KR20120064839A - Enviromental-friendly thermoplastic composition for deco-sheet and manufacturing method thereof - Google Patents

Abstract

PURPOSE: An environment-friendly thermoplastic resin composition is provided to melt-mixing graft copolymer type acrylic rubber and/or butadiene rubber with a thermoplastic resin, thereby obtaining excellent processability, appearance, thermal resistance, printability, adhesion, and elongation. CONSTITUTION: An environment-friendly thermoplastic resin composition comprises a substrate layer. The thermoplastic substrate layer comprises a rubber selected from a acrylic rubber, butadiene rubber, and a mixture thereof. The rubber is dispersed into the substrate layer. The rubber content in the substrate layer is 5-70 weight%. The acrylic rubber and the butadiene rubber is used in form of a graft copolymer. The rubber is graft polymerized by a styrene monomer and a cyancyano monomer. The substrate layer additionally comprises 0.01-5.0 parts by weight of an antioxidant, and 0.01-5.0 parts by weight of a UV absorber based on 100.0 parts by weight of thermoplastic resin.

Description

ENVIROMENTAL-FRIENDLY THERMOPLASTIC COMPOSITION FOR DECO-SHEET AND MANUFACTURING METHOD THEREOF}

The present invention relates to an eco-friendly decoration sheet (hereinafter referred to as a decor sheet), and more particularly, to an acrylic rubber-vinyl cyan-styrene-based and / or acrylonitrile-butadiene-styrene terpolymer resin and a styrene-vinyl cyan-based. It relates to a resin composition for environmentally friendly decor sheet comprising a resin composition composed of a copolymer.

Various decor sheets are used to decorate the surface of materials such as synthetic wood. Paper, PVC, PP, etc. have been mainly used as a material of the decor sheet.

Paper decor sheet is vulnerable to moisture and difficult to use as it is sensitive to environmental changes, and paper is impregnated with various resins, but impregnation costs are expensive.

Accordingly, plasticized polyvinyl chloride decor sheet, also known as PVC decor sheet has been developed and used, and has excellent lapping properties and formability due to its excellent workability, elongation, and heat deformation. However, PVC decor sheet has problems related to dioxins and heavy metals generated during incineration by using stabilizers and phthalate-based plasticizers containing heavy metals to improve processability, and it is not suitable for environmentally friendly products due to the high amount of volatile organic compounds released. For this reason, the development of applying various eco-friendly materials to the decor sheet is actively underway.

As an alternative environmentally friendly material, Korean Patent 2001-0086917 proposes a method of replacing polyvinyl chloride decor sheet through a polyolefin resin. However, polyolefin-based resins have disadvantages such as difficulty in molding such as adhesion to calender, poor surface printing and poor adhesion of sheets, and complicated process such as having to treat primer on substrate layer in order to increase adhesion. have.

Korean Patent 2006-0125086 proposes a solution to solve the problem of sticking to the calendar when molding the polyolefin-based resin and to solve the appearance quality. However, the complicated process such as primer treatment and the problem of poor lapping properties still exist.

Accordingly, there is a continuing need for a new eco-friendly decor sheet that reduces adhesiveness during calendering, has excellent processing stability, excellent appearance quality after processing, no heavy metal components, and good adhesion.

It is an object of the present invention to provide a new eco-friendly decor sheet containing no harmful substances such as heavy metals or phthalate plasticizers.

It is another object of the present invention to provide a resin composition for decorating sheet, which is excellent in calender molding and T-Die processability, and in particular, can realize product appearance quality, heat resistance, printability, adhesiveness and ductility as a decorating sheet. It is.

Still another object of the present invention is to provide a film for producing a decorate sheet manufactured using the resin composition for decorating sheet.

Still another object of the present invention is to provide a multi-layered decor sheet including the film.

Still another object of the present invention is to provide a new decor sheet having a simple and effective structure, by having a corresponding adhesive force to the PVC decor sheet, it is possible to omit layers introduced by the polyethylene-based sheets for improved adhesion.

In order to achieve the above object, the decor sheet according to the present invention is characterized in that the acrylic rubber and / or butadiene rubber comprises a thermoplastic resin base layer dispersed in a matrix resin.

