KR20180036100A - Composition of Adhesive Tie-Resin for Polypropylene and PVC Multi-Layer Adhesion - Google Patents

Abstract

Disclosed is an adhesive resin composition for PVC/polypropylene multilayer bonding, comprising polypropylene, polyethylene vinyl acetate, polyethylene acrylic acid, and alpha-olefin copolymers of specific composition which can replace existing liquid type adhesives. The present invention provides an adhesive resin composition for PVC/polypropylene multilayer bonding, comprising: (A) 30-60 wt% of a polypropylene resin; (b) 10-50 wt% of polyethylene vinyl acetate; (c) 10-40 wt% of a polyethylene acrylic acid copolymer; and (d) 2-20 wt% of an alpha-olefin block copolymer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive resin composition for PVC / polypropylene multi-

The present invention relates to an adhesive resin composition for multi-layer PVC / polypropylene bonding, and more particularly to an adhesive resin composition for PVC / polypropylene multi-layer bonding, which comprises polypropylene, polyethylene vinyl acetate, polyethylene acrylic acid and alpha-olefin To an adhesive resin composition for PVC / polypropylene multi-layer adhesion comprising a copolymer.

Polyvinyl chloride (PVC) has excellent flexibility, weather resistance, waterproofness, and printing properties, and is used for indoor and outdoor advertising sheets and decor sheets.

PVC can also be used as a multi-layer film or sheet for specific applications through bonding with other substrates. For example, Publication No. 1995-060918 refers to a technology for the manufacture of a multi-layered sheet of PE / PVC laminated with polyethylene (PE) with chemical resistance characteristics in PVC with softness and oil resistance.

However, PVC and polyolefin have a problem that the interlayer separation easily occurs due to a lack of adhesive force between them. Therefore, there is a need for a multi-layer structure technique comprising a PVC / adhesive layer / polyolefin to which an adhesive layer has been added to maintain interlaminar adhesion.

PVC / adhesive layer / polyolefin multi-layer structure, the need for adhesive layer is mentioned. However, in most cases, the emphasis is placed on the characteristics of multi-layer structures and their applications, so that detailed description of the adhesive layer material technology is omitted or a technique for using a liquid adhesive as an adhesive layer is introduced. have. For example, in Publication No. JR 1995-060918, an adhesive varnish such as a two-part type acrylic resin, a polyester resin, a vinyl chloride resin, a vinegar resin, etc., and a hardener varnish such as a polyurethane resin (tolylene diisocyanate, diphenylmethane diisocyanate) And the use of two-component mixed adhesives. As a further example, the publication No. JR 1997-201863 mentions an adhesive resin layer as a PVC / adhesive resin layer / polyolefin, but does not mention a detailed adhesive resin composition and describes the use of a liquid adhesive.

However, liquid adhesives have disadvantages in terms of environmental issues due to the use of solvents and economic efficiency in terms of manufacturing process. Accordingly, in the present invention, a resin-type adhesive resin composition capable of producing a simple multi-layer film or sheet of PVC / adhesive resin / polyolefin through coextrusion or capable of multilayer molding through a hot pressing process is mentioned.

In addition, what is to be described in more detail in the present invention is to limit the polyolefin layer to polypropylene (PP) in the PVC / adhesive resin / polyolefin structure. Since PP is not compatible with PE, adhesive resin should be developed according to the structure of PVC / adhesive resin / PE, PVC / adhesive resin / PP.

Korean Patent Laid-Open Publication No. 2013-0006365 (2013.01.16) Japanese Patent Application Laid-Open No. 1995-060918 (1995.06.28) Japanese Laid-Open Patent Publication No. 1997-201863 (2008.02.08) Korean Patent Registration No. 0441035 (2008.07.10) Korean Patent Publication No. 2009-0027046 (Mar. 16, 2009) Korean Patent Publication No. 2009-0119583 (2009.11.19)

DISCLOSURE Technical Problem Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a resin for bonding by using a composition comprising a polypropylene, a polyethylene vinyl acetate, a polyethylene acrylic acid and a alpha-olefin copolymer, It is an object of the present invention to provide an adhesive resin composition for multi-layer bonding of PVC / polypropylene which can solve the problems caused by the use of a volatile solvent in a liquid type adhesive and applicable to multilayer molding or hot pressing.

