JPS61276A - Bondable resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has excellent adhesion and can be bonded at a relatively low temp., consisting of a copolymer of an olefin with an unsaturated carboxylic acid and a saponified copolymer of an olefin with a vinyl ester compd. CONSTITUTION:A non-crosslinked bondable resin compsn. consists of 20-80wt% copolymer (A) of an olefin with 1-25mol% of an unsaturated carboxylic acid and 80-20wt% saponificate obtd. by partially saponifying a copolymer (B) of an olefin with 1-50mol% of a vinyl ester compd.

Description

DETAILED DESCRIPTION OF THE INVENTION [I] Object of the Invention The present invention relates to an economically useful adhesive resin composition having excellent low temperature adhesion properties. More specifically, it is an adhesive resin composition comprising a saponified product of an olefin copolymer (A) of an olefin and an unsaturated carboxylic acid and an olefin copolymer (B) of an olefin and a vinyl ester compound; The copolymerization ratio of the unsaturated carboxylic acid in the olefin copolymer (A) is 1 to 25 mol%, and the copolymerization ratio of the vinyl ester compound in the olefin copolymer (B) is 1 to 50 mol%. The saponified product relates to a non-crosslinked adhesive resin composition obtained by partially saponifying the olefin copolymer (B), and has excellent adhesive properties and can be bonded at relatively low temperatures. It is an object of the present invention to provide an adhesive resin composition that is not only economically advantageous but also economically advantageous.

[II] Background of the Invention Although it is known that polyvinyl alcohol, saponified vinyl ester polymers, etc. have adhesive properties by themselves, their adhesive properties are not satisfactory.

A thermoplastic polymer composition obtained by mixing an epichlorohydrin polymer with a thermoplastic polymer having an alcoholic hydroxyl group (hydrosil group) in the molecule is known (Japanese Patent Publication No. 31172/1983). In order to fully exhibit adhesive properties, a high bonding temperature is required.

A resin composition comprising a saponified copolymer of ethylene and vinyl acetate in which 86% or more of the vinyl acetate groups have been saponified, and a thermoplastic olefin copolymer containing 10 to 3 mol% of unsaturated carboxylic acid. has also been proposed, but this composition is a packaging resin composition that is easy to cut with a knife or the like while having gas permeation resistance. Since the content of unsaturated carboxylic acid in the thermoplastic olefin copolymer used is within a small range, no mention is made of the adhesive resin composition.

In addition, unsaturated carboxylic acid or its acid anhydride copolymerized with polyvinyl alcohol having a saponification degree of 85% or less
Olefin containing 0% by weight or less! ! 7
1&#, ah,, 6e17,1□. , 6, □Sho 55-12
No. 7450), but this invention relates to a resin composition for producing a heat-retaining film, and its purpose is to improve the uniform dispersibility of polyvinyl alcohol and an olefin copolymer, which have moisturizing properties. Therefore, it cannot be used as an adhesive resin.

[II[] Structure of the Invention Based on the above, the present inventors have searched various ways to easily obtain a resin composition with excellent adhesive properties, and have developed an olefin-based copolymer of an olefin and an unsaturated carboxylic acid [ 20 to 80% by weight (hereinafter referred to as "copolymer (A)") and an olefin polymer of olefin and vinyl ester compound [hereinafter referred to as "copolymer (B)"]
An adhesive resin composition consisting of 80 to 20% by weight, #
The copolymerization ratio of unsaturated carboxylic acid in the copolymer (A) is 1
~25 mol%, the copolymerization ratio of the vinyl ester compound in the copolymer (B) is 1 to 50 mol%, and the saponified product is a non-crosslinked product obtained by partially saponifying the copolymer (B). The present inventors discovered that the adhesive resin composition of 2007 is an economically advantageous (simple) adhesive resin composition that is capable of adhesion at relatively low temperatures, has good adhesion, and is economically advantageous (simple). invention has been achieved.