In the present invention, the base layer is not limited in theory, but includes acrylic rubber and / or butadiene rubber, and can easily adhere to windows and doors, especially windows such as PVC, and has good color expression. It can have impact resistance and weather resistance.

In the present invention, the base layer may be prepared by melting and mixing acrylic rubber and / or butadiene rubber with a thermoplastic resin compatible with the rubber, preferably flowability and processability as a film on the base layer in the decor sheet, And a styrene-based copolymer, more preferably a styrene-vinyl cyan-based copolymer, so that the matrix resin can have good physical properties at the hardness, tensile strength, and tear strength required for the manufactured decor sheet.

In the present invention, the acrylic rubber may be a rubber having a low temperature Tg as the main component of the acrylic monomer in the range of -10 to -50 ℃, preferably an acrylic monomer having 2 to 8 carbon atoms, for example, an alkyl acrylate monomer Preferably, it consists of ethyl acrylate, butyl acrylate, ethylhexyl acrylate, etc., More preferably, it is butyl acrylate.

In addition, the butadiene-based rubber is a butadiene-based rubber polymer grafted by emulsion polymerization or bulk polymerization method using styrene and acrylonitrile in the presence of polybutadiene mainly composed of butadiene-based monomers.

In the present invention, the base layer may include acrylic rubber and / or butadiene rubber in the range of 5-70% by weight, more preferably 10-50% by weight, more preferably 15-25% by weight. . In a preferred embodiment of the present invention, the base material layer is preferably used in a ratio of 9: 1 to 1: 9 in the ratio of acrylic rubber and butadiene rubber so as to have a weather resistance and impact resistance properly, more preferably Is most preferably used in a weight ratio of 8: 2 to 2: 8, and more preferably 7: 3 to 3: 7.

In a preferred embodiment of the present invention, the acrylic rubber and / or butadiene rubber is graft acrylic rubber and / or graft by graft polymerization the surface of the resin with a high Tg resin such as styrene, acrylonitrile, methyl methacrylate It may be made of butadiene rubber to improve the kneading with the matrix resin, the graft polymerization is preferably a mixture of monomers containing a matrix resin component. For example, acrylic rubber or butadiene rubber is acrylic rubber (butadiene rubber) graft-polymerized with styrene and vinyl cyan monomer in order to improve kneading when styrene-vinyl cyan copolymer matrix resin is used. It is preferred to be used as the vinyl cyan-styrene graft polymer.

In one embodiment of the present invention, the acrylic rubber graft body and butadiene rubber graft body may be prepared by mixing each of the powder form, and then used, and the acrylic rubber graft body and butadiene rubber graft body is a latex, respectively It is also possible to mix in a state, a latex mixing method of coagulation drying to prepare a powder. In addition, the latex mixture is prepared by kneading the acrylic rubber and butadiene rubber in the form of latex, and then grafted by using a premixed-after-grafting method of grafting, or the acrylic rubber and butadiene rubber in the form of latex, and then grafted A line graft polymerization-post-mixing method in which the copolymer copolymer latex is mixed is also possible, and may be optionally selected and used according to the needs of those skilled in the art.

In one embodiment of the present invention, the acrylic rubber-vinyl cyan-styrene graft copolymer or acrylonitrile-butadiene-styrene graft copolymer resin may be prepared by emulsion polymerization, first, an acrylic monomer or After polymerizing a butadiene monomer to prepare a rubbery polymer latex, it is prepared by graft polymerization of a vinyl cyan monomer-styrene monomer, preferably an acrylonitrile-styrene monomer.

In a preferred embodiment of the present invention, the acrylic rubber-vinyl cyan-styrene graft copolymer resin uses an acrylic monomer, for example, an alkyl acrylate monomer having 2 to 8 carbon atoms to prepare a rubbery polymer latex. Preferably, ethyl acrylate, butyl acrylate, ethylhexyl acrylate, etc. can be used, More preferably, it is butyl acrylate.

