or an acid anhydride thereof. The curing accelerator according to claim 1, wherein the curing accelerator is at least one compound selected from the group consisting of a tertiary amine, a tertiary amine alcohol, a tertiary amine phenol, a compound of amidazoles, a boric acid ester, a Lewis acid, Wherein the composition has a pot life of at least 2 hours at a temperature of 60 캜 for the composition of the final resin. The method of claim 1, wherein the inorganic filler is selected from the group consisting of silica, alumina, aluminum silicate, magnesium silicate, titanium dioxide, calcium carbonate, talc, clay and metal oxides such as aluminum hydroxide, magnesium hydroxide, And the viscosity of the final resin composition is from 3,000 to 25,000 centipoise at 60 DEG C. 5. The thermosetting resin composition according to claim 1, [3] The granular texture of claim 1, wherein the granular texture comprises: (a) an organic filler that is commercially available, (b) particles produced by crushing artificial stone, and (3) Wherein the thermosetting resin composition is used singly or in combination. [2] The method according to claim 1, wherein the G) radical polymerization monomer is a radically polymerizable monomer of a single functional group exhibiting a liquid state at room temperature or a multifunctional (meth) acrylate mixture with a radical polymerizable monomer of a single functional group Thermosetting resin composition. The thermosetting resin composition according to claim 1, wherein H) the thermoplastic resin is at least one resin selected from the group consisting of polystyrene and polymethyl methacrylate. ※ Note: It is disclosed by the contents of the first application.