In order to solve the above-mentioned problems, the present invention provides a thermoplastic resin composition comprising: (a) 30 to 60% by weight of a polypropylene resin; (b) 10 to 50% by weight of polyethylene vinyl acetate; (c) 10 to 40% by weight of a polyethylene acrylic acid copolymer; And (d) 2 to 20% by weight of an alpha-olefin block copolymer.

(I) 1-10% by weight of a tackifier; (ii) 0.05 to 2.0% by weight of an antioxidant; Or (iii) 2 to 15% by weight of a polypropylene modified with maleic anhydride or a derivative thereof.

Wherein the polypropylene has a density of 0.89 to 0.92 g / cm 3 and a melt flow rate (MFR) of 0.5 to 10 g / 10 min at a temperature of 230 캜 under a load of 2.16 kg and a propylene content of 2.0 to 3.5% To provide a resin composition.

The polyethylene vinyl acetate has a density of 0.86 to 0.91 g / cm 3 and a melt flow rate (MFR) of 0.5 to 25.0 g / 10 min under a load of 190 ° C and a load of 2.16 kg and a vinyl acetate content of 12 to 35% By weight of the adhesive resin composition.

The polyethylene acrylic acid ester has a density of 0.86 to 0.92 g / cm 3, a melt flow rate (MFR) of 0.5 to 25.0 g / 10 min at a temperature of 190 캜 under a load of 2.16 kg, and an acrylic acid content of 4 to 30% By weight of the adhesive resin composition.

Olefin block copolymer having a density of 0.86 to 0.91 g / cm 3 and a melt flow rate (MFR) of 0.5 to 20.0 g / 10 min at a temperature of 190 캜 under a load of 2.16 kg and an ethylene-alpha olefin block copolymer or propylene - < / RTI > alpha olefin block copolymer.

The alpha-olefin block copolymer may also be an ethylene / propylene block copolymer, an ethylene / octene block copolymer, an ethylene / butene block copolymer, an ethylene / hexene block copolymer or a propylene / ethylene block copolymer, , A propylene / butene polymer, and a propylene / hexene copolymer.

And the modified polypropylene has a maleic anhydride graft ratio of 0.5 to 10% by weight and a molecular weight of 100,000 or less.

Further, the multilayered film prepared by adhering PVC and polypropylene using the above adhesive resin composition was allowed to stand at room temperature for 24 hours, and the peel strength of the film measured by applying Peel speed of 100 mm / min on the basis of ASTM D882 was 0.5 kgf / 15 mm or more.

According to the present invention, the adhesive resin composition of the present invention contains polypropylene, polyethylene vinyl acetate, polyethylene acrylic acid, and alpha-olefin copolymer in an optimal range, It is possible to exhibit excellent adhesion performance between respective layers and appropriate flexibility at the time of press multilayer forming.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The inventors of the present invention have observed that there is an environmental problem due to the use of a solvent of PVC / polyolefin bonding using a conventional liquid type adhesive, and that adhesion failure due to non-uniform application of liquid phase occurs. As a result of intensive studies, When an adhesive resin composition containing polypropylene, polyethylene vinyl acetate, polyethylene acrylic acid and alpha-olefin copolymer in an optimum range is used, not only a multilayer sheet can be produced by a simple method but also applicable to a hot pressing method And reached the present invention.

Accordingly, the present invention provides a polypropylene resin composition comprising: (a) 30 to 60% by weight of a polypropylene resin; (b) 10 to 50% by weight of polyethylene vinyl acetate; (c) 10 to 40% by weight of a polyethylene acrylic acid copolymer; And (d) 2 to 20% by weight of an alpha-olefin block copolymer.