The acrylic monomer for preparing the rubbery polymer latex is mixed with a small amount of copolymerizable monomer, preferably 20 wt% or less, more preferably 15 wt% or less, and even more preferably 10 wt% or less. Particles can be produced, for example monomers such as butadiene, styrene. The acrylic monomer may further include a small amount of a multifunctional acrylate monomer for graft polymerization of the acrylic monomer.

In a preferred embodiment of the present invention, the butadiene-based graft copolymer is a butadiene-based rubber grafted by emulsion polymerization or bulk polymerization method using styrene and acrylonitrile in the presence of polybutadiene mainly containing butadiene-based monomers. The preferable content as a polymer is 20-50 weight%.

In the present invention, the acrylic rubber (or butadiene rubber) -vinyl cyan-styrene graft copolymer resin is 50-80 parts by weight of the acrylic rubber (or butadiene rubber) styrene monomer and vinyl cyan monomer mixture 20-50 parts by weight, the styrene-based monomer and the vinyl cyanide monomer may be mixed in a weight ratio of 80: 20-60: 40.

In the present invention, the styrene-based monomer may be used as an aromatic vinyl monomer, styrene, alpha-methyl styrene, para-methyl styrene, vinyl toluene and a mixture of two or more thereof, preferably styrene.

In the present invention, the vinyl cyanide monomer includes acrylonitrile, methacrylonitrile, and the like, and preferably acrylonitrile.

In the present invention, the styrene-vinyl cyan copolymer is a copolymer of a styrene monomer and a vinyl cyan monomer, preferably a styrene-acrylonitrile copolymer.

In the present invention, the method for producing the styrene-vinyl cyan-based copolymer is not particularly limited as long as it can satisfy the above molecular weight and viscosity range, and can be prepared using conventional emulsion polymerization, block polymerization or suspension polymerization. Can be.

In the practice of the present invention, the thermoplastic resin base layer is an acrylic rubber-vinyl cyan-styrene graft copolymer and / or an acrylonitrile-butadiene-styrene graft copolymer is an acrylic rubber of thermoplastic resin and / or Butadiene-based rubber may be kneaded with the matrix resin so as to have a range of 5-70% by weight, preferably 30 to 80% by weight of the graft copolymer, matrix resin, for example, styrene-vinyl cyanide It is preferred that the copolymer is kneaded at 20-70% by weight.

In the present invention, the resin composition constituting the base layer may include an antioxidant of 0.01 to 5.0 parts by weight, preferably 0.01 to 1.0 based on 100 parts by weight of the resin in order to prevent oxidation during processing. In the practice of the invention, the antioxidant is Irganox a-541 from ADEKA.

In the present invention, it is preferable to use a UV absorber to prevent the discoloration by ultraviolet rays during use after wrapping the processed decorative sheet in the profile. Although not limited in theory, the ultraviolet absorbent may be used to prevent ultraviolet discoloration of butadiene mainly used in a quaternary copolymer, and may be used in an amount of 0.01-5.0 parts by weight, preferably 0.01 -1.0, based on 100 parts by weight of the resin composition. It is preferable to use in the range of.

The ultraviolet absorber may be used a conventional ultraviolet absorber used for preventing discoloration of plastics, preferably TibaUV-P is Shiva Special.

In the present invention, the styrene-vinyl cyan-based copolymer, the acrylic rubber-vinyl cyan-styrene terpolymer or the acrylonitrile-butadiene-styrene terpolymer, the antioxidant and the ultraviolet absorber are used for the composition using a mixer. After mixing with it can be prepared through calendering or T-Die extrusion process.

The present invention in one aspect, the base layer made of a thermoplastic resin containing an acrylic rubber and / or butadiene rubber; Optionally a decorative layer; And it provides a decor sheet characterized in that it comprises a protective layer.

In the present invention, the thermoplastic base material layer including the acrylic rubber and / or butadiene rubber is a layer adhered to a PVC profile or wood molding by fusion or adhesion. The acrylic rubber is a product made by polymerizing an acrylic monomer and rubberized, and the butadiene rubber is a product made by polymerizing a butadiene monomer and rubberized, and the acrylic rubber or butadiene rubber is 5 to 70 wt%, more preferably 10- It is preferably used in the range of 30% by weight, more preferably 12-25% by weight. The acrylic rubber or butadiene rubber is more preferably used by graft polymerization of the surface.

