KR101718943B1 - Decoration sheet compostion and decoration sheet using thereof - Google Patents

Abstract

The present invention relates to an eco-friendly decorative sheet composition and a decorative sheet using the eco-decorating sheet composition. More particularly, the present invention relates to an eco-friendly decorative sheet composition comprising an eco- Decorating sheet.
The eco-friendly decorative sheet according to the present invention exhibits physical properties similar to those of conventional polyvinyl chloride, but has superior processability and printing properties than conventional polyvinyl chloride. Also, problems related to chlorine gas, dioxin and heavy metals And is less environmentally friendly because the amount of volatile organic compounds emitted is small.

Description

TECHNICAL FIELD The present invention relates to an eco-friendly decorative sheet composition and a decorative sheet using the eco-friendly decorative sheet composition.

The present invention relates to an eco-friendly decorative sheet (hereinafter referred to as a decorative sheet), and more particularly to an eco-friendly decorative sheet comprising a resin composition comprising an acrylic rubber-vinyl chloride-styrene type terpolymer resin and a styrene- To a resin composition for a sheet.

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

The paper decor sheet is vulnerable to moisture and sensitive to environmental changes, so that it is difficult to use as it is. Although paper is impregnated with various resins, there is a problem that the impregnation cost is high.

As a result, plasticized polyvinyl chloride decoctate sheet, aka PVC decorative sheet, has been developed and used, and polyvinyl chloride itself has been extensively used because of its excellent processability, elongation, and heat shaping. However, the use of stabilizers and phthalate plasticizers containing heavy metals to improve the processability of PVC Deco Sheet has problems related to dioxin and heavy metals generated during incineration, and it is not suitable for eco-friendly products due to high emission of volatile organic compounds. For this reason, the development of applying a variety of environmentally friendly materials to decorative sheets is actively underway.

As an alternative environment-friendly material, Korean Patent No. 2001-0086917 proposes a method of replacing polyvinyl chloride deco sheet with a polyolefin resin. However, the polyolefin-based resin has a disadvantage that it is difficult to form, such as being adhered to a calendar, and the surface printing defect and the sheet adhesion force are deteriorated. Moreover, the process is complicated and the appearance quality is inferior because the base layer needs to be treated with a primer It is holding.

Korean Patent Publication No. 2006-0125086 discloses a method of solving the problems of sticking to a calendar when molding such a polyolefin resin and solving the appearance quality. However, there are still problems of complicated processes such as primer treatment and poor physical properties of lapping.

Accordingly, there is a continuing need for a novel eco-friendly decorative sheet which has excellent adhesion to a calender and is excellent in processing stability, excellent in appearance quality after processing, does not contain a heavy metal component, and has good adhesion.

It is an object of the present invention to provide a decorative sheet of a new environmentally friendly material free from harmful substances such as heavy metals and phthalate plasticizers.

Another object of the present invention is to provide a resin composition for decor sheet which is excellent in calender molding and T-die processability, and which can realize excellent appearance quality, heat resistance, printability, adhesiveness and ductility, .

It is still another object of the present invention to provide a film for producing a decor sheet, which is produced by using the resin composition for a decor sheet.

It is still another object of the present invention to provide a multi-layer decorative sheet comprising the film.

Another object of the present invention is to provide a novel decor sheet having a simple and effective structure by having the adhesive force corresponding to the PVC decor sheet so that the polyethylene-based sheets can omit the layers introduced for improving the adhesion.

In order to attain the above object, the decor sheet according to the present invention is characterized in that a substrate layer including an acrylic rubber is formed.

In the present invention, the base layer is not limited theoretically, but includes acrylic rubber, so that polar molecules can be formed and easily adhered to a window, particularly to a window such as PVC, good color developability, And weatherability.

In the present invention, the base layer may be prepared by mixing an acrylic rubber and a thermoplastic resin compatible with the acrylic rubber, and preferably the base layer is provided with a flowability and workability as a film, A styrene-based copolymer, more preferably a styrene-based vinylene copolymer, can be used so as to have good physical properties in terms of hardness, tensile strength, and tear strength required for the styrene-based copolymer.