The present invention also relates to a composition comprising (i) 1-10% by weight of a tackifier; (ii) 0.05 to 2.0% by weight of an antioxidant; Or (iii) 2 to 15% by weight of a polypropylene modified with maleic anhydride or a derivative thereof. Although the modified polypropylene and the tackifier are not essential elements for the manifestation of the adhesion force, the addition of the modified polypropylene and the tackifier have the effect of further increasing the peel strength. The antioxidant reduces the browning, decomposition or gel generation of the resin due to deterioration. . The antioxidant may also include a phenolic primary antioxidant or a phosphate-based secondary antioxidant.

Such an antioxidant is contained in an amount of 0.05 to 2.0% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.1 to 0.5% by weight, based on the total resin composition in consideration of the adhesive strength between the substrate of the adhesive layer, % Can be included.

Examples of the polypropylene resin include propylene homopolymer (Homo Propylene), propylene / ethylene random copolymer, propylene / ethylene block copolymer, or ethylene / propylene / alpha-olefin terpolymer Can be used.

The polyethylene vinyl acetate may have a density of 0.86 to 0.91 g / cm 3, a melt flow rate (MFR, 230 ° C, 2.16 kg load) of 0.5 to 25 g / 10 min, and a vinyl acetate content of 12 to 35 wt% . When the polyethylene vinyl acetate resin is used in the density and the melt flow rate range, it is suitable for improving the adhesion between PVC and the polypropylene base material.

The polyethylene acrylic acid copolymer may have a density of 0.86 to 0.92 g / cm 3, a melt flow rate (MFR, 230 ° C, 2.16 kg load) of 0.5 to 25 g / 10 min, and an acrylic acid content of 4 to 30 wt% have. When the polyethylene acrylic acid copolymer resin is used in the density and the melt flow rate range, it is suitable for improving the adhesion between PVC and the polypropylene substrate.

The alpha olefin block copolymer is preferably an ethylene / alpha-olefin block copolymer such as an ethylene / propylene block copolymer or an ethylene / octene block copolymer, an ethylene / butene block copolymer, or an ethylene / hexene block copolymer Or propylene / alpha-olefin block copolymers such as propylene / ethylene block copolymers, propylene / octene block copolymers, propylene / butene copolymers, propylene / hexene copolymers and the like may be used. The density is 0.86 to 0.91 g / cm 3, and the melt flow rate is 0.5 to 20 g / 10 min. When the alpha olefin block copolymer resin is used in the above density and melt flow rate range, it is suitable for improving the adhesion between PVC and polypropylene base material.

The polypropylene modified with maleic anhydride or a derivative thereof can be produced by a reaction extrusion method or a solution method in which maleic anhydride or a derivative thereof is subjected to a modification process. Polypropylene resin, 0.02 to 1% by weight of peroxide initiator, and 0.7 to 10% by weight of maleic anhydride or a derivative thereof. The graft ratio of the resin to maleic anhydride or its derivative is 0.1 to 10 By weight based on the weight of the modified polyolefin resin. The modified polyolefin preferably has a molecular weight of 100,000 or less. When the molecular weight exceeds 100,000, mixing with other resins becomes difficult, and the adhesive force can be reduced.

In the present invention, the term "peroxide initiator" refers to a compound capable of forming a radical in the polypropylene resin to enable the maleic anhydride graft reaction to be carried out on the polypropylene. Particularly, the peroxide initiator may be 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, [DTBPH, 2,5- peroxide, etc. may be used.

Such a peroxide initiator may be included in an amount of 0.02 to 1% by weight based on the polypropylene resin composition, particularly considering the adhesive strength between the PVC and the polypropylene substrate.

In the present invention, the adhesive resin composition for a multilayer film not only has higher adhesiveness but also has a high flexibility and elasticity so that a tackifier can be added to the multilayer film in order to ensure high moldability in the process of producing a coextruded multilayer film . Examples of the tackifier include an aromatic petroleum resin, an aliphatic petroleum resin, a petroleum resin, a hydrogenated petroleum resin, rosin acid, rosin ester, a hydrogenated rosin resin, a coumarone resin, a terpene resin, Butene can be used.