In the present invention, the base layer may form a single layer base layer of the same component or may be formed in a multi-layered form in which the content of the constituents, for example, acrylic rubber or butadiene rubber is different. Substrate layers in a multi-layered form can be prepared by known methods such as bonding, fusion, or coextrusion of two substrate layers.

In the practice of the present invention, in the case of a multi-layered base layer, it may be composed of a general base layer not containing a pigment and a color base layer including a pigment for decoration so as to improve the decor of the decor sheet, and The color base layer may differ only in color and the same components. Also possible are forms in which both color and composition are different.

In a preferred embodiment of the present invention, the multilayer base layer is composed of a lower base layer having a high content of acrylic rubber or butadiene rubber and a high base material layer having a low content of acrylic rubber or butadiene rubber and having good color expression. It is good. The upper base layer is made of a monochromatic color including a pigment, and the acrylic rubber or butadiene rubber content is low, so that the weatherability of the base layer may be particularly good weather resistance resin, in the case of monochromatic decor sheet, the printing layer may be omitted.

In the decor sheet of the present invention, the substrate layer may be selectively formed with a printing layer, surface printing is possible through a known printing method. In one embodiment of the invention, the printed layer may be formed by printing a gravure printing, transfer printing, etc. on the upper substrate layer. However, when the base layer of the decor sheet is composed of a lower base layer and an upper base layer and a solid color is formed in the upper base layer, the printed layer may be omitted.

A protective layer may be formed on an upper surface of the decor sheet of the present invention, and the manufacture of the protective layer is a surface treatment layer which may increase the scratch resistance of the printed layer or the color base layer of the product and increase the commercial property. The surface treatment layer is a layer formed by applying and curing a urethane acrylate-based ultraviolet curable resin for imparting fouling resistance to the top, and embossing may be performed if necessary.

The eco-friendly decoration sheet according to the present invention exhibits properties similar to those of the existing polyvinyl chloride decor sheet or PP decor sheet, and is excellent in processability, printability, and weather resistance compared to conventional PVC and PP decor sheets, and is incinerated or fired. City chlorine gas, dioxin and heavy metals do not occur, and the amount of volatile organic compounds emitted is less environmentally friendly.

Hereinafter, the present invention will be described in more detail with reference to Examples. This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

Various performance evaluation on the film and process produced in Examples and Comparative Examples of the present invention was carried out by the following measuring method.

(1) flexibility

Flexibility was determined by measuring Shore A hardness using a Shore Durometer by ASTM D2240.

(2) processability

The sheet was processed using calendering, and the sheet was classified into ◎, ,, and △ grades by visually judging the appearance state and the degree of melting.

◎: Excellent appearance and melting state

○: Partial appearance scratches or defects such as partial yellowing during melting

△: Difficult to process as a sheet due to a large amount of scratches or poor yellowing during melting

(3) tensile strength

As a vertical tensile strength test, a standard test was performed at 23 ° C ± 2 with No. 1 specimen in accordance with KS M 3001. The unit is kgf / cm ² . Deco sheets require a tensile strength of 350 or higher.

(4) tear strength

The standard tear strength test was conducted at 23 ℃ ± 2 in accordance with KS M 3001. The unit is N / cm. Deco sheets require a tear strength of at least 10.

(5) pencil hardness

As a pencil hardness test, a standard test was performed at a temperature of 23 ° C. ± 2 with a load of 500 g according to KS N ISO 15814 method.

(6) Weathering test

Xenon arc lamp type weather resistance test method using a weather-o-meter device and xenon lamp according to KS B 5549 method, temperature of 63 ° C, roughness of 0.35 W / m2 and 50% The color fading degree was measured for 2,000 hours under the condition of humidity of and measured by the color difference (ΔE) after irradiation and the color before irradiation.