In the present invention, the acrylic rubber may be a rubber having an acrylic monomer as a main component having a low temperature Tg in the range of -10 to -50 DEG C, preferably an acrylic monomer having 2 to 8 carbon atoms, for example, an alkyl acrylate monomer , Preferably ethyl acrylate, butyl acrylate, ethylhexyl acrylate and the like, and more preferably butyl acrylate.

In the practice of the present invention, the acrylic rubber may be prepared by polymerizing the surface of the acrylic rubber with a resin having a high Tg such as styrene, acrylonitrile, or methyl methacrylate to increase the kneadability of the base layer with other resins, Graft polymers of acrylic rubber, core-shell polymers of acrylic rubber, and the like. In a preferred embodiment of the present invention, in order to improve the kneadability of the acrylic rubber with the styrene-vinyl cyanide copolymer, an acrylic rubber-vinylcyano-styrene type terpolymer, which is graft-polymerized with a styrene- A cohesive resin can be used.

In one embodiment of the present invention, the acrylic rubber-vinyl chloride-styrene-based ternary copolymer resin can be usually prepared by emulsion polymerization. First, an acrylic monomer is polymerized to prepare a rubber-like polymer latex, - styrene-based monomers, preferably acrylonitrile-styrene monomers.

In the preferred embodiment of the present invention, the acrylic rubber-vinyl chloride-styrene type ternary copolymer resin uses an acrylic monomer, for example, an alkyl acrylate monomer having 2 to 8 carbon atoms, in order to prepare a rubber-like polymer latex, Preferably, ethyl acrylate, butyl acrylate, ethylhexyl acrylate and the like can be used, and still more preferred is butyl acrylate.

The acrylic monomer for preparing the rubbery polymer latex is mixed with a small amount of a copolymerizable monomer, preferably 20% by weight or less, more preferably 15% by weight or less, still more preferably 10% by weight or less, For example, monomers such as butadiene, styrene and the like. The acrylic monomer may further contain a small amount of a polyfunctional acrylate monomer for graft polymerization of the acrylic monomer.

In the practice of the present invention, the acrylic rubber-vinyl chloride-styrene-based ternary copolymer resin may be composed of 50 to 80 parts by weight of acrylic rubber and 20 to 60% by weight of a mixture of a styrene monomer and a vinylcyanate monomer, The amount of the monomer and the vinyl cyanide monomer may be mixed in a weight ratio of 80:20 to 60:40.

In the present invention, the styrene-based monomer may be an aromatic vinyl monomer such as styrene, alpha-methylstyrene, para-methylstyrene, vinyltoluene, and mixtures of two or more thereof, preferably styrene.

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

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

In the present invention, the production method of the styrene-based vinyl cyanide copolymer is not particularly limited as long as it can satisfy the above-mentioned molecular weight and viscosity range, and can be produced by using ordinary emulsion polymerization, bulk polymerization or suspension polymerization .

In the present invention, the acrylic rubber-vinyl chloride-styrene type terpolymer is preferably used in an amount of 30 to 80% by weight of the thermoplastic resin, and when the content of the terpolymer is less than 30% by weight, Can be remarkably lowered. If it is 80% by weight or more, workability, thermal stability and tensile strength may be lowered.

In the present invention, the styrene-based vinyl chloride copolymer is preferably used in a range of 20 to 70% by weight in the thermoplastic resin constituting the base layer. When the content is less than 20% by weight, And the tensile strength is lowered. When the content is 70% by weight or more, workability and impact strength may be lowered.

In the present invention, the resin composition constituting the base layer may contain an antioxidant in an amount of 0.01 to 5.0 parts by weight, preferably 0.01 to 1.0 part by weight 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 of ADEKA.

In the present invention, it is preferable to use an ultraviolet absorber in the composition so that the processed decor sheet is prevented from being discolored by ultraviolet rays after being wrapped in a profile. The ultraviolet absorber may be used to prevent ultraviolet discoloration of butadiene used in the quaternary copolymer, and may be used in an amount of 0.01-5.0 parts by weight, preferably 0.01-1.0 parts by weight, per 100 parts by weight of the resin composition Is preferably used in the range of

The ultraviolet absorber may be a conventional ultraviolet absorber used to prevent discoloration of the plastic, preferably TINUVIN-P of Ciba Specialty Co.,

In the present invention, the styrene-vinyl cyanide copolymer, the acrylic rubber-vinyl chloride-styrene type ternary copolymer, the antioxidant and the ultraviolet absorber are mixed with a composition using a mixer, and then calendered or T- Die extrusion process.