[■] Detailed description of the invention (A) Copolymer (A) The copolymer (A) used in the present invention is obtained by copolymerizing an olefin and an unsaturated carboxylic acid. solid at 50~]70°C
It is desirable to have fluidity at a melting temperature of (preferably from 70°C to 50°C) and to have low crystallinity.

The olefin is preferably an olefin having 2 to 12 carbon atoms, and preferable olefins include ethylene, propylene, butene-1, and the like. Examples of unsaturated carboxylic acids include compounds such as acrylic acid, methacrylic acid, efacrylic acid, maleic acid, and fumaric acid.

The present invention also includes products obtained by saponifying the ester group of an olefin copolymer of an olefin and an unsaturated carboxylic acid ester such as ethyl acrylate or methyl methacrylate, and performing a neutralization reaction such as demetalization treatment. It can be used as a copolymer of

Among the above copolymers (A), those with appropriate fluidity at the melt processing temperature, moderately low crystallinity, and a high content of unsaturated carboxylic acid necessary for exhibiting high reactivity are industrially produced. Copolymers of olefins and unsaturated carboxylic acids obtained by high-pressure radical polymerization are preferred because they are easy to polymerize, and copolymers of ethylene and acrylic acid and copolymers of ethylene and methacrylic acid are particularly preferred. . In these copolymers, each unsaturated carboxylic acid unit is incorporated into the backbone of each polymer.

As mentioned above, it is desirable that the copolymer (A) of the present invention has appropriate fluidity at the melt processing temperature.
Measured under the conditions of 90°C and a load of 2.1 ftkg, hereinafter rM, 1. J ) is preferably 0.5 g/10 minutes or more (preferably 5 g/+o minutes -L). Also,
The copolymerization ratio of unsaturated carboxylic acid in this copolymer (A) is 1 to 25 mol%, preferably 2 to 25 mol%, and particularly preferably 5 to 20 mol%. If the copolymerization ratio of the unsaturated carboxylic acid in the copolymer (A) is less than 1 mol %, the adhesiveness of the composition of the present invention is insufficient.

On the other hand, even if it exceeds 25 mol %, the adhesiveness will not be further improved and it will not be economical. In the case of a copolymer of ethylene and acrylic acid, the copolymerization ratio of acrylic acid must be 3 to 45% by weight.

The copolymer (A) may be a copolymer consisting of ethylene and an unsaturated carboxylic acid, but it may also be a multicomponent copolymer of ethylene and an acrylic ester and/or a methacrylic ester. Polymers can also be used.Furthermore, olefinic polymers with a high copolymerization ratio of unsaturated carboxylic acids can be used with non-carboxylic acids such as olefinic polymers (low-crystalline polymers such as high-pressure polyethylene are preferable). The composition may be diluted with a polymer. However, it is preferable that the multi-component copolymer and the composition have a copolymerization ratio of M, 1. and the unsaturated carboxylic acid within the above range.

(B) Copolymer (B) Copolymer (B) is obtained by combining an olefin with a vinyl ester compound. The olefin is preferably an olefin having 2 to 12 carbon atoms, such as ethylene, propylene, butene-1, and the like. The vinyl ester compound is preferably a vinyl ester derived from a lower aliphatic carboxylic acid such as vinyl acetate or vinyl butyrate. Among the copolymers (B), copolymers of ethylene and vinyl acetate are preferably used because they are widely produced industrially.

The copolymerization ratio of the vinyl ester compound in the copolymer (B) is 1 to 50 mol%, preferably 2 to 30 mol%, and particularly preferably 8 to 18 mol%.

If the copolymerization ratio of the vinyl ester compound in the copolymer (B) is less than 1 mol %, the adhesiveness of the resulting composition will not be satisfactory. - On the other hand, even if it exceeds 50 mol%, the adhesiveness will not be further improved. Regarding this copolymerization ratio range for a copolymer of ethylene and xenyl acetate, the copolymerization ratio of vinyl acetate must be 3 to 75% by weight.

CC>Saponified product The saponified product of the copolymer (B) used in the present invention is solid at room temperature, and has a 5O-170 (preferably 70-
It is preferable to have fluidity at a melting temperature of 150°C.

