JPH0141667B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel adhesive resin composition. For more details, metal, glass, ceramics,
The present invention relates to an improved adhesive resin composition that has high adhesion to both wood base materials and various polymeric materials even under low temperature adhesive conditions. Generally, laminates made of polymeric materials, particularly polyolefins, and metals have attracted wide attention as structural materials because they combine the high strength of metals with the lightweight and inexpensive advantages of polyolefins. However, polyolefins do not have polar groups in their molecules, and simply adhering them together does not provide a satisfactory adhesion effect and does not result in a laminate that can be put to practical use. Therefore, in the past, attempts have been made to use various adhesive resins when manufacturing polyolefin and metal laminates. For example,
- Ethylene-glycidyl (meth)acrylate copolymer shown in Publication No. 27527, Japanese Patent Publication No. 1987-
Polyolefins graft-modified with unsaturated carboxylic acids or acid anhydrides as shown in Japanese Patent Publication No. 19238, and ethylene as shown in Japanese Patent Publication No. 42-6178.
There are many types, including unsaturated carboxylic acid copolymers and ionomers in which part of the carboxylic acid groups of the ethylene-unsaturated carboxylic acid copolymers shown in Japanese Patent Publication No. 7149/1988 are crosslinked with metal ions. However, with these adhesive resins, it is difficult to obtain adhesives that are sufficiently satisfactory for practical use under low-temperature adhesive conditions. In addition, particularly in laminated sheath cable applications, balanced and high adhesion properties are required for both the metal tape and the resin of the outer protective layer, such as polyethylene.
Alternatively, there is a strong desire to develop resins for low-temperature adhesive processing in order to reduce energy costs. Therefore, as a result of intensive studies to improve the drawbacks of conventional adhesive resins, the present inventors developed an ethylene copolymer (A) containing a specific functional group and a (meth)acrylic acid ester polymer. The inventors have discovered that a composition consisting of (B) exhibits excellent adhesion to various polymeric materials and metals, glass, ceramics, wood substrates, etc. even under relatively low-temperature adhesion conditions, leading to the present invention. That is, the present invention provides an ethylene copolymer (A) and a (meth)acrylic acid ester polymer containing one or more functional groups selected from epoxy groups, dicarboxylic acid groups, and carboxylic acid anhydride groups. The present invention relates to an adhesive resin composition characterized by comprising (B) or an ethylene polymer (C) other than the above-mentioned ethylene copolymer (A). According to the present invention, a novel adhesive resin composition has a well-balanced high adhesion to both various polymeric materials and metals, glass, ceramics, wood base materials, etc. even under relatively low temperature adhesive processing conditions. provide something. The present invention will be explained in detail below. Ethylene copolymers (A) having one or more functional groups selected from epoxy groups, dicarboxylic acid groups, and carboxylic acid anhydride groups can be produced by high-pressure radical polymerization, solution polymerization, emulsion polymerization, etc. Ethylene and monomers copolymerizable with ethylene having the above functional groups, such as α,β-unsaturated glycidyl esters, α,β-unsaturated glycidyl ethers, α,β-unsaturated dicarboxylic acids and their It can be obtained by copolymerizing with an unsaturated monomer such as anhydride. Specific examples of unsaturated monomers include glycidyl methacrylate, glycidyl acrylate,
Examples include allyl glycidyl ether, 2-methylallyl glycidyl ether, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, and heimic anhydride. The amount of these unsaturated monomers is about 0.01 to about 20 mole percent, preferably about 0.1 to about 10 mole percent. Furthermore, Special Publication No. 37-18392, Special Publication No. 52-
