KR101414058B1 - Resin sheet having pearl-like luster or pattern and bathtubs using the same - Google Patents

Abstract

The present invention relates to a resin sheet having a pearl-like luster or a pearl-like pattern and to a bathtub using the same. More specifically, the present invention relates to a resin sheet having a pearl-like luster or a pearl-like pattern, comprising: (i) a skin layer containing impact-resistant modified PMMA resin, (ii) a core layer containing general PMMA resin and a pearl mater batch, and (iii) a base layer containing ABS resin; and a bathtub using the same. According to the present invention, the resin sheet manufactured can be applied to furniture, kitchenware, bathtubs, shower booths, etc., thereby raising the value thereof as the resin sheet has a pearl-like luster or a pearl-like pattern with excellent surface gloss and aesthetic appreciation while having mechanical properties such as weather resistance, impact resistance, scratch resistance and stress cracking resistance.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin sheet having a pearl luster or pattern and a bathtub using the resin sheet.

The present invention relates to a resin sheet having a pearly luster or pattern and a bathtub using the same, and more particularly to a resin sheet having a skin layer containing i) an impact resistant modified PMMA resin; ii) a core layer containing a generic PMMA resin and a perlmaster batch; And iii) a base layer containing an ABS resin, and a bathtub using the resin sheet.

Resin products based on plastic materials are used in many areas of daily life in modern people. Depending on the field of use, various properties and physical properties required for resin products, such as household appliances, furniture, food or cosmetic packaging containers, kitchen utensils, bathtubs or shower booths, In order to enhance the value, the surface of the resin product requires aesthetics including a beautiful gloss and a pattern, and various prior arts related thereto are known.

Among these prior arts, the blend resin product of the styrene-butadiene block copolymer and the crystalline polypropylene homopolymer has excellent mechanical properties such as impact strength and exhibits a beautiful pearl pattern or gloss. However, the weather resistance, scratch resistance, It has a disadvantage that it is difficult to apply it to applications such as a bathtub or a shower booth because of its low stress cracking resistance (Patent Document 1).

A decorative sheet containing a mica-based pearl pigment coated with titanium on an acrylic resin base layer such as polymethyl methacrylate (PMMA) is known in consideration of high transparency, weather resistance and scratch resistance of an acrylic resin, Although transparency, weather resistance and scratch resistance are improved by using a resin base material, it has been disclosed that a general PMMA resin used as a base layer has low impact resistance, and copolymers corresponding to acrylic rubbers can also be used as base layers However, it is difficult to have a satisfactory level of impact resistance in the entire sheet as a simple structure sheet in which such a resin component is used only in the base layer, so that application fields such as bathtubs are not mentioned (Patent Document 2).

On the other hand, the upper layer is composed of a polymethyl methacrylate (PMMA) homopolymer and the lower layer is composed of a blend of PMMA and acrylonitrile-butadiene-styrene (ABS) resin for use in a product frequently contacting cold / Layered resin sheet is known, and weather resistance and impact resistance are good, but resistance to stress cracking is unsatisfactory and does not exhibit a pearl pattern or gloss (Patent Document 3).

In addition, the applicant of the present patent application has already manufactured and extruded an extruded resin containing a core layer made of ABS resin and a skin layer containing a blend of PMMA and styrene-acrylonitrile (SAN) resin, It was possible to show a pearl feeling without using an expensive additive. However, the mechanical properties such as weather resistance and scratch resistance were deteriorated over a long time, and there was a limit to maintaining the pearl luster (Patent Document 4).

Therefore, the inventors of the present invention have found that when the substrate layer is used as an impact resistant resin to improve the impact resistance of the entire resin sheet, and the surface of the resin sheet is coated with the impact resistant modified PMMA resin having both gloss and impact resistance, It is possible to produce a resin sheet having a pearl luster or pattern having excellent surface gloss and aesthetics as well as mechanical properties such as scratch resistance and stress cracking resistance and can be produced by processing the resin sheet in accordance with a known molding method The present invention can be applied to a product such as a bathtub and the like.

Patent Document 1: U.S. Patent No. 4,499,238 Patent Document 2. European Patent Publication No. 1 655 149 Patent Document 3. Korean Patent Registration No. 10-0256913 Patent Document 4: Korean Patent Registration No. 10-0875272

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a pearlescent material having superior surface gloss and aesthetics, while having excellent mechanical properties such as weatherability, impact resistance, scratch resistance, A resin sheet having gloss or pattern, and a bathtub using the resin sheet.