According to one aspect of the present invention, there is provided a laminate comprising: a base layer made of a thermoplastic resin including an acrylic rubber; Decorative layer; And a protective layer on the surface of the decorative sheet.

In the present invention, the thermoplastic substrate layer containing the acrylic rubber is a layer adhered to a PVC profile or a wood molding by fusion or adhesion. The acrylic rubber is a product obtained by polymerizing an acrylic monomer and rubberized, and the acrylic rubber in the base layer is preferably used in a range of 15 to 65 wt%. More preferably, the acrylic rubber is used by graft-polymerizing the surface thereof.

In the present invention, the base layer may be a single-layer base layer of the same component or may be formed in a multi-layered form in which the content of components, for example, acrylic rubber, is different. The multi-layered base layer can be produced using known methods such as adhesion, fusion, or co-extrusion of the two substrate layers.

In the practice of the present invention, in the case of a multilayer substrate layer, it may be composed of a general substrate layer not containing a pigment and a color substrate layer containing a pigment for decorating so as to improve the decorating property of the decor sheet, The color substrate layer may be different in color only and the components may be the same. It is also possible that both the color and the composition are different.

In the preferred embodiment of the present invention, the multi-layer base layer preferably comprises a lower base layer having a high content of acrylic rubber and a high impact strength, and an upper base layer having a low acryl rubber content and good color developability. The upper base layer is made of a monochromatic color including pigments, and the content of the acrylic rubber is low, so that a super weather-resistant resin having particularly good weatherability of the base layer can be obtained. In the case of a monochrome decor sheet,

In the decorative sheet of the present invention, a printing layer can be selectively formed on the base layer, and surface printing is possible through a known printing method. In one embodiment of the present invention, the print layer may be printed with gravure printing, transfer printing, or the like on the upper base layer to form a print pattern. However, in the case where the base layer of the decorative sheet comprises a lower base layer and an upper base layer and a monochrome color is formed on the upper base layer, the print layer may be omitted.

The protective layer may be formed on the top surface of the decorative sheet of the present invention and is a surface treatment layer which can enhance the scratch resistance of the print layer or the color substrate layer of the product to be manufactured, The surface treatment layer is a layer formed by coating and curing a urethane acrylate-based ultraviolet ray hardening resin for imparting stain resistance to the uppermost portion, and embossing can be performed if necessary.
In the present invention, it is preferable that the decor sheet has a Shore A hardness of 70 to 99.

A new environmentally friendly decor sheet is provided by the present invention. The deco sheet according to the present invention provides a physical property corresponding to PVC without using PVC, thereby replacing the PVC-based decor sheet and fundamentally solving the environmental pollution problems that may occur during manufacture, use and combustion of PVC .

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

Various performance evaluations on the films and processes produced in Examples and Comparative Examples of the present invention were carried out by the following measurement methods

(1) flexibility

Flexibility was determined by measuring Shore A hardness using a shore durometer according to ASTM D2240.

(2) Processability

The sheet was processed by calendering, and the state of appearance of the sheet, the degree of melting and the like were visually judged and classified into?,?, And? Grades.

◎: Excellent appearance and melting state

○: Appearance Scratches are partially generated or some yellowing occurs when melted.

?: A large amount of scratches or defects such as yellowing upon melting cause difficulty in processing as a sheet

(3) Tensile strength

The vertical tensile strength test was carried out in accordance with KS M 3001, using a one-piece specimen at 23 ° C ± 2 standard test. The unit is kgf / cm ² .

(4) Tear strength

The vertical tear strength test was carried out in accordance with the KS M 3001 standard at a temperature of 23 ° C ± 2. The unit is N / cm.