As shown in Japanese Patent No. 30546, an ethylene homopolymer can be produced by grafting an unsaturated monomer having the aforementioned functional group onto a copolymer. In addition to the above-mentioned components, the ethylene copolymer (A) used in the present invention further contains unsaturated ester monomers as a third component, such as methyl acrylate, ethyl acrylate, methyl methacrylate, Copolymers obtained by copolymerizing unsaturated carboxylic acid esters such as butyl acrylate and unsaturated vinyl esters such as vinyl acetate and vinyl propionate can also be used. The melt index of the ethylene copolymer (A) generally needs to be within a range that is easy to process, and is usually 0.1~
300g/10 minutes, preferably 0.5-50g/10 minutes. The (meth)acrylic acid ester polymer (B) used in the present invention has the general formula (However, in the formula, R ₁ is hydrogen or a methyl group, and R ₂ is an alkyl group having 1 to 4 carbon atoms.)
Specifically, methyl acrylate polymer, methyl methacrylate polymer, ethyl acrylate polymer, butyl acrylate polymer, methyl methacrylate-butyl acrylate copolymer, and other unsaturated monomers (but (excluding unsaturated carboxylic acids such as acrylic acid and methacrylic acid), for example, those further copolymerized with styrene, acrylonitrile, etc. Among these, preferred are methyl methacrylate polymers and copolymers mainly composed of methyl methacrylate. In the present invention, other types of polymers may be added as long as the effects of the present invention are not impaired. When added, an ethylene polymer (C) other than the ethylene copolymer (A) is preferably used. Examples of the ethylene polymer (C) include at least one polymer selected from ethylene homopolymers, ethylene-α-olefin copolymers, and ethylene-unsaturated ester copolymers. The method for producing these polymers is not particularly limited, and known methods such as high-pressure radical polymerization, solvent polymerization, and solution polymerization can be applied. In addition, as the ethylene-α-olefin copolymer, ethylene-propylene copolymer,
Ethylene-1-butene copolymer, ethylene-1-
Examples include pentene copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-1-hexene copolymer, and ethylene-1-heptene copolymer. Examples of ethylene-unsaturated ester copolymers include ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-vinyl ester copolymer.
Examples include ethylene-unsaturated carboxylic acid ester copolymers such as methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer. Among them, ethylene-unsaturated vinyl ester copolymer and
Particularly preferred are ethylene-unsaturated carboxylic acid ester copolymers. When the ethylene polymer (C) is a copolymer, the ethylene content is 50 mol% or more, preferably 80 to 99 mol%. ethylene polymer
The melt index for (C) is 0.1 to 300g/10
min, preferably 0.5 to 50 g/10 min. The proportion of each component in the adhesive resin composition of the present invention is such that the total amount of ethylene copolymer (A) and ethylene polymer (C) is 50 to 99% by weight of the whole, and (meth)acrylic acid ester polymer (B) is 1 to 50% by weight, and the ratio of ethylene copolymer (A) in the total amount of ethylene copolymer (A) and ethylene polymer (C) is 10 to 100% by weight
It is. Preferably, the total amount of the ethylene copolymer (A) and the ethylene polymer (C) is 80 to 95% by weight of the whole,
(Meth)acrylic acid ester polymer (B) is 5 to 20
% by weight, and ethylene copolymer (A) in the total amount of ethylene copolymer (A) and ethylene polymer (C)
The proportion is 15-100% by weight. If the (meth)acrylic acid ester polymer (B) component is less than 1% by weight, no effect of improving adhesion is observed. Also, 50% by weight
