KR100898555B1 - Curable Composition Having Good Scratch-Resistance and Processability, Cured Article Thereof, and Method for Preparing the Same - Google Patents

Abstract

Curable composition of the present invention is 100 parts by weight of the curable resin; And 2 to 30 parts by weight of inorganic particles having a Mohs hardness of 3 or more. The cured product of the present invention is a cured composition of the curable composition. In the curing process, the inorganic particles settle down to form a surface layer in the final product, thereby forming a surface having excellent scratch resistance, and also having excellent workability such as cutting. .

Cured resin, inorganic particles, silica, curable resin composition, scratch resistance, processability

Description

Curable Composition Having Good Scratch-Resistance and Processability, Cured Article Thereof, and Method for Preparing the Same}

Figure 1 shows the initial state after pouring the curable composition of the present invention to the molding cell.

2 is a view showing the inorganic particles are settled down during the curing of the curable composition of the present invention.

3 is a schematic view showing a cured product in which the inorganic particles according to the present invention form a surface layer.

Brief description of the main symbols in the drawing

1: Inorganic Particles 2: Curable Resin

3: surface layer 5: forming cell

10: hardened | cured material

Field of invention

This invention relates to the resin curable composition, hardened | cured material, and its manufacturing method which were excellent in workability and scratch resistance. More specifically, the present invention mixes specific inorganic particles and curable resins at a predetermined ratio, so that the inorganic particles settle down to form a surface layer of the final product during the curing process, thereby forming a surface having excellent scratch resistance and at the same time cutting, etc. It is related with the resin hardened | cured material excellent in workability, and its manufacturing method.

Background of the Invention

Recently, cured resins that are widely used as building interior materials can be classified into acrylic, unsaturated polyester, epoxy and the like according to the base resin used. In the case of the acrylic and the unsaturated polyester type, it is widely used as a top plate material such as artificial marble by mixing with a large amount of inorganic material. In particular, in the case of cured resins using aluminum hydroxide, calcium carbonate, or the like as inorganic materials, the demand continues to increase due to their easy processability.

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 a cured resin has excellent workability but has a disadvantage in that scratch resistance is weak and its use is limited.

In order to improve the scratch resistance, there is a method for preparing a mixture of hardened inorganic materials, such as granules of natural stone, with European Patent No. 0786325 and European Patent No. 1027205. However, such a method may have excellent scratch resistance, but has a disadvantage in that it requires a special processing tool used for processing natural stone due to low workability such as cutting.

Therefore, in order to solve the above problems, the present inventors mix specific inorganic particles and curable resins at a predetermined ratio, so that the inorganic particles settle down to form the surface layer of the final product during the curing process, and thus have excellent scratch resistance and workability. It is about to develop a cargo.

An object of the present invention is to provide a curable composition, a cured product, and a method for producing the same having both excellent scratch resistance and workability.

Another object of the present invention is to provide a cured resin and a method for producing the same, which do not lower the inherent physical properties of the cured product with the improvement of scratch resistance.

Another object of the present invention is to provide a cured product and a method for producing the inorganic particles to form the surface layer of the final product.

The above object of the present invention can be achieved by the following description. Hereinafter, the content of the present invention will be described in detail.

Summary of the Invention

The present invention provides a curable composition excellent in scratch resistance. The curable composition comprises 100 parts by weight of the curable resin and 2 to 30 parts by weight of inorganic particles having a Mohs hardness of 3 or more.

The inorganic particles may have a Mohs hardness of 3 or more, and silica, alumina, natural stone powder, and the like may be used.

In the present invention, the curable resin has a maximum viscosity of 1,000 cps or less at 50 ° C.

In one embodiment of the present invention, the curable resin may include one or more crosslinking agents, coupling agents, inorganic fillers, curing initiators, marble chips, curing accelerators.

The present invention provides a method for producing a cured product having excellent scratch resistance using the curable composition. The method includes mixing inorganic particles having a Mohs hardness of 3 or more with the curable resin to prepare a curable composition; And it consists of a step of hardening by heating up the said curable composition step by step at 25-160 degreeC.

The present invention also includes a cured product produced by the above production method. The cured product is characterized in that the inorganic particles form a surface layer. Hereinafter, the content of the present invention will be described in detail below.