Here, the petroleum resin is a light yellow or blackish brown thermoplastic resin having a weight average molecular weight of 2,000 or less, which is obtained by polymerizing an unsaturated hydrocarbon in a high-temperature pyrolysis fluid such as naphtha, as an acid catalyst. The aromatic petroleum resin is a resin produced by using C9 oil as a main raw material among the oil produced in the olefin process during the naphtha cracking process, and has a softening point of about 80 to 150 ° C and a weight average molecular weight of about 600 to 1,500. The main component of the aromatic petroleum resin is a copolymer of styrene vinyltoluene, alpha -methylstyrene, and indene. Also, the aliphatic petroleum resin is a resin prepared from C5 oil as a raw material among the oil produced in the olefin process during the naphtha cracking process, and has a softening point of about 70 to 100 ° C and a weight average molecular weight of about 800 to 2,000. The major component of the aliphatic petroleum resin is a copolymer of isoprene, piperylene-2-methylbutene-1, and the like. The aliphatic petroleum resin may comprise a petroleum resin prepared from dicyclopentadiene as a raw material. Further, the hydrogenated petroleum resin is a resin formed by adding hydrogen to the aromatic petroleum resin and the aliphatic petroleum resin, and the properties are colorless and transparent, and the overall stability, such as ultraviolet stability, is excellent. The hydrogenated petroleum resin may include a petroleum resin prepared from dicyclopentadiene as a raw material and added with hydrogen.

Such a tackifier may be contained in an amount of 1 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 5% by weight based on the total resin composition in consideration of the adhesive strength between the substrate of the adhesive layer, 3% by weight.

The adhesive resin composition for multi-layer adhesion according to the present invention includes the polypropylene resin, the polyethylene vinyl acetate, the polyethylene acrylic acid copolymer, the alpha-olefin block copolymer, the tackifier and the antioxidant in a simple mixture . In addition, in order to realize improved elasticity and flexibility while securing higher adhesive force and mechanical properties, the adhesive resin composition for multi-layer bonding is preferably a polypropylene resin, a polyethylene vinyl acetate, a polyethylene acrylic acid copolymer, an alpha-olefin block copolymer, A reactive extrudate between the agent and the antioxidant. Such a reaction extrudate can be obtained by reacting the above components. Specifically, the reaction extrudate may be formed by melt extruding the components at a temperature of from 150 to 220 캜. The reaction extrusion can be carried out using a twin screw extruder, and a polypropylene resin, a polyethylene vinyl acetate, a polyethylene acrylic acid copolymer, an alpha-olefin block copolymer and an antioxidant at a temperature ranging from 150 to 220 & The tackifier containing the petroleum resin having a low molecular weight may be introduced through a main feeder, and the tackifier may be introduced through a side feeder.

Conventionally, adhesive materials for multilayer films are mainly manufactured by using a solution method or the like. Such conventional adhesive materials are not suitable for mass production or have not sufficient moldability or flexibility, so that they are not suitable for the production process of a coextruded multilayer film There was a certain limit. On the contrary, the adhesive resin composition for multi-layer bonding according to the present invention contains the above-mentioned specific components and they are formed by reaction extrusion to form a composite body. As a result, the adhesive resin composition exhibits excellent adhesive performance, flexibility and impact resistance It can be easily applied to various manufacturing processes such as a coextruded multilayer film manufacturing process while ensuring mechanical properties. The reaction extrudate can be obtained in the form of a film or the like in the form of a pellet which is easy to be molded.

Hereinafter, a specific embodiment of the present invention will be described.

Example

(1) Production of adhesive resin composition for multilayer film

Each component was mixed with the composition (unit: wt%) shown in the following Table 1 and extruded at a temperature of 150 to 220 ° C by a 40 mm twin-screw extruder to prepare an adhesive resin composition for a multilayer film.

