KR101931756B1 - Enviromental-friendly thermoplastic composition for deco-sheet and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an eco-friendly decorative sheet using a thermoplastic resin composition, and more particularly to an eco-friendly decorative sheet using an acrylic rubber-vinyl cyano-styrene copolymer, a ternary copolymer of an acrylonitrile-butadiene-styrene polymer, Based decorative sheet comprising a resin composition made of a styrene-based vinyl-based copolymer.
The eco-friendly decorative sheet according to the present invention exhibits a similar level of physical properties as conventional polyvinyl chloride decor sheet and PP decor sheet, but is superior in workability, printability and weather resistance to conventional PVC and PP decor sheet. There is no problem related to chlorine gas, dioxin and heavy metals at the time, and the amount of volatile organic compounds emitted is small, which is more environmentally friendly.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting resin composition for an environmentally friendly decorative sheet, and a decorative sheet using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to an environmentally friendly decorating sheet (hereinafter referred to as a decorative sheet), and more particularly to an eco-friendly decorative sheet (hereinafter, referred to as " decorative sheet ") which comprises an acrylic rubber-vinylene chloride- And a resin composition comprising the copolymer.

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 have.

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, the problems such as complicated processes such as primer treatment and poor physical properties of lapping still remain.

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.

To attain the above object, the decor sheet according to the present invention is characterized in that the acrylic rubber and / or the butadiene rubber include a thermoplastic resin base layer in which the matrix resin is dispersed.

In the present invention, the base layer includes acrylic rubber and / or butadiene rubber, though it is not limited theoretically. The base layer can be easily adhered to windows, especially PVC windows, It is possible to have impact resistance and weather resistance.

In the present invention, the base layer can be produced by melt-mixing an acrylic rubber and / or a butadiene rubber with a thermoplastic resin compatible with the rubber, and preferably, And a styrene-based copolymer, more preferably a styrene-based vinylene copolymer, may be used as the matrix resin so as to have good physical properties in terms of hardness, tensile strength and tear strength required for the decorative sheet to be produced.

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.

The butadiene rubber is a butadiene rubber polymer grafted by emulsion polymerization or bulk polymerization using styrene and acrylonitrile in the presence of a butadiene monomer-based polybutadiene.

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

In a preferred embodiment of the present invention, the acrylic rubber and / or butadiene rubber is graft-polymerized with a resin having a high Tg such as styrene, acrylonitrile or methylmethacrylate to obtain a graft acrylic rubber and / Butadiene rubber to enhance the kneading property with the matrix resin, and it is preferable to use a monomer mixture containing the matrix resin component as the graft polymerization. For example, when an acrylic rubber or a butadiene-based rubber is used, a styrene-vinyl cyanide copolymer matrix resin is preferably used in which an acryl rubber (butadiene rubber) -acrylate rubber (graft copolymer), which is graft-polymerized with a styrene- It is preferably used as a vinyl cyano-styrene type graft polymer.

In one embodiment of the present invention, the acryl rubber graft copolymer and the butadiene rubber graft copolymer may be prepared in powder form and mixed with each other, and the acrylic rubber graft copolymer and the butadiene rubber graft copolymer may be used in the form of a latex , And then coagulated and dried to prepare a powder. In the latex mixing, an acrylic rubber and a butadiene rubber are prepared in the form of a latex and kneaded. Then, the grafting is carried out by using a pre-grafting method in which a grafting is carried out or a latex type of acrylic rubber and butadiene rubber, Graft polymerization-post-mixing method in which the latex copolymer latex is mixed with the latex, and may be arbitrarily selected depending on the needs of those skilled in the art.

In one embodiment of the present invention, the acrylic rubber-vinyl chloride-styrene graft copolymer or acrylonitrile-butadiene-styrene graft copolymer resin may be prepared by emulsion polymerization, Butadiene-based monomer to prepare a rubber-like polymer latex, and then graft-polymerizing the vinyl cyanide monomer-styrene monomer, preferably acrylonitrile-styrene monomer.