Detailed Description of the Invention

The curable composition excellent in scratch resistance of the present invention comprises 100 parts by weight of the curable resin and 2 to 30 parts by weight of inorganic particles having a Mohs hardness of 3 or more.

The inorganic particles used in the present invention are particles having a Mohs hardness of 3 or more, and have a specific gravity higher than that of the curable resin forming the substrate layer.

If an inorganic particle having an Mohs hardness of 3 or less, such as aluminum hydroxide, is used, the hardness of the surface layer formed by the inorganic particles is not high enough, thereby insufficient to implement the effects of the present invention.

Therefore, the inorganic particles are required to have a Mohs hardness of 3 or more, and if the Mohs hardness is 3 or more, any of those conventionally used in the art to which the present invention pertains may be used.

Preferably they are silica, alumina, natural stone powder, and mixtures thereof, More preferably, they are silica.

The silica is most preferred in that it has a sufficiently high specific gravity of 2.0 or more, and has a high Mohs hardness of 5.0 or more, as well as a cured product having a beautiful appearance.

In the present invention, the particle size of the inorganic particles is preferably 1 to 800 µm. If the size of the inorganic particles is 1 μm or less, it is difficult to form the surface layer by the inorganic particles because the sedimentation due to the difference in specific gravity is not sufficiently performed.

The content of the inorganic particles is preferably 2 to 30 parts by weight based on 100 parts by weight of the curable resin. If the content of the inorganic particles exceeds 30 parts by weight, the workability is sharply lowered and cannot be processed with a general processing tool, and if it is less than 2 parts by weight, a sufficient thickness layer cannot be formed and scratch resistance is reduced.

The curable resin forms a substrate layer, and any resin capable of curing may be used. For example, the curable resin may be an acrylic resin, an unsaturated polyester resin, an epoxy resin, a monomer of a styrene resin, or a (co) polymer thereof, and maintain a viscosity to achieve the object of the present invention. In order to achieve this, a mixture of the monomer and the (co) polymer may be used. Moreover, a viscosity can be adjusted by adding a thickener as needed. The thickener is well known by those skilled in the art to which the present invention pertains, and the selection and content of the thickener can be easily carried out.

Acrylic resin of the said curable resin is preferable at the point which can manufacture the hardened | cured material which has the outstanding light resistance.

In the present invention, the viscosity of the curable resin is preferably 1,000 cps or less, more preferably 800 cps or less, most preferably 700 cps or less at 50 ° C. When it exceeds 1000 cps, the sedimentation to the bottom is not sufficient due to the difference in specific gravity of the inorganic particles and the curable resin, thereby reducing the effect of the present invention.

In one embodiment of the present invention, the curable resin may include one or more crosslinking agents, coupling agents, inorganic fillers, curing initiators, marble chips, curing accelerators.

The crosslinking agent is for the curable resin to have a crosslinked structure, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycerol trimethacrylate, trimethyl propane trimethacrylate and bisphenol A dimethacrylate. Functional methacrylate, cyanurate-based crosslinking agent, diallyl terephthalate, diallyl phthalate, vinyltoluene, divinylbenzene and the like may be used, but are not necessarily limited thereto.

The coupling agent is to help the inorganic material and the resin, and can be easily implemented by those skilled in the art to which the present invention pertains. The coupling agent may be preferably a silane coupling agent such as 3- (trimethoxycyryl) propylmethacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, and the like, but is not necessarily limited thereto.

The inorganic filler may be any one of inorganic powders commonly used in the art, such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, but is curable in a range that does not reduce the effect of the present invention for supplementing physical properties such as soft transparency. Add with resin to form substrate layer.

As the curing initiator, peroxides such as benzoyl peroxide, lauroyl peroxide, butyl hydroperoxide, cumyl hydroperoxide or azo compounds such as azobisisobutylonitrile are used. The content of the curing initiator used in the present invention is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the curable resin.

The curing accelerator is for increasing the curing rate, an organic metal salt, an organic amine or the like may be used.

The marble chip is classified into 0.1 to 10 mm using various sizes of shreds after crushing the artificial marble products made of the same composition as the base using a hammer mill crusher or cutter type crusher. In the case of a marble chip having a large particle size or a specific gravity, the marble chip is easily precipitated in the curable resin, and a surface layer can be formed together with the inorganic particle layer of the present invention.

