KR19990074181A - Adhesive resin composition - Google Patents

Abstract

The present invention provides an ethylene vinyl acetate-based adhesive resin composition having excellent film formability, weather resistance, and adhesion to a metal, the composition comprising: 40 to 70 parts by weight of component (A) and 3 to 30 weight of component (B) And 5 to 20 parts by weight of component (C), 5 to 20 parts by weight of component (D) and 5 to 20 parts by weight of component (E).

(A) Ethylene vinyl acetate copolymer which satisfies the following conditions ① to ②:

① Vinyl acetate content: 10-20 wt%

② Melt Index (MFR (E): ASTM 1283.E): 5 ~ 20g / 10min (190 ℃)

(B) Modified ethylene vinyl acetate copolymer graft-modified with unsaturated carboxylic acid or derivatives thereof, satisfying the following conditions ① to ③:

① Vinyl acetate content: 3 ~ 20 wt%

② Graft modification amount of unsaturated carboxylic acid or its derivatives: 0.1 to 10 parts by weight

③ Melt Index (MFR (E): ASTM 1283.E): 0.1 ~ 20g / 10min (190 ℃)

(C) Styrene homopolymer or styrene-butadiene binary copolymer having a melt index (MFR (G): ASTM 1283.G) of 10 to 40 g / 10 minutes (230 ° C. temperature).

(D) Ethylene α-olefin copolymer, which satisfies the following conditions ① to ②:

① Melt Index (MFR (E): ASTM 1283.E): 1.0 ~ 20g / 10min (190 ℃)

② Density: 0.850 ~ 0.900g / cm3

(E) Petroleum resin which satisfies the following conditions ① to ②:

① Hydrocarbon resin and its hydrogenated substance consisting of C ₄ system, C ₅ system or C ₉ system

② Softening Point (ASTM E28 ~ 58): 90 ~ 120 ℃

The composition of the present invention described above can be used in metal-plastic composite panels for building interior and exterior materials because it has excellent adhesion with metals without treating adhesives or tackifiers.

Description

Adhesive resin composition

The present invention relates to an ethylene vinyl acetate-based adhesive resin composition, and more particularly, ethylene vinyl acetate-based adhesive that can be used in metal-plastic composite panels for building interior and exterior materials due to its excellent film formability, weather resistance and adhesion to metal. It relates to a resin composition.

In recent years, metal-plastic composite building interior and exterior materials in which metals such as aluminum and plastics are composited are used for high-quality building appearance and light weight in construction. However, metals and plastics lack adhesion to each other, so an adhesive for this is indispensable. In general, adhesives used for this purpose include solvent type adhesives, non-type hot melts, and curable adhesive resins, but solvent type adhesives have a problem in that a working environment and productivity are lowered due to volatilization of a solvent, Formulation hot melt has a problem that does not have a strong heat resistance and weather resistance enough to use as a building material. In addition, when the curable adhesive resin is used, it has excellent heat resistance but has a disadvantage in terms of long-term weather resistance due to curing of the resin.

Therefore, many studies have been conducted to overcome these disadvantages, and in particular, various adhesive resin compositions using ethylene vinyl acetate copolymer have been prepared, examples of which are as follows.

Japanese Patent Laid-Open No. 7-286151 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, an adhesive scavenger, and a wax, but this has a problem in that it is impossible to form a film and lacks adhesive strength and durability.

In addition, Japanese Patent Application Laid-open No. Hei 8-003526 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, an tackifier, and a styrenic block copolymer, but this also has a problem in that film molding is impossible and the adhesive strength is insufficient. .

In addition, Japanese Patent Application Laid-Open No. 3-68640 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, a polyethylene modified with an unsaturated carboxylic acid or a derivative thereof, a monovinyl aromatic hydrocarbon olefin block copolymer elastomer, and an ethylene α-olefin copolymer. Although it is presented, the adhesive expression temperature is high, there is a problem that the productivity is low and the adhesion is insufficient.

Accordingly, the present inventors have repeatedly studied to solve the above problems, and as a result, modified ethylene vinyl acetate copolymers, styrene polymer resins, and ethylene α-olefins graft-modified with unsaturated carboxylic acid or derivatives thereof. The present invention has been completed by knowing that the copolymer and the petroleum resin can provide an adhesive resin composition which is excellent in film formability and adhesive durability and capable of exhibiting adhesion even at a lower temperature.

Accordingly, an object of the present invention is to provide an ethylene vinyl acetate-based adhesive resin composition excellent in film formability, weather resistance and adhesion to a metal.

In order to achieve the above object, the adhesive resin composition according to the present invention comprises 40 to 70 parts by weight of the following (A) component, 3 to 30 parts by weight of (B) component, 5 to 20 parts by weight of (C) component, (D 5 to 20 parts by weight of the component and 5 to 20 parts by weight of the component (E).