According to an aspect of the present invention, there is provided a laminate comprising: i) a skin layer containing an impact resistant modified PMMA resin; ii) a core layer containing a generic PMMA resin and a perlmaster batch; And iii) a base layer containing an ABS resin.

The impact resistant modified PMMA resin is a copolymer resin of an MMA monomer and an ethyl acrylate or butyl acrylate monomer.

The impact resistant modified PMMA resin is a blend resin of PMMA resin, MBS resin, MABS resin, SBC resin or ABS resin.

Wherein the core layer comprises 70 to 90% by weight of a general PMMA resin and 10 to 30% by weight of a pearl master batch.

The pearl master batch is characterized by comprising 98 to 99.5% by weight of general PMMA and 0.5 to 2% by weight of particles of gold, silver, aluminum, titanium, manganese, chromium, magnesium or their mixture.

The particles have an average particle diameter of 50 to 200 μm.

Wherein the core layer further comprises any one selected from the group consisting of marble, mica pigment, pearl powder, glass powder, and mixtures thereof.

The thickness of the skin layer is 7 to 8% of the total thickness of the resin sheet.

And the core layer has a thickness of 7 to 8% of the total thickness of the resin sheet.

Further, the present invention provides a bathtub using the resin sheet having the perlite gloss or pattern.

Since the resin sheet produced according to the present invention has a pearly luster or a pattern having excellent mechanical properties such as weather resistance, impact resistance, scratch resistance and stress cracking resistance, and excellent surface gloss and aesthetics, , Bathtubs, shower booths, etc., and the value of the product can be increased.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a structural view of a resin sheet having a perlite gloss or pattern according to the present invention. Fig.
2 is a photograph of a prototype of a resin sheet having perlite gloss or pattern according to the present invention.
3 is a photograph of a bathtub formed by using a resin sheet having a perlite gloss or pattern according to the present invention.

Hereinafter, a resin sheet having a perl glossy or pattern according to the present invention and a bathtub using the same will be described in detail with reference to the accompanying drawings.

In the present invention, as shown in the constitution diagram of Fig. 1, there is provided a method for producing a laminate comprising i) a skin layer containing an impact resistant modified PMMA resin; ii) a core layer containing a generic PMMA resin and a perlmaster batch; And iii) a base layer containing an ABS resin.

First, ABS (acrylonitrile-butadiene-styrene) resin is used as the polymer material constituting the base layer 10 of the resin sheet 100 according to the present invention. ABS resin is a copolymer having acrylonitrile chemical resistance, butadiene impact resistance and styrene excellent processability and is widely used as a material for furniture or bathtubs.

In addition, the core layer 20 of the present invention contains a general PMMA resin and a perlmaster batch 40. The above-mentioned general PMMA resin has physical properties inherent to PMMA and is not modified by other components State. General PMMA has excellent transparency, gloss and molding processability and is widely used as a material for plastic products. Especially, since it has weatherability and scratch resistance, PMMA is not easily discolored due to ultraviolet rays and weathering, and is excellent against scratches of external stimuli. And is suitable as a material used for the core layer 20 of the resin sheet 100 according to the present invention. In addition, the perforated master batch 40 is mixed with the general PMMA resin of the core layer 20 to form a perforated gloss or pattern on the resin sheet.

When the content of the general PMMA resin forming the core layer 20 is less than 70% (when the content of the perlmer master batch exceeds 30% by weight), the dispersibility with the PMMA resin is inferior and the content thereof becomes 90% The core layer 20 may contain 70 to 90% by weight of a general PMMA resin and 10 to 30% by weight of a pearl master batch (the content of the perlmer master batch may be less than 10% by weight) By weight.

On the other hand, a master batch is usually prepared in the form of a chip or a pellet by blending a polymer material and a functional additive in order to add functionality to a polymer material such as plastic or rubber. In the present invention, A functional additive exhibiting gloss or pattern is previously compounded and molded into a pellet form. As the functional additive exhibiting such pearl luster or pattern, metal particles such as gold, silver, aluminum, titanium, manganese, chrome, magnesium or mixture particles thereof can be used. Among them, .

That is, the perlmaster batch 40 of the present invention is characterized by comprising 98 to 99.5% by weight of general PMMA and 0.5 to 2% by weight of particles of gold, silver, aluminum, titanium, manganese, chromium, magnesium, It is difficult to obtain a uniform pellet in which the metal particles are evenly distributed during the processing according to the blend of the pearl master batch 40.