Composition (% by weight) Example Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polypropylene 40 40 16 35 60 Ethylene-alpha olefin block copolymer 5 10 5 20 10 Polyethylene vinyl acetate 22.8 30.8 60.8 18.8 11.8 Polyethylene acrylic acid copolymer 24 14 10 18 10 Modified polypropylene 5 5 5 5 5 Tackifier 3 3 3 3 3 Antioxidant 0.2 0.2 0.2 0.2 0.2

(2) Production of multilayer film

The PVC film produced by the single layer, the adhesive resin film and the polypropylene (PP) film produced by the adhesive resin composition (Examples 1 and 2 and Comparative Examples 1 to 3) were hot pressed to form a multilayer laminate (PVC / Adhesive resin / PP). The hot pressing temperature was lapped at 180 C for 30 seconds at 50 bar.

Experimental Example

(1) Peel strength measurement

The peel strength of the multi-layer film prepared by the above example was measured at room temperature for 24 hours and then applied at a peel rate of 100 mm / min on the basis of ASTM D882. The results are shown in Table 2 below.

division Example Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Peel strength (kgf / 15mm) 0.8 0.7 0.2 0.1 0.1

As shown in Table 2, according to the adhesive resin composition prepared according to the embodiment of the present invention, peel strength can be improved by applying a peel rate of 100 mm / min based on ASTM D882.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (9)

(a) 30 to 60% by weight of a polypropylene resin;
(b) 10 to 50% by weight of polyethylene vinyl acetate;
(c) 10 to 40% by weight of a polyethylene acrylic acid copolymer; And
(d) 2 to 20% by weight alpha-olefin block copolymer;
/ RTI > wherein the adhesive resin composition for PVC / polypropylene multi-layer adhesion comprises a thermoplastic resin. The method according to claim 1,
(i) 1-10% by weight of a tackifier;
(ii) 0.05 to 2.0% by weight of an antioxidant; or
(iii) 2 to 15% by weight of a polypropylene modified with maleic anhydride or a derivative thereof;
Wherein the adhesive resin composition further comprises an adhesive resin. The method according to claim 1,
Wherein the polypropylene has a density of 0.89 to 0.92 g / cm 3 and a melt flow rate (MFR) of 0.5 to 10 g / 10 min under a load of 2.16 kg at a temperature of 230 캜 and a propylene content of 2.0 to 3.5% Composition. The method according to claim 1,
Characterized in that the polyethylene vinyl acetate has a density of 0.86 to 0.91 g / cm 3 and a melt flow rate (MFR) of 0.5 to 25.0 g / 10 min at a temperature of 190 캜 under a load of 2.16 kg and a vinyl acetate content of 12 to 35% . The method according to claim 1,
Characterized in that the polyethyleneacrylic acid has a density of 0.86 to 0.92 g / cm 3 and a melt flow rate (MFR) of 0.5 to 25.0 g / 10 min at a temperature of 190 캜 under a load of 2.16 kg and an acrylic acid content of 4 to 30% . The method according to claim 1,
Wherein the alpha-olefin block copolymer has a density of 0.86 to 0.91 g / cm 3 and a melt flow rate (MFR) of 0.5 to 20.0 g / 10 min at a temperature of 190 ° C under a load of 2.16 kg and an ethylene-alpha olefin block copolymer or propylene- Wherein the adhesive resin composition is an alpha olefin block copolymer. The method according to claim 6,
Wherein said modified alpha-olefin block copolymer is an ethylene / propylene block copolymer, an ethylene / octene block copolymer, an ethylene / butene block copolymer, or an ethylene / hexene block copolymer. 3. The method of claim 2,
Wherein the modified polypropylene has a maleic anhydride graft ratio of 0.5 to 10% by weight and a molecular weight of 100,000 or less. The method according to claim 1,
When the peel strength of the film measured by applying a peel rate of 100 mm / min on the basis of ASTM D882 after leaving the multilayer film prepared by adhering PVC and polypropylene using the adhesive resin composition at room temperature for 24 hours was 0.5 kgf / 15 mm or more.