In the preferred embodiment of the present invention, the acrylic rubber-vinyl chloride-styrene graft copolymer resin uses an acrylic monomer, for example, an alkyl acrylate monomer having 2 to 8 carbon atoms, to prepare a rubber-like polymer latex , Preferably ethyl acrylate, butyl acrylate, ethylhexyl acrylate and the like, and still more preferably 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 a preferred embodiment of the present invention, the butadiene-based graft copolymer is a butadiene-based graft copolymer which is grafted by emulsion polymerization or bulk polymerization using styrene and acrylonitrile in the presence of a polybutadiene having a butadiene- The preferred content as the polymer is 20 to 50% by weight.

In the practice of the present invention, the acrylic rubber (or butadiene rubber) -vinylcyano-styrene graft copolymer resin is prepared by mixing 50 to 80 parts by weight of an acrylic rubber (or butadiene rubber) with a styrenic monomer and a vinylcyanate monomer mixture 20 to 50 parts by weight, and the styrene-based monomer and the vinylcyanide monomer may be mixed at 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 conventional emulsion polymerization, bulk polymerization or suspension polymerization .

In the practice of the present invention, it is preferable that the thermoplastic resin base layer is made of an acrylic rubber-vinylene chloride-styrene graft copolymer and / or an acrylonitrile-butadiene-styrene graft copolymer, Butadiene-based rubber may be kneaded with the matrix resin so that the content of the butadiene-based rubber is in the range of 5-70% by weight, preferably 30-80% by weight of the graft copolymer, and a matrix resin, It is preferable that the copolymer is kneaded at 20 to 70% by weight.

In the present invention, the resin composition constituting the base layer may contain 0.01 to 5.0 parts by weight, preferably 0.01 to 1.0, of an antioxidant 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 composition of styrene-vinyl cyanide copolymer, acrylic rubber-vinyl chloride-styrene type terpolymer or acrylonitrile-butadiene-styrene type terpolymer, antioxidant and ultraviolet absorber , Followed by calendering or T-die extrusion processing.

According to one aspect of the present invention, there is provided a thermoplastic resin composition comprising: a substrate layer made of a thermoplastic resin containing an acrylic rubber and / or a butadiene rubber; Optionally a decorative layer; And a protective layer on the surface of the decorative sheet.

In the present invention, the thermoplastic base layer containing the acrylic rubber and / or butadiene rubber is a layer adhered to the PVC profile or wood molding by fusion or adhesion. The acrylic rubber is a product obtained by polymerizing an acrylic monomer and rubberizing the butadiene rubber. The butadiene rubber is a product obtained by polymerizing a butadiene monomer. The acrylic rubber or the butadiene rubber in the base layer contains 5 to 70% by weight, more preferably 10- To 30% by weight, and more preferably 12-25% by weight. More preferably, the acrylic rubber or the butadiene rubber is graft-polymerized on the surface thereof.

In the present invention, the base layer may be a monolayer base layer of the same component or may be formed in a multi-layered form in which the content of the constituent components, for example acrylic rubber or butadiene 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 is composed of a lower base layer having a high content of acrylic rubber or butadiene rubber and a high impact strength, and an upper base layer having a low content of acrylic rubber or butadiene rubber and good color developability It is good. The upper base layer is made of a monochromatic color including a pigment and can be made into a super weather-resistant resin having a low content of acrylic rubber or butadiene rubber and having particularly good weatherability of the base layer. In the case of a monochromatic 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 decor sheet of the present invention. The protective layer may be a surface treatment layer which enhances the scratch resistance of the printed layer or the color substrate layer of the product to enhance the commercial properties. 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.

The eco-friendly decorative sheet according to the present invention exhibits a similar level of physical properties as conventional polyvinyl chloride decor sheet and PP decor sheet, but is superior in workability, printability and weather resistance to conventional PVC and PP decor sheet. There is no problem related to chlorine gas, dioxin and heavy metals at the time, and the amount of volatile organic compounds emitted is small, which is more environmentally friendly.

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 . Deco sheets require a tensile strength of 350 or more.

(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. Deco sheets require a tear strength of 10 or more.

(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.

(6) Weathering test

Xenon arc lamp type weathering test method, a weather-o-meter apparatus and a xenon lamp were used in accordance with KS B 5549, and a temperature of 63 ° C, an illuminance of 0.35 W / The degree of discoloration was measured for 2,000 hours under the condition of the humidity of the sample, and the color difference after the irradiation and the color difference (? E) before the irradiation were measured.