The above-mentioned additives such as crosslinking agents, coupling agents, inorganic fillers, curing initiators, marble chips, curing accelerators, and the like may be mixed and applied to the curable resin, but the highest viscosity of the curable resin exceeds 1,000 cps (50 ° C.). Do not add.

The present invention provides a method for producing a cured product using the curable composition.

The manufacturing method of the hardened | cured material of this invention consists of mixing the inorganic particle of a Mohs hardness 3 or more with curable resin, manufacturing a curable composition, and hardening the said curable composition.

During the curing process, the inorganic particles of the curable composition are settled downward by the difference in specific gravity with the curable resin, as shown in FIG. 2, and the curable resin has a lower viscosity due to an increase in temperature. In this case, in order for the inorganic particles to sufficiently settle down, the maximum viscosity of the curable resin should be 1,000 cps or less (based on 50 ° C.).

The curing temperature gradient is preferably increased by curing stepwise from 25 ° C to 160 ° C, more preferably 25-120 ° C.

The curing process may be prepared in a continuous process by pouring the curable composition into a molding cell as shown in Figure 1, step by step in a hot air oven at 25 ~ 160 ℃, or by pouring the curable composition on a transfer conveyor belt.

The final cured cured product has a structure in which inorganic particles form a surface layer as shown in FIG. 3.

The cured product produced according to the present invention has excellent workability with good surface scratch resistance. Therefore, it can be applied as the top of various counters such as sink top plate, vanity vanity top, counters of banks and general stores, interior wall materials of product stores, bathtubs, sink bowls and various interior sculptures, and interior and exterior materials of buildings. have. In addition, by crushing the cured product of the present invention can be applied to marble chips for artificial marble.

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

Example 1

100 parts by weight of methylmethacrylate acrylate syrup (hereinafter referred to as resin syrup) prepared by mixing 35% polymethyl methacrylate and 65% methylmethacrylate, 3 parts by weight of trimethyl propane trimethacrylate, lauroyl A curable composition was prepared by mixing 10 parts by weight of silica particles having an average particle size of 25 microns with inorganic particles to a curable resin mixed with 2 parts by weight of peroxide.

The curable composition prepared above was poured into a glass molding cell of 300 × 600 × 15 mm, placed in a room temperature (25 ° C.) hot air oven, and the oven temperature was gradually raised to 120 ° C. to cure. After curing was completed, the workability and scratch resistance of the cured product cooled to room temperature were measured, and the results are shown in Table 1. In addition, the viscosity of the curable resin used in the production was measured and shown in Table 1.

Example 2

Bisphenol A diglycidyl ether type epoxy resin (epoxy equivalent 190) 100 parts by weight, methyl ethylhydrophthalic anhydride material (acid anhydride equivalent 160) 93 parts by weight as an acid anhydride curing agent, 4 as a curing accelerator A curable composition was prepared by mixing 10 parts by weight of silica particles having an average particle size of 25 microns with a curable resin mixed with 1 part by weight of phosphonium bromide. A cured product was prepared in the same manner as in Example 1 except that the temperature of the curing oven was gradually raised from 60 ° C to 160 ° C.

Example 3

Propylene glycol 46 parts by weight, ethylene glycol 138 parts by weight, dieethylene glycol 110 parts by weight, phthalic hydride 202 parts by weight, maleic hydride 241 parts by weight, hydroquinone 0.04 parts by weight, dibutyl phthalate 0.66 parts by weight, A curable composition was prepared by mixing 10 parts by weight of silica particles having an average particle size of 25 microns with inorganic particles to 100 parts by weight of an unsaturated polyester curable resin mixed with 262.3 parts by weight of a styrene monomer, and stepping the temperature of the curing oven from 60 ° C. to 160 ° C. A cured product was prepared in the same manner as in Example 1 except that the temperature was increased.

Comparative Example 1

100 parts by weight of methylmethacrylate acrylate syrup (hereinafter referred to as resin syrup) in a mixture of 50% polymethyl methacrylate and 50% methylmethacrylate, 3 parts by weight of trimethyl propane trimethacrylate, lauroyl peroxide A cured product was prepared in the same manner as in Example 1, except that inorganic particles were not used in the curable resin mixed with 2 parts by weight.