(A) Ethylene vinyl acetate copolymer which satisfies the following conditions ① to ②:

① Vinyl acetate content: 10-20 wt%

② Melt Index (MFR (E): ASTM 1283.E): 5 ~ 20g / 10min (190 ℃)

(B) Modified ethylene vinyl acetate copolymer graft-modified with unsaturated carboxylic acid or derivatives thereof, satisfying the following conditions ① to ③:

① Vinyl acetate content: 3 ~ 20 wt%

② Graft modification amount of unsaturated carboxylic acid or its derivatives: 0.1 to 10 parts by weight

③ Melt Index (MFR (E): ASTM 1283.E): 0.1 ~ 20g / 10min (190 ℃)

(C) Styrene homopolymer or styrene-butadiene binary copolymer having a melt index (MFR (G): ASTM 1283.G) of 10 to 40 g / 10 minutes (230 ° C. temperature).

(D) Ethylene α-olefin copolymer, which satisfies the following conditions ① to ②:

① Melt Index (MFR (E): ASTM 1283.E): 1.0 ~ 20g / 10min (190 ℃)

② Density: 0.850 ~ 0.900g / cm3

(E) Petroleum resin which satisfies the following conditions ① to ②:

① Hydrocarbon resin and its hydrogenated substance consisting of C ₄ system, C ₅ system or C ₉ system

② Softening Point (ASTM E28 ~ 58): 90 ~ 120 ℃

Other objects and applications of the present invention will become apparent to those skilled in the art from the construction and function of the following invention.

Hereinafter, the present invention will be described in more detail.

Since the adhesive resin composition of the present invention has excellent film formability and good productivity, the adhesive resin composition may be used in metal-plastic composite panels for building interior and exterior since it has excellent adhesive strength, durability, and low temperature adhesive strength.

In the adhesive resin composition of the present invention, the component (A) has a vinyl acetate content of 10 to 20% by weight, and a melt index (MFR (E)) measured by the ASTM 1283.E method is 5 to 20 g / 10 minutes. Ethylene vinyl acetate copolymer, which is (190 DEG C), is contained in an amount of 40 to 70 parts by weight based on the total weight of the composition. When the melt index of the component (A) is 5 g / 10 min or less, the adhesive strength is insufficient, and when it is 20 g / 10 min or more, the kneading property with other components used in the present invention is poor. In addition, when the content of vinyl acetate is less than 10% by weight, the adhesive strength is insufficient, and when the content exceeds 20% by weight, heat resistance and film formability are insufficient. In addition, when the content of the component (A) is 40 parts by weight or less or 70 parts by weight or more with respect to the total weight of the composition, it does not give sufficient adhesive force.

The modified ethylene vinyl acetate copolymer (B) used in the present invention is obtained by graft reaction of an ethylene vinyl acetate copolymer having a vinyl acetate content of 3 to 20% by weight with an unsaturated carboxylic acid or a derivative thereof. Or the graft modification amount of the derivative is 0.1-10 weight part. The reaction between the ethylene vinyl acetate copolymer and the unsaturated carboxylic acid or derivatives thereof is generally performed by simple heating using a radical initiator in the presence or absence of a catalyst. In the present invention, the unsaturated carboxylic acid or derivative thereof used for graft modification of ethylene vinyl acetate is specifically maleic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methacrylic. Butyl acid, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleic acid, dimethyl ester of maleic acid, monomethyl ester of itaconic acid, dimethyl ester of itaconic acid, monomethyl ester of itaconic acid, monomethyl ester of itaconic acid, Acrylic acid amide, methacrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-NN-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-di Butylamide, Fmaric acid-N-monoethylamide, Fmaric acid-N, N-dibutylamide, maleimide, N-butylmale Imides, N-phenylmaleimide, and the like.

Further, the melt index of component (B) is 0.1 to 20 g / 10 minutes (190 ° C. temperature), preferably 5 to 15 g / 10 minutes, and is contained in an amount of 3 to 30 parts by weight based on the total weight of the composition. ) When the content of the component is less than 3 parts by weight, the adhesive strength is not expressed and when the content exceeds 30 parts by weight, the adhesive strength does not improve.

In addition to the components (A) and (B), the composition according to the present invention contains styrene homopolymer or styrene-butadiene binary copolymer as component (C) in an amount of 5 to 20 parts by weight. The component (C) has a melt index of 10 to 40 g / 10 minutes, preferably 10 to 20 g / 10 minutes, measured by the ASTM 1283.G method. If the melt index of component (C) is less than 10g / 10 minutes or more than 40g / 10 minutes, melt kneading with other components is not good, and if the content of component (C) is less than 5 parts by weight, the weather resistance is insufficient and 20% When it exceeds a part, adhesive force falls.