?:? E <3

?: 3?? E <5

?: 5?? E <8

X: 8? DELTA E

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 polymer and a catalyst were added thereto, and 15 parts by weight of an acrylonitrile monomer and 35 parts by weight of a styrene monomer were mixed together while the temperature was elevated and stirred. The resulting mixture was continuously added with an emulsifier solution, and the mixture was aged at a high temperature to remove unreacted residual monomers. Magnesium sulfate was added thereto, followed by agglomeration, washing with water and drying 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 top base layer containing color and a base substrate layer having no color, 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 butadiene rubber-styrene-vinylene terpolymer is prepared by polymerizing a butadiene monomer, which is a rubbery polymer, with a conventional catalyst, an emulsifying agent, a crosslinking agent, etc. after stirring by stirring through emulsion polymerization, 15 parts by weight of acrylonitrile monomer and 35 parts by weight of styrene monomer were mixed with the emulsifier solution continuously while being heated and stirred, and the mixture was aged at a high temperature to remove unreacted residual monomers. Then, sulfuric acid Magnesium was added, coagulated, washed, and dried to prepare a terpolymer.

The styrene-based vinyl chloride copolymer resin was prepared by mixing 70% by weight of a styrene monomer and 30% by weight of an acrylonitrile monomer, adding an initiator, an emulsifier, water and a monomer using a general emulsion polymerization method to prepare a copolymer having a weight average molecular weight of 130,000 .

, 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 (130,000), 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 3

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

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 4

In Example 3, 30% by weight of an acrylic rubber-styrene-vinylene-cyanide terpolymer was used, 10% by weight of a butadiene rubber-styrene-vinylene chloride type ternary copolymer and 60% by weight of SAN . &Lt; / RTI &gt;

Comparative Example 1

In Example 3, 5% by weight of an acrylic rubber-styrene-vinylene chloride type ternary copolymer, 4% by weight of a butadiene rubber-styrene-vinylene chloride type ternary copolymer and 91% by weight of SAN Was used as the catalyst.

Comparative Example 2

In Example 3, 4% by weight of an acrylic rubber-styrene-vinylene-based ternary copolymer, 5% by weight of a butadiene rubber-styrene-vinylene-cyanide ternary copolymer, and 91% by weight of SAN Was used as the catalyst.

Comparative Example 3

In Example 3, 60% by weight of an acrylic rubber-styrene-vinylene-based ternary copolymer, 11% by weight of a butadiene rubber-styrene-vinylene chloride type ternary copolymer, and 29% by weight of SAN Was used as the catalyst.

Comparative Example 4

In the same manner as in Example 3, except that 70 wt% of the acrylic rubber-styrene-vinylene cyanide terpolymer was used, 10 wt% of the butadiene rubber-styrene-vinylene cyanide terpolymer and 20 wt% Was used as the catalyst.

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 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 or more HB or more 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, and in Comparative Examples 3 and 4, the tensile strength was as low as 350 or less.

Claims (11)

A lower substrate layer attached to a surface of the profile,
A printing layer formed on an upper surface of the lower substrate layer,
A multi-layer decorative sheet comprising a surface protective layer formed on an upper portion of a print layer,
Wherein the lower base layer comprises 30 to 80% by weight of a graft copolymer comprising a mixture of an acrylic rubber-styrene-vinyl cyanide terpolymer and a butadiene rubber-styrene-vinyl cyanide terpolymer, Wherein the thermoplastic resin comprises 15 to 25% by weight of a mixture of an acrylic rubber and a butadiene-based rubber. The eco-friendly decor sheet according to claim 1, wherein the thermoplastic resin is a thermoplastic resin comprising 20 to 70% by weight of a vinyl cyano copolymer.
delete delete The acrylic rubber-styrene-vinylene terocyanate terpolymer and the butadiene rubber-styrene-vinylene terpolymer copolymer according to claim 1, wherein the acrylic rubber-styrene-vinylene chloride terpolymer is graft-polymerized with a styrene- Graft copolymer. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; 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. delete The eco-friendly decor sheet according to claim 1, wherein the base layer is a multi-layer base layer in which base layers differing in hue or composition are laminated. delete delete delete delete