If the value exceeds 100%, not only will there be no significant adhesion improvement effect, but the processability, flexibility, and mechanical strength of the ethylene copolymer (A) or even the ethylene polymer (C) will be reduced. benefits such as this will be lost. If the ethylene copolymer (A) component is less than 1% by weight, the content of functional groups in the composition will be too low and sufficient adhesiveness will not be obtained. When the ethylene polymer (C) is used, an economically advantageous composition can be obtained since it has a synergistic effect on adhesive performance and also functions as an extender. When the adhesive resin composition of the present invention is produced by mixing various polymers, the mixing method is not particularly specified, and any known technique such as an extruder, Banbury mixer, mixing roll, etc. is used to melt the polymers. There are methods such as kneading. The adhesive resin composition of the present invention may further contain coloring inhibitors such as stabilizers, lubricants, surfactants, inorganic fillers, foaming agents, and pigments. The base material to be bonded with the adhesive resin composition of the present invention may be various polymeric materials, such as polyethylene, olefinic copolymers such as ethylene-unsaturated ester copolymers, polypropylene, ethylene-propylene copolymers, styrene-based Polymers, vinyl chloride polymers, polyesters, polyamides, saponified products of ethylene-vinyl acetate copolymers, metals such as aluminum, iron, nickel, zinc, copper, and chromium, glass, ceramics, paper, and wood can be used. can. As a method for producing, for example, a metal-to-metal or metal-to-polyolefin laminate using the adhesive resin composition of the present invention, any known technique such as a known lamination method, a coating method, or a combination of both can be applied. For example, in the production of films or sheets, extrusion coating methods, dry lamination methods, coextrusion molding methods, etc. can be applied.
Further, a method of placing a film of the adhesive resin composition of the present invention on the surface of a metal, a polyolefin film or sheet, glass, etc. and heating it to adhere it;
Similarly, there is a method in which the adhesive resin composition of the present invention is coated with powder or solution on the surface of metal, polyolefin film or sheet, glass, etc., and then heated and bonded, and also between these substrates. There is a method in which the adhesive resin composition of the present invention is interposed and heat-press bonded. Bonding is generally carried out at 70-350°C. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. In the examples, the content of maleic anhydride was determined by dissolving the resin in xylene and then performing neutralization titration with alcoholic NaOH using phenolphthalein as an indicator. Further, the content of glycidyl methacrylate was determined from the characteristic absorption of the infrared spectrum. The adhesion to aluminum in the adhesion test is soft aluminum (150μ) / adhesive resin (60 to 80μ) / soft aluminum (150μ)
With this configuration, use a heat sealer at 120-180℃, 5
sec, 5Kg/ ^cm2 , 180° angle, 100
Evaluation was made using the tensile speed of mm/min. Adhesion test adhesion to polyethylene was performed using a press at 180℃ for 3 minutes, 10 minutes using a composition of soft aluminum (200μ)/adhesive resin (60~80μ)/polyethylene (2mm).
Glue under the conditions of Kg/cm ² and bend the aluminum.
Evaluation was performed at an angle of 180° and a pulling speed of 100 mm/min.
As the polyethylene, a pressed sheet of DFDJ0588 manufactured by Nippon Unicar Co., Ltd. was used. Examples 1 to 4 and Comparative Example 1 Ethylene copolymer (A-1) and methyl methacrylate polymer (manufactured by Sumitomo Chemical Co., Ltd.) containing melt index 7 g/10 min, 2.2 mol% glycidyl methacrylate, and 1.8 mol% vinyl acetate. Mix Sumipetx - BLO, Melt Index 13),
It was re-granulated using an extruder at a temperature of 180°C. Table 1 shows the results of an adhesion test of the obtained adhesive resin composition using a T-die film of 60 to 80 μm. Comparative Example 1 shows the results of an adhesion test in which methyl methacrylate polymer (SumiPex - BLO, manufactured by Sumitomo Chemical Co., Ltd.) was not mixed.