Further, the composition according to the present invention has a melt index of 0.1 to 20 g / 10 minutes (190 DEG C), preferably 1 to 10 g / 10 minutes, and a density of 0.850 to The ethylene α-olefin copolymer, which is 0.900 g / cm 3 and preferably 0.87-0.88 g / cm 3, is contained in an amount of 5 to 20 parts by weight based on the total weight of the composition. When content of (D) component is less than 5 weight part, adhesive force is not enough, and when it exceeds 20 weight part, heat resistance will fall and film formability will become bad. As an alpha olefin contained in the ethylene- alpha -olefin copolymer of (D) component, C3-C20 alpha olefin can be used, Specifically, propylene, 1-butene, 4-methyl-1- pentene, 1-hexene, 1-octene, 1-decene, 1-tetracene and the like can be used, and such α-olefins can be used alone or as a mixture of two or more thereof.

In addition, the composition according to the present invention is a petroleum resin of a hydrocarbon resin or a hydrogenated substance thereof having a softening point of 90 to 120 ° C. and a C ₄ system, C ₅ system or C ₉ system measured by ASTM E28 to 58 as the component (E). 5 to 20 parts by weight, based on the total weight of the composition. When the content of the component (E) is less than 5 parts by weight, the adhesive strength is insufficient, and when the content of the component (E) exceeds 20 parts by weight, blocking is likely to occur, which causes problems in handling.

Further, in the adhesive resin composition of the present invention, in addition to the components (A) to (E), various antioxidants, ultraviolet absorbers, photoprotective agents, lubricants, antistatic agents, inorganic or organic fillers well known in the art as needed. Can be suitably selected and blended by those skilled in the art without difficulty.

Hereinafter, the present invention will be embodied through the examples.

Evaluation methods of various physical properties used in the following Examples and Comparative Examples were carried out by the following test methods.

(1) Film formability:

It was evaluated by three grades.

○: Stable molding

(Triangle | delta): Although it is a film-shaped film | membrane, stable shaping | molding is bad (frequently bursts or interrupts)

▲: molding itself is impossible

(2) Fish eye number

The number of fish eyes per 600 cm 2 was measured.

(3) Adhesive force (1):

A test piece composed of 200 μm aluminum / 50 μm adhesive resin film / 2 mm polyethylene sheet, having a length of 15 cm and a width of 15 mm was prepared, and then extruder was used at a temperature of 150 ° C. under a pressure of 5 kg / cm 2. After bonding for 2 minutes and quenching, peeling was carried out at 180 ° C. at a peel rate of 200 m / min in a universal tensile machine, and the LOAD value (unit: kg / 15 mm) per 15 mm of the test piece was measured.

(4) adhesive strength (2):

Adhesion was measured after aging for 1000 hours at a temperature of 63 ° C. and a humidity of 50% in a WEATHER-O-METER (Xenon arc) at a temperature of 63 ° C. and a humidity of 50%.

(5) adhesion expression temperature:

After preparing the same test piece as the test method of the adhesive force (1), by molding for each temperature using an extruder was measured the temperature at which the adhesive force begins to express.

EXAMPLE 1

(A) 40 parts by weight of ethylene-vinyl acetate (EVA) (B) 20 parts by weight of (B) maleic anhydride modified ethylene-vinyl-acetate (M-EVA), (C) 15 parts by weight of styrene-based polymer resin (PS), ( D) Add 10 parts by weight of ethylene-propylene copolymer (EPR) and 5.0 parts by weight of (E) petroleum resin, mix each component with Henschel mixer, and use L / D 26, 40 mm diameter single screw extruder. After melting, kneading and granulation, the resultant was dried in a convection oven, and a film having a thickness of 50 μm was formed using a die diameter 50 mm upward inflation film molding machine. Various physical properties of the obtained moldings were measured in accordance with the method described above, and the results are shown in Table 1 below.

[Examples 2 to 5]

Except for containing the components (A) to (E) in the content shown in Table 1, to carry out in the same manner as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.

[Comparative Examples 1 and 2]

Except for containing the components (A) to (E) in the amounts shown in Table 1, and was carried out in the same manner as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.

[Comparative Example 3]

A molded product was obtained in the same manner as in Example 1 except for containing 20 parts by weight of maleic anhydride-modified high density polyethylene (M-PE) based on the total weight of the composition instead of maleic anhydride-modified ethylene-vinyl-acetate (B). The results of measuring the physical properties are shown in Table 1 below.