The average particle diameter of the gold, silver, aluminum, titanium, manganese, chromium, magnesium or mixture thereof is preferably 50 to 200 μm. When the average particle diameter of the particles is less than 50 μm, And if it exceeds 200 μm, the miscibility with the general PMMA resin is lowered during the blending process of the perlmaster batch 40.

In the present invention, the general PMMA resin, which is a polymer material of the general core layer 20, is excellent in weather resistance and scratch resistance, but has a low impact resistance due to inherent characteristics of an acrylic resin. By using an ABS resin excellent in impact resistance as the base layer 10, the impact resistance of the entire resin sheet 100 is improved.

On the other hand, the general PMMA resin is excellent in surface gloss and scratch resistance, but is not only poor in impact resistance, but also resistant to frequent contact with cold and hot water, soap, detergent, and chemicals, and has low resistance to stress cracking. Therefore, in the present invention, an impact resistant modified PMMA resin is used to improve the impact resistance of the surface of the resin sheet 100, to be resistant to the environment, and to be applied to products such as bathtubs, By forming the skin layer 30 of the resin sheet 100, the impact resistance is remarkably improved without deteriorating the surface gloss and scratch resistance inherent in PMMA, and resistance and stress resistance to cold and hot water, soap, detergent, The cracking property can be improved.

As the impact-modified PMMA resin, a copolymer resin or a blend-type resin having a PMMA block in a resin and containing a rubber-like resin component can be used. As the copolymer type, a copolymer resin in which an acrylic rubber block such as polyacrylate is mixed with a PMMA block as a copolymer resin of MMA (methyl methacrylate) monomer and ethyl acrylate or butyl acrylate monomer can be preferably used have.

In addition, the blend type may include a PMMA resin, an MBS (methyl methacrylate-butadiene-styrene) resin, a MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) resin, an SBC (thermoplastic styrene block copolymer) It is preferable to use a blend resin of an ABS (acrylonitrile-butadiene-styrene) resin, more preferably PMMA-MBS resin which is a blend of PMMA resin and MBS resin.

In addition, the resin sheet 100 of the present invention can be obtained by mixing the perlmaster batch 40 with the core layer 20 and by forming the skin layer 30 to improve the surface gloss, The core layer 20 may further include any one selected from the group consisting of marble, mica pigment, pearl powder, and glass powder, which are well-known pearlescent polish agents, as the case may be, The toning agent may preferably be selected in consideration of the dispersibility with a general PMMA resin having an average particle diameter of 5 to 20 占 퐉 which is a material of the core layer 20.

The core layer 20 and the skin layer 30 of the present invention are easily laminated on the substrate layer 10 in the order of 7 to 8% of the total thickness of the resin sheet 100, It is not only excellent in weatherability, but also satisfies mechanical properties such as weather resistance, impact resistance, scratch resistance and stress cracking resistance, and can be applied to furniture, kitchen utensils, bathtubs or shower booths Thereby enhancing the value of the product.

The resin sheet 100 of the present invention is manufactured into a multi-layered sheet including the skin layer 30, the core layer 20, and the base layer 10 by coextrusion. The ABS resin used as the base layer 10 is a commercially available raw material in the form of pellets, but the components of the skin layer 30 and the core layer 20 are uniformly kneaded in an extruder and then molded into pellets We prepare material. The components of each layer were fed into the feed block with a triple co-extruder maintained at the melting temperature of each resin or higher to form a base layer 10 containing ABS resin / core layer 20 containing a general PMMA resin and a perl master batch, / The skin layer 30 containing the impact resistant modified PMMA resin. The laminated resin layer is processed into a sheet form from a die to produce a multi-layered sheet (100).

In addition, the thickness of the resin sheet 100 produced in the present invention can obtain a uniform thickness by accurately controlling the extrusion amount of each resin introduced into the feed block from the triple co-extruder.

Hereinafter, specific examples will be described in detail.

( Example  One)

As the impact modifier PMMA, MMA / butyl acrylate copolymer resin pellets (monomer weight ratio 70/30, first pellet), general PMMA resin and pearl master batch (Second pellet) and an ABS resin pellet (third pellet) were prepared. The first to third pellets were put into a feed block through a triple extruder set at different temperatures of 260 ° C, 235 ° C and 250 ° C, respectively, to form a skin layer, a core layer and a base layer. The laminated resin was passed through a die and processed into a sheet to obtain a multi-layered resin sheet. The thickness of the skin layer and the core layer was adjusted to 7.5% (300 μm) of the entire sheet thickness, To prepare a resin sheet.