The copolymer (B) is partially saponified by a widely known method to obtain a saponified product. Preferably, the degree of saponification is 30-80%. If the degree of saponification exceeds 80%, the adhesive strength at relatively low temperatures tends to decrease.

(D) Composition and production thereof In producing the composition of the present invention, the copolymer (A
) and the saponified copolymer (B) are in a weight ratio of 20/80 to 80/20, and 30/70 to 70.
/30 is preferred, and 40/60 to 60/40 is particularly preferred. If the composition ratio of the saponified substance in the copolymer (B) is high, only the adhesion to fibrous materials such as paper and cloth will be strong, but the adhesion to metals will be insufficient.

- On the other hand, if it is too small, the adhesion to the metal is sufficient.
Adhesion to paper or cloth becomes insufficient, which is not preferable.

In order to produce the composition of the present invention, the copolymer (A) and the saponified product of the copolymer (B) may be uniformly mixed.

As a mixing method, tri-blending may be performed using a mixer such as a Henschel mixer, which is commonly used in the field of olefin polymers, or a mixer such as a Banbury mixer, Niegoo, roll mill, or screw extruder may be used. There is a method of melting and kneading using At this time, a more uniform composition can be produced by dry blending and melt-kneading the resulting mixture in advance. The composition thus obtained may be used in the form of powder for adhesion described later, or may be used as pellets. It may also be used by forming into a film, sheet, etc. Note that the temperature required for kneading and molding is usually 50 to 1700C, preferably 70 to 150C.

In producing the ml composition of the present invention, stabilizers against oxygen, ultraviolet rays and heat, electrical property improvers, lubricants, metal deterioration inhibitors, flame retardants, and electrostatic agents commonly used in the field of olefin polymers are used. Additives such as inhibitors, processability improvers, and anti-tack agents may be added to the extent that they do not impair the properties of the composition of the present invention.

The adhesive resin composition of the present invention obtained in this manner is non-crosslinkable in woody terms, and its gel fraction (polymer sample is placed in a wire mesh and extracted with Soxhlet using boiling xylene for 6 hours; (calculated by dividing the remaining amount by the sample amount) is less than 10%.

(E) Adhesion When adhering the adhesive resin composition obtained by the present invention to other substances, the adhesion temperature is generally 70 to 200°C.
℃, preferably 80 to 170℃.

Adhesion can be achieved even at temperatures exceeding 200°C, but even if the temperature exceeds 200°C, the adhesive strength not only does not increase but may even decrease, so there is no point.

The adhesive resin composition of the present invention can also be used by dissolving it in a solvent that can dissolve both the copolymer (A) and the saponified product of the copolymer (B). Furthermore, these can also be dispersed in an aqueous system and used as an emulsion type adhesive.

[V] Effects and Applications of the Invention The adhesive resin composition obtained by the present invention has the characteristics that the adhesive temperature can be significantly lowered and the adhesive strength is greater than that of conventional hot-melt adhesives. There is. The range of applications for adhesion is wide: surfaces such as metals and alloys such as aluminum, iron and copper, glass, polyamides, polyesters, polysulfones, polyimides and modified olefinic polymers obtained by grafting monomers with polar groups. Examples include synthetic resins with polar groups.

Furthermore, since the composition itself has good moldability into films, sheets, etc. at low temperatures, it is possible to produce films, sheets, etc. that can be sealed at low temperatures. Furthermore, as one of the laminated base materials, it is possible to impart low-temperature sealing properties to other base materials.

The composition obtained by the present invention can be used in a wide variety of ways in order to exhibit the above-mentioned effects.

In particular, it is expected to be used as a material for parts of various electrical devices, electronic devices, automobiles, etc. because of its excellent moldability, electrical insulation properties, and adhesive properties.

[VI] Examples and Comparative Examples The present invention will be explained in more detail with reference to Examples below.

Example 1 A copolymer of ethylene and acrylic acid with an acrylic acid content of 25% by weight [N, 1.55 (Ig/I (1 min,
Melting point: 83° C., 50 parts by weight of pellets of F, hereinafter referred to as rEAA (1), and a copolymer of ethylene and vinyl acetate (M, I) containing 31.2% by weight of vinyl acetate.