Comparative Example 2

A cured product was prepared in the same manner as in Example 1, except that 10 parts by weight of aluminum hydroxide (Moss hardness of about 2.5) particles having an average particle size of 35 microns were used as the inorganic particles.

Comparative Example 3

A cured product was prepared in the same manner as in Example 1, except that 50 parts by weight of silica particles having an average particle size of 25 microns were used as the inorganic particles.

Comparative Example 4

A cured product was prepared in the same manner as in Example 1, except that 1 part by weight of silica particles having an average particle size of 25 microns were used as the inorganic particles.

Comparative Example 5

A cured product was prepared in the same manner as in Comparative Example 1 except that 10 parts by weight of silica particles having an average particle size of 25 microns were further used as the inorganic particles.

The cured resin produced by the above Examples and Comparative Examples was measured in the physical properties shown in Table 1 below.

(1) Viscosity: The viscosity was measured at 50 degreeC using the Brookfield viscometer.

(2) Scratch resistance: The pencil hardness value was measured according to JIS K 5400.

(3) Workability: Using Festool saw blade Φ160 × 20mm TF 48, the number of cuttings up to the point of saw blade replacement was measured once and repeatedly cut to 500mm length.

TABLE 1

As shown in Table 1, Comparative Example 1 using only a curable resin can be seen that the scratch resistance is inferior. Comparative Example 2 using aluminum hydroxide as the inorganic particles can be seen that the scratch resistance is significantly reduced. In addition, even when silica particles are used as inorganic particles, as in Comparative Example 3, when the content of the inorganic particles is too high, rapid deterioration of workability occurs. When the amount of the inorganic particles is too small, as in Comparative Example 4, sufficient scratch resistance is achieved. Observation was not possible. When the silica particles were added in an appropriate amount as in Comparative Example 5, when the viscosity of the curable resin was excessively high, it was observed that a sufficient amount of the silica particles were not placed on the surface, so that scratch resistance was not improved. On the other hand, the curable resin composition prepared in Examples 1 to 3 can be confirmed that not only the workability but also the scratch resistance.

This invention has the effect of providing the curable composition, hardened | cured material, and its manufacturing method which simultaneously have the outstanding scratch resistance and workability, without reducing the physical property inherent to hardened | cured material.

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 (10)

100 parts by weight of curable resin; And 2 to 30 parts by weight of inorganic particles having a Mohs hardness of 3 or more; Curable composition excellent in scratch resistance comprising a. The curable composition having excellent scratch resistance according to claim 1, wherein the inorganic particles are selected from the group consisting of silica, alumina, natural stone powder and mixtures thereof. The method of claim 1, wherein the curable resin is selected from the group consisting of acrylic resins, unsaturated polyester resins, epoxy resins, monomers of styrene resins, (co) polymers thereof and mixtures of the monomers and (co) polymers. Curable composition excellent in scratch resistance, characterized by the above-mentioned. The curable composition having excellent scratch resistance according to claim 1, wherein the curable resin has a maximum viscosity of 1,000 cps or less at 50 ° C. The curable composition of claim 1, wherein the curable resin includes at least one crosslinking agent, a coupling agent, an inorganic filler, a curing initiator, a marble chip, and a curing accelerator. 2 to 30 parts by weight of inorganic particles having a Mohs hardness of 3 or more are mixed with 100 parts by weight of the curable resin to prepare a curable composition; And Step-temperature-curing the curable composition at 25 to 160 ° C .; Method for producing a cured product excellent in scratch resistance, characterized in that it comprises a step. 7. The method of claim 6, wherein the inorganic particles are selected from the group consisting of silica, alumina, natural stone powder, and mixtures thereof. The method of claim 6, wherein the curable resin has a maximum viscosity of 1,000 cps or less at 50 ° C. 7. The method of claim 6, wherein the curable resin includes at least one crosslinking agent, a coupling agent, an inorganic filler, a curing initiator, a marble chip, and a curing accelerator. Hardened | cured material manufactured by the method of any one of Claims 6-9, Comprising: An inorganic particle forms a surface layer.

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