◎: ΔE <3

○: 3≤ΔE <5

△: 5≤ΔE <8

X: 8≤ΔE

Example 1

The acrylic rubber-styrene-vinyl cyan terpolymer is prepared by first heating and then stirring a butyl acrylate monomer, which is a rubbery polymer, using a conventional catalyst, emulsifier, crosslinking agent, etc. through emulsion polymerization. 15 parts by weight of acrylonitrile monomers and 35 parts by weight of styrene monomers were mixed with the addition of 50 parts by weight of polymer, a catalyst, and the like, mixed with an emulsifier solution, added continuously, and aged at high temperature to remove unreacted residual monomers. Phosphorus magnesium sulfate was added to agglomerate, washed with water, and dried to prepare a terpolymer.

Styrene-vinyl cyan-based copolymer resin is a copolymer having a weight average molecular weight of 160,000 by mixing 70% by weight of styrene monomer and 30% by weight of acrylonitrile monomer by adding an initiator, an emulsifier, water and a monomer using a common emulsion polymerization method. Was prepared.

A composition ratio of 40% by weight of the ternary copolymer and 60% by weight of SAN (160,000) was added, and 0.3 parts by weight of an antioxidant and 0.3 parts by weight of an ultraviolet absorber were added, followed by uniform mixing using a Henschel mixer.

The prepared resin composition was produced as an upper base material layer containing color and a base material layer without color through calendering (180 ° C.), and the upper base material layer and the base base material layer were adhered to each other. The print layer was printed on the upper limb base layer, and the surface treatment layer was formed by applying and curing a urethane acrylate ultraviolet curable resin.

Example 2

Butadiene rubber-styrene-vinyl cyan terpolymer is prepared by first heating the butadiene monomer, which is a rubbery polymer, using a conventional catalyst, an emulsifier, a crosslinking agent, and the like through an emulsion polymerization method to prepare a polymer. 15 parts by weight of acrylonitrile monomers and 35 parts by weight of styrene monomers were mixed with 50 parts by weight and a catalyst and the like were heated and stirred. The mixture was added continuously with an emulsifier solution and aged at a high temperature to remove unreacted residual monomers. Magnesium was added to agglomerate, washed with water, and dried to prepare a terpolymer.

Styrene-vinyl cyan-based copolymer resin is a copolymer having a weight average molecular weight of 130,000 by adding an initiator, an emulsifier, water, and a monomer using a common emulsion polymerization method by mixing 70% by weight of styrene monomer and 30% by weight of acrylonitrile monomer Was prepared.

A composition ratio of 40% by weight of the ternary copolymer and 60% by weight of SAN (130,000) was added, and 0.3 parts by weight of the antioxidant and 0.3 parts by weight of the ultraviolet absorber were added, followed by uniform mixing using a Henschel mixer.

The prepared resin composition was prepared through a calendering (180 ° C.) process to produce an upper substrate layer containing color and a base substrate layer without color, thereby adhering the upper substrate layer and the underlying substrate layer. The print layer was printed on the upper limb base layer, and the surface treatment layer was formed by applying and curing a urethane acrylate ultraviolet curable resin.

Example 3

20% by weight of the acrylic rubber-styrene-vinyl cyan terpolymer prepared in Example 1, 20% by weight of the butadiene rubber-styrene-vinyl cyan terpolymer prepared in Example 2, A SAN having a molecular weight of 160,000 in Example 1 was used at a composition ratio of 60% by weight, 0.3 parts by weight of antioxidant and 0.3 parts by weight of ultraviolet absorber were added, and then uniformly mixed using a Henschel mixer.

The prepared resin composition was prepared through a calendering (180 ° C.) process to produce an upper substrate layer containing color and a base substrate layer without color, thereby adhering the upper substrate layer and the underlying substrate layer. The print layer was printed on the upper limb base layer, and the surface treatment layer was formed by applying and curing a urethane acrylate ultraviolet curable resin.

Example 4

30 wt% of the acrylic rubber-styrene-vinyl cyan terpolymer, 10 wt% of the butadiene rubber-styrene-vinyl cyan terpolymer, and 60 wt% of the SAN in a composition ratio Except that it was carried out in the same manner.