[Comparative example 4]

Of the components (A) to (E), only (A), (C) and (D) components are added in the amounts shown in Table 1 below, and maleic anhydride-modified high density polyethylene (M-PE) is 10 parts by weight based on the total weight of the composition. , Except that the shell styrene-ethylene-butadiene-styrene terpolymer block copolymer (SEBS) containing 5 parts by weight of the same as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in the following table 1 is shown.

[Comparative Example 5]

Same as Example 1 except adding only the components (A) and (E) in the amounts shown in Table 1 among the components (A) to (E), and further containing 20 parts by weight based on the total weight of the composition. It was carried out to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Resin composition (part by weight) A 40 45 50 55 60 55 65 50 60 60 25 B 20 25 30 20 20 20 20 - - - - M-PE - - - - - - - 20 10 - - C 15 15 10 10 10 15 - 15 15 - - D 10 5 5 5 5 10 5 10 10 - - E 5 10 5 10 5 - 10 5 - 20 50 Wax - - - - - - - - - 20 - SEBS - - - - - - - - 5 - - SIS - - - - - - - - - - 25 Film processability ○ ○ ○ ○ ○ ○ ○ △ △ △ ▲ fish eye 3 4 2 4 5 4 4 20 3 3 - Adhesive force (1) 5.7 6.0 6.2 5.6 5.4 3.2 5.0 5.2 5.2 3.5 2.5 Adhesion (2) 5.8 6.2 6.3 5.8 5.6 3.1 2.2 5.3 5.0 3.6 1.0 Adhesion Temperature 115 110 115 110 110 120 110 135 135 135 100 A: Ethylene-vinyl-acetate (EVA) Vinyl acetate content: 20 parts by weight, MFR (E): 18 B: Maleic anhydride modified ethylene-vinyl-acetate (M-EVA) graft content: 1.0 part by weight, MFR (E ): 4, density: 0.95 C: styrene polymer resin (PS) Cheil Industries "HF-2660", MFR (E): 8, density: 1.04 D: ethylene-propylene copolymer (EPR) "Kumho Petrochemical KEP- 020P "E: Petroleum resin" Kolon Petroleum resin HP-100 ", Softening point: 95-105 degreeC M-PE: Maleic anhydride modified high density polyethylene graft content: 1.0 weight part, MFR (E): 3, Density: 0.96 SEBS: Shell styrene-ethylene-butadiene-styrene ternary block copolymer "Grayton G-1642" wax: Namyoung emulsified paraffin wax DP-140, melting point: 60 to 65.6 ° C SIS: styrene isoprene block copolymer "SHELL company TR -107 "

As can be seen from the above description, the ethylene vinyl acetate-based adhesive resin composition of the present invention is a maleic anhydride-modified ethylene-vinyl-acetate (B), styrene-based polymer resin (C), in ethylene-vinyl-acetate (A), It is manufactured by adding ethylene-propylene copolymer (D) and petroleum resin (E) to have excellent film formability, weather resistance, and adhesion to metal. Therefore, it is a metal-plastic composite for building interior and exterior materials without treating adhesives or tackifiers. It can be used for panels.

Claims (1)

In ethylene vinyl acetate type adhesive resin composition, The following (A) component 40-70 weight part, (B) component 3-30 weight part, (C) component 5-20 weight part, (D) component 5-20 weight part, and (E) component 5-20 weight part An ethylene vinyl acetate-based adhesive resin composition, characterized by containing in an amount. (A) Ethylene vinyl acetate copolymer which satisfies the following conditions ① to ②: ① Vinyl acetate content: 10-20 wt% ② Melt Index (MFR (E): ASTM 1283.E): 5 ~ 20g / 10min (190 ℃) (B) Modified ethylene vinyl acetate copolymer graft-modified with unsaturated carboxylic acid or derivatives thereof, satisfying the following conditions ① to ③: ① Vinyl acetate content: 3 ~ 20 wt% ② Graft modification amount of unsaturated carboxylic acid or its derivatives: 0.1 to 10 parts by weight ③ Melt Index (MFR (E): ASTM 1283.E): 0.1 ~ 20g / 10min (190 ℃) (C) Styrene homopolymer or styrene-butadiene binary copolymer having a melt index (MFR (G): ASTM 1283.G) of 10 to 40 g / 10 minutes (230 ° C. temperature). (D) Ethylene α-olefin copolymer, which satisfies the following conditions ① to ②: ① Melt Index (MFR (E): ASTM 1283.E): 1.0 ~ 20g / 10min (190 ℃) ② Density: 0.850 ~ 0.900g / cm3 (E) Petroleum resin which satisfies the following conditions ① to ②: ① Hydrocarbon resin and its hydrogenated substance consisting of C ₄ system, C ₅ system or C ₉ system ② Softening Point (ASTM E28 ~ 58): 90 ~ 120 ℃