200g/10 minutes) of pellets saponified to 70% (melting point 87°C)
Tri-blending was performed using a Henschel mixer for 1 minute. Using an extruder, the obtained mixture was heated to 120 to 1
Pelle 71 was produced by melt-kneading at 40°C.

The obtained beret 21 was further heated to T- in the same temperature range.
The Gui film was molded to produce a film with a thickness of 50-80 microns.

Using the obtained film, a hard aluminum foil with a thickness of 50 microns whose surface was cleaned with acetone was used as a sandwich of aluminum/film/aluminum.
Using a press at the temperature shown in the table for 30 seconds or 1
After preheating for minutes, at the same temperature, 1 at 20 kg/crn'.
Pressure was applied for 0 minutes. Afterwards, a tanza-shaped sample with a width of 2511II11 was prepared from this sandwich, which was left to cool, in a constant temperature room with a relative humidity of 54% and a temperature of 21℃.
Adhesive strength (T-type peel strength) was measured using a tensile tester based on IS K-f1854 at a tensile speed of 200 mm and 7 minutes. The results obtained are shown in Table 1. As is clear from this table, the composition of the present invention exhibits high adhesive strength at any bonding temperature, but the composition of the present invention has excellent low-temperature adhesion.

In addition, in both cases, the adhesive layer suffered cohesive failure.

Table 1 Example 2 EAA (1) 50 parts by weight and vinyl acetate content of 2
Example 1: 50 parts by weight of a 45% saponified product (melting point 79'0) of a copolymer of ethylene and vinyl acetate (M, 1.20 g/10 min) Triblending was carried out in the same manner as in Example 1. The obtained mixture was used to produce a pellet under the same conditions as in Example 1, and a film was produced. The adhesive strength of the obtained film was measured in the same manner as in Example 1. The results obtained are shown in Table 2.

Table 2 1) Example of cohesive failure in which the aluminum foil was cut and the rest was in the adhesive layer 3 Copolymer of ethylene and acrylic acid with an acrylic acid content of 25% by weight (M, 1.200 g/10 min, (melting point 88°C) 50 parts by weight and vinyl acetate content 2
Copolymer of ethylene and vinyl acetate (M
, 1.20g/10min) of 70% saponified product (melting point 8
50 parts of 7'C) were triblended in the same manner as in Example 1. A pellet was produced from the obtained mixture under the same conditions as in Example 1, and a film having a thickness of 50 microns was produced in the same manner as in Example 1 using this pellet. Using the obtained film as an adherend, a 6-nylon sheet, each having a thickness of 1 mm, was used. Manufactured by Electric Company, product name: Ultem (formerly TE11)
A moon sheet and a polysulfone sheet (manufactured by Union Carbide Co., trade name: Rubble (Rade)) were press-bonded at a temperature of 160°C under a pressure of 20 kg/crn'. After the pressure bonding, the cooled sample was 25m wide in a constant temperature room with a humidity of 54% and a temperature of 21'O.
+s and a short piece with a bonded part length of 12.5 mm was made. JIS K-
Based on the 8850 tensile shear strength measurement method, the adhesive strength was measured in the same thermostatic chamber at a tensile rate of 10II+m/min. The results obtained are shown in Table 3.

Table 3 1) A: Interfacial peeling between adherend and adhesive layer B: Destruction of adherend

Claims (1)

[Scope of Claims] 20 to 80% by weight of an olefinic copolymer (A) of an olefin and an unsaturated carboxylic acid and 80 to 20% by weight of a saponified product of an olefinic polymer (B) of an olefin and a vinyl ester compound %, and the copolymerization ratio of the unsaturated carboxylic acid in the olefin copolymer (A) is 1 to 2.
5 mol%, the copolymerization ratio of the vinyl ester compound of the olefin copolymer (B) is 1 to 50 mol%, and the saponified product is a partially saponified olefin copolymer (B). A non-crosslinked adhesive resin composition.