[Table] Example 5 and Comparative Example 2 Ethylene copolymer (A-
2) 85% by weight and 15% by weight of methyl methacrylate polymer (Sumipetx-BLO manufactured by Sumitomo Chemical Co., Ltd.) were mixed and re-granulated using an extruder at a temperature of 180°C. 60-80μT of the obtained adhesive resin composition
Table 2 shows the results of an adhesion test using Daifilm. Table 2 shows the results of an adhesion test in which no methyl methacrylate polymer was added as a comparative example.

[Table] Examples 6 to 8 and Comparative Examples 3 to 4 Ethylene copolymer (A-1) containing glycidyl methacrylate (2.2 mol%) and vinyl acetate (1.8 mol%) and methyl methacrylate polymer (Sumitomo Chemical Sumipetsux - BLO) 15% by weight
and ethylene-vinyl acetate (3.5 mol%) copolymer (melt index 6 g/10 minutes),
It was re-granulated using an extruder at a temperature of 180°C. Table 3 shows the results of an adhesion test of the obtained adhesive resin composition using a 60-80 μT die film. Table 3 shows the results of the adhesion test as a comparative example when neither the ethylene copolymer (A-1) nor the methyl methacrylate polymer was added.

[Table] Examples 9 to 11 Ethylene copolymer containing 2.2 mol% glycidyl methacrylate and 1.8 mol% vinyl acetate (A
-1) Mix 40% by weight of methyl methacrylate polymer (Sumipetx - BLO manufactured by Sumitomo Chemical Co., Ltd.) with 15% by weight of polyethylene or 45% by weight of polyethylene or ethylene copolymer as component (C), and use an extruder to
Re-granulation was carried out at a temperature of °C. Table 4 shows the results of an adhesion test of the obtained adhesive resin composition using a 60-80 μT die film.

【table】

[Table] Comparative Examples 5 to 10 In Examples 9 to 11, ethylene copolymer (A
Table 5 shows the results of the adhesion test in the case where 1) or the methyl methacrylate polymer was not added.

[Table] Examples 12-15 Ethylene copolymer containing 2.2 mol% glycidyl methacrylate and 1.8 mol% vinyl acetate (A
-1) Or, 85% by weight of a modified product (A-2) in which maleic anhydride (0.1% by weight) is grafted onto an ethylene-vinyl acetate (3.5 mol%) copolymer and methyl methacrylate as the main component (B). 15% by weight of the obtained copolymer was mixed and re-granulated using an extruder at a temperature of 180°C. 60 of the obtained adhesive resin composition
Table 6 shows the results of an adhesion test using ~80 μT-Die Film.

[Table] Examples 16 to 17 and Comparative Examples 11 to 12 As an ethylene copolymer containing a carboxylic anhydride group, a modified polymer having a melt index of 0.8 g/10 minutes and a maleic anhydride graft amount of 0.23% by weight was used. Chain low density polyethylene (density 0.935g/cm ³
…JIS K6760; A-3) and methyl methacrylate polymer (SumiPex BLO manufactured by Sumitomo Chemical Co., Ltd., melt index 13 g/10 minutes), or in addition, as an ethylene polymer, a linear chain polymer with a melt index of 3.0 g/10 minutes mixed with low density polyethylene (density 0.934g/cm ³ JIS K6760; C-4),
It was re-granulated using an extruder at a temperature of 200°C. Table 7 shows the results of an adhesion test using the obtained film in the same manner as in Example 1. Furthermore, Table 7 shows the results of the adhesion test as a comparative example when no methyl methacrylate polymer was added.

【table】

Claims (1)

[Scope of Claims] 1. An ethylene copolymer (A) containing one or more functional groups selected from epoxy groups, dicarboxylic acid groups, and carboxylic acid anhydride groups and a (meth)acrylic acid ester system. An adhesive resin composition comprising a polymer (B) or an ethylene polymer (C) other than the above-mentioned ethylene copolymer (A). 2. The adhesive resin composition according to claim 1, wherein the ethylene copolymer (A) contains 0.01 to 20 mol% of functional groups. 3 The ethylene polymer (C) is an ethylene homopolymer,
The adhesive resin composition according to claim 1, which is at least one polymer selected from ethylene-α olefin copolymer and ethylene-unsaturated ester copolymer. 4 The total amount of ethylene copolymer (A) and ethylene polymer (C) is 50 to 99% by weight, the (meth)acrylic acid ester polymer (B) is 1 to 50% by weight, and ethylene The ratio of ethylene copolymer (A) in the total amount of copolymer (A) and ethylene polymer (C) is 10 to 100% by weight
The adhesive resin composition according to claim 1. 5 The total amount of ethylene copolymer (A) and ethylene polymer (C) is 80 to 95% by weight, the (meth)acrylic acid ester polymer (B) is 5 to 20% by weight, and The ratio of the ethylene copolymer (A) in the total amount of the polymer (A) and the ethylene polymer (C) is 100% by weight,
An adhesive resin composition according to claim 1.