(5) Pencil hardness

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

Example 1

The acrylic rubber-styrenic-vinyl cyanide terpolymer is prepared by polymerizing butyl acrylate monomer, which is a rubbery polymer, with a conventional catalyst, emulsifier, crosslinking agent and the like after stirring and stirring, 50 parts by weight of a polymer and 50 parts by weight of a catalyst were added, and 15 parts by weight of an acrylonitrile monomer and 35 parts by weight of a styrene monomer were mixed while being heated and stirred. The resulting mixture was continuously added with an emulsifier solution and then aged at a high temperature to remove unreacted residual monomers. Magnesium sulfate was added, coagulated, washed, and dried to prepare a terpolymer.

The styrene-vinyl-cyanate copolymer resin was prepared by mixing 70% by weight of a styrene monomer and 30% by weight of an acrylonitrile monomer, and adding an initiator, an emulsifier, water and a monomer using a general emulsion polymerization method to obtain a copolymer having a weight average molecular weight of 160,000 .

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

The resin composition thus prepared was calendered (180 DEG C) to prepare a colorless upper base layer and a colorless base resin layer, and the upper base layer and the lower base layer were adhered to each other. The printed layer was printed on the upper base layer and the surface treated layer was formed by applying and curing a urethane acrylate-based ultraviolet curing resin.

Example 2

The procedure of Example 1 was repeated except that 50 wt% of the ternary copolymer and 50 wt% of SAN were used.

Example 3

In the same manner as in Example 1, except that a ternary copolymer was used in an amount of 60 wt% and a SAN was used in a 40 wt% composition ratio.

Comparative Example 1

The procedure of Example 1 was repeated except that 30% by weight of the ternary copolymer and 70% by weight of SAN were used.

Comparative Example 2

In the same manner as in Example 1, except that a ternary copolymer was used in an amount of 70% by weight and a SAN was used in a proportion of 30% by weight.

Comparative Example 3

The procedure of Example 1 was otherwise repeated except that the ternary copolymer was used in an amount of 80 wt% and the SAN was used in a composition ratio of 20 wt%.

Table 1 shows the results of measuring the flexibility, workability, and physical properties of the decor sheet prepared in the above Examples and Comparative Examples.

Example Example Example Comparative Example Comparative Example Comparative Example One 2 3 One 2 3 polymer ASA 40 50 60 30 70 80 SAN (16 million) 60 50 40 70 30 20 flexibility Hardness 92 91 91 97 84 83 Processability Processability ○ ◎ ◎ △ △ △ Surface strength Pencil hardness HB or more HB or more HB or more HB or more Less than B Less than B Properties The tensile strength 396 382 371 457 340 315 Properties Phosphorus strength 11.9 12 12.1 7.1 13.1 14.3

Claims (13)

A multi-layer decorative sheet comprising a substrate layer adhered to a surface of a profile, a print layer formed on an upper surface of the substrate layer, and a surface protective layer formed on a surface of the print layer,
The base layer is a thermoplastic resin consisting of 30 to 80% by weight of an acrylic rubber-styrene-vinylene-based ternary copolymer and 20 to 70% by weight of a styrene-based vinyl cyanide copolymer,
Wherein the base rubber layer comprises 15 to 65% by weight of acrylic rubber. delete delete The eco-friendly decorative sheet according to claim 1, wherein the acrylic rubber-styrene-vinylene terocyanate terpolymer is a copolymer resin obtained by graft-polymerizing styrene-based and vinylcyanide monomers on an acrylic rubber. delete delete The eco-friendly decorative sheet according to claim 1 or 4, wherein the substrate 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 in 100 parts by weight of the thermoplastic resin. The eco-friendly deco sheet according to any one of claims 1 to 4, further comprising an emboss layer on the surface of the protective layer. The eco-friendly decor sheet according to claim 1, wherein the base layer is a single layer or a multilayer base layer. The eco-friendly decor sheet according to claim 9, wherein the multi-layer base layer comprises a lower base layer not containing a pigment and an upper base layer containing a pigment. The eco-friendly decor sheet according to claim 1, wherein the acrylic rubber is a rubber having a Tg of -50 to -10 ° C. The eco-friendly deco sheet according to claim 1, wherein the decor sheet has a Shore A hardness of 70 to 99. The eco-friendly deco sheet according to claim 10, wherein the multilayer base layer has a rubber content of the lower base layer greater than a rubber content of the upper base layer.