( Example  2)

A resin sheet having a thickness of 4 mm was produced in the same manner as in Example 1, except that PMMA-MBS blend resin was used as the impact resistant modified PMMA.

( Comparative Example )

The skin layer was formed of MMA / methyl acrylate copolymer resin (monomer weight ratio 80/20), and the pearl master batch had aluminum particles having an average particle size of 250 m, and the skin layer had a thickness of 400 m A resin sheet having a thickness of 4 mm was prepared in the same manner as in Example 1. [

( Test Example )

The mechanical properties and pearliness of the resin sheet prepared in Examples 1 and 2 and Comparative Example and the aluminum powder-containing PMMA sheet and aluminum powder-containing ABS sheet having the same thickness as the control group were measured by the following method.

(1) Weatherability was measured according to the ultraviolet ray test method based on the artificial promoting weatherability test standard, and the color difference (ΔE) was compared after 200 hours.

(2) Izod impact strength was measured according to ASTM D256 method for impact resistance.

(3) A known pencil hardness measurement method was used for the scratch resistance.

(4) The stress cracking resistance was measured according to the ASTM D1693 method.

(5) The surface gloss was measured by a gloss meter at 60 占 according to JIS K7105 method.

(6) The pearl luster or pattern can be observed with the naked eye to give a very beautiful pearl luster or pattern (?), A beautiful pearl luster or pattern (?), A pearl luster or a weak pattern (?), (X).

Sample Weatherability
(? E) Impact resistance
(kg.cm/cm) Scratch resistance Stress cracking resistance
(hr) Surface gloss
(%) Pearl Example 1 0.2 8.2 H 1,900 81 ◎ Example 2 0.2 9.1 H 1,900 80 ◎ Comparative Example 0.4 6.4 HB 1,700 75 ○ PMMA / Aluminum 0.6 1.6 2H 700 85 △ ABS / Aluminum 9.6 17.3 3B 500 50 ×

As shown in Table 1, the resin sheets prepared from Examples 1 and 2 of the present invention had better mechanical properties such as weather resistance, impact resistance, scratch resistance and stress uniformity than the resin sheets and the control sheet prepared from Comparative Examples And the surface gloss was comparable or even better in some physical properties. It was observed that aluminum particles having an average particle diameter of 200 占 퐉 were mixed in the core layer to exhibit a very beautiful pearl luster or pattern. Particularly, it can be seen that the stress cracking resistance is increased almost three times as compared with the PMMA / aluminum powder sheet as the control group. This is because the skin layer of the resin sheet is made of a PMMA copolymer Resin or a blend resin of PMMA and rubber-like resin is used.

Therefore, the resin sheet of the present invention is excellent in mechanical properties such as weather resistance, impact resistance, scratch resistance and stress cracking resistance, and has a pearly luster or pattern with excellent aesthetics. Therefore, the resin sheet is suitable for furniture, kitchen utensils, bathtubs, It can be applied to increase the value of the product.

In particular, from the resin sheet having the perl glossy or pattern of the present invention shown in Fig. 2, a bathtub of a desired shape can be easily produced as shown in Fig. 3 by a known molding method.

100. Resin sheet
10. Base layer
20. Core layer
30. Skin layer
40. Pearl Master Placement

Claims (10)

i) a skin layer containing an impact resistant modified PMMA resin consisting of a blend of PMMA resin and MBS resin;
ii) a core layer containing a generic PMMA resin and a perlmaster batch; And
and iii) a base layer containing an ABS resin. delete delete The resin sheet according to claim 1, wherein the core layer comprises 70 to 90% by weight of a general PMMA resin and 10 to 30% by weight of a pearl master batch. The pearl master batch according to claim 1, wherein the pearl master batch comprises 98 to 99.5% by weight of general PMMA and 0.5 to 2% by weight of particles of gold, silver, aluminum, titanium, manganese, chromium, A resin sheet having gloss or pattern. 6. The resin sheet according to claim 5, wherein the particles have an average particle diameter of 50 to 200 mu m. The resin composition according to claim 1, wherein the core layer further comprises any one selected from the group consisting of marble, mica pigment, pearl powder, glass powder, and mixtures thereof. Sheet. The resin sheet according to claim 1, wherein the thickness of the skin layer is 7 to 8% of the total thickness of the resin sheet. The resin sheet according to claim 1, wherein the thickness of the core layer is 7 to 8% of the total thickness of the resin sheet. 9. A bathtub molded from a resin sheet having perlite gloss or pattern according to any one of claims 1 to 9.

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