Comparative Example 1

In Example 3, the composition ratio of 5% by weight of the acrylic rubber-styrene-vinyl cyan terpolymer, 4% by weight of butadiene rubber-styrene-vinyl cyan terpolymer, 91% by weight of SAN The same procedure was followed except that it was used.

Comparative Example 2

In Example 3, the composition ratio of 4% by weight of the acrylic rubber-styrene-vinyl cyan terpolymer, 5% by weight of butadiene rubber-styrene-vinyl cyan terpolymer, 91% by weight of SAN The same procedure was followed except that it was used.

Comparative Example 3

In Example 3, the composition ratio of 60% by weight of the acrylic rubber-styrene-vinyl cyan terpolymer, 11% by weight of butadiene rubber-styrene-vinyl cyan terpolymer, and 29% by weight of SAN The same procedure was followed except that it was used.

Comparative Example 4

In Example 3, the composition ratio of 70% by weight of the acrylic rubber-styrene-vinyl cyan terpolymer, 10% by weight of butadiene rubber-styrene-vinyl cyan terpolymer, and 20% by weight of SAN The same procedure was followed except that it was used.

Table 1 shows the results of measuring the flexibility, processability and physical properties of the decorative sheet produced in Examples and Comparative Examples.

Example Example Example Example Comparative example Comparative example Comparative example Comparative example One 2 3 4 One 2 3 4 polymer g-ASA 40 0 20 30 5 4 60 11 g-ABS 0 40 20 10 4 5 11 60 SAN 60 60 60 60 91 70 29 29 flexibility Hardness 93 98 95 93 97 98 83 81 Processability Processability ○ △ ○ ◎ △ △ △ △ Surface strength Pencil hardness HB or more HB or more HB or more HB or more HB and above HB and above Less than B Less than B Properties The tensile strength 381 420 392 383 459 435 340 313 Properties Phosphorus strength 12.1 13 12.3 11.9 7.1 9.3 13.4 14.1 Properties Weatherability ◎ ○ △ ○ △ △ ○ ◎

In Comparative Examples 1 and 2, the tear strength was as low as 10 or less, and in Comparative Examples 3 and 4, the tensile strength was as low as 350 or less.

Claims (11)

In the multi-layer decor sheet, eco-friendly decor sheet, characterized in that a thermoplastic base layer comprising a rubber selected from the group consisting of acrylic rubber, butadiene rubber, and mixtures thereof. The eco-friendly decor sheet according to claim 1, wherein the rubber is in a form dispersed in a thermoplastic base layer. According to claim 1, wherein the base layer is eco-friendly decor sheet, characterized in that the content of the rubber of 5-70% by weight. The eco-friendly decor sheet of claim 1, wherein the acrylic rubber and the butadiene rubber are used in the form of a graft copolymer obtained by graft polymerization of rubber with styrene and vinyl cyan monomers. The eco-friendly decor sheet according to any one of claims 1 to 4, wherein the base layer further comprises 0.01 to 5.0 parts by weight of an antioxidant and 0.01 to 5.0 parts by weight of an ultraviolet absorber to 100 parts by weight of the thermoplastic resin. . According to claim 1, wherein the decor sheet is a substrate layer; Optionally a decorative layer; And an environmentally friendly decor sheet comprising a surface protective layer. According to claim 1, wherein the substrate layer is eco-friendly decor sheet, characterized in that the multi-layer substrate layer laminated or bonded to the base layer having a different color or composition. A base layer made of a thermoplastic resin containing acrylic rubber and butadiene rubber; A print layer optionally formed on the base layer; And an environmentally friendly decor sheet comprising a protective layer. The eco-friendly decor sheet according to claim 8, wherein the base layer is a single layer or a multilayer base layer. The eco-friendly decor sheet of claim 8, wherein the multilayer base layer comprises a lower base layer not containing a pigment and an upper base layer including a pigment. A lower base layer made of a thermoplastic resin including an acrylic rubber and a butadiene rubber;
A collar upper base layer made of a thermoplastic resin having a lower rubber content than the lower base layer;
A print layer optionally formed; And
Eco-friendly decor sheet made of the protective layer.