JPS6028662B2 - laminate - Google Patents

Description

[Detailed description of the invention] The present invention relates to a laminate.

Specifically, it is a copolymer whose main component is ethylene or a Q-olefin, particularly a Q-olefin having 3 to 8 carbon atoms, and which contains a carboxylic acid group in the side chain, or a polymer in which the carboxylic acid is ionically cross-linked with metal ions. Adding a small amount of a carbonate compound or oxide compound represented by the general formula or (in the formula, R, R2, R3, R4 each represents a hydrogen atom or an alkyl group) to
Plastics, metals, leather, paper, woven fabrics, glass, ceramics, etc. are firmly adhered to resin molded products made of modified copolymers obtained by cross-fertilizing the above copolymer resins in a molten state using adhesives. The present invention relates to a laminate made of

Copolymers of ethylene and unsaturated carboxylic acids, copolymers crosslinked with metal ions such as sodium, magnesium, and zinc, polyethylene and polypropylene with unsaturated carboxylic acids such as acrylic acid and maleic anhydride. Or olefin copolymers having carboxylic acid groups on side bells, such as modified olefin copolymers obtained by grafting unsaturated carboxylic acid anhydrides, etc., can be used on various substrates, such as metals and paper, especially in the melt pillow state. It is widely used as various adhesives and film base materials because it has excellent adhesive properties to glass, wood, woven fabrics, etc. In particular, metal ion-based copolymers of ethylene and unsaturated carboxylic acids are generally known as ionomer resins, and the resin can be easily molded as the crosslinked structure is cut and plasticized during heat molding. In contrast, the cooled molded product once again exhibits excellent properties as a crosslinked resin. In other words, ionomer resin is a very strong enemy, and in addition to having appropriate elasticity and flexibility, it also has excellent abrasion resistance, cold resistance, impact resistance,
It is a resin with oil resistance, and in recent years has been widely used not only as a base material for various films, but also in molded products such as shoe soles, golf ball covers, automobile bumper guards, hoses, and tubes. Olefin copolymers having carboxylic acid groups in their side chains, such as ionomer resins, exhibit excellent adhesion in the molten state as described above, but on the other hand, molded products of such copolymers can be used in various ways when cooled. It is not always easy to bond it to the base material, as is the case with ordinary olefin resins.

For example, it is impossible to bond a molded product made of ionomer resin to other plastics, rubber, metal, wood, leather, etc. with a common adhesive, or to form a coating film that tightly adheres to the surface of the molded product using paint. This is extremely difficult and usually requires special physical or chemical treatments on the resin surface. For this reason, conventionally, there have been disadvantages such as complicated processing steps and limited applications. The purpose of the present invention is to improve the adhesion performance of modified resin molded products obtained from olefin copolymers having carboxylic acid groups in the side chains such as ionomer resins, thereby providing a laminate with other materials using an adhesive. There is something to do. Molded articles made of this modified resin have the ability to be particularly effective when used with urethane adhesives, anchor coating agents, and paints.
The resin molded article made of the modified copolymer of the present invention preferably has the general formula or (in the formula, R, R2, R3, and R4 represent a hydrogen atom or an alkyl group) during melt molding of the copolymer resin. It can be obtained by adding and kneading a small amount of a carbonate compound or oxide compound.

The copolymer resin used in the present invention is generally an olefin copolymer having a carboxylic acid group in the side chain, and examples include copolymers containing ethylene and acrylic acid, methacrylic acid, etc. as essential components, or copolymers containing these as essential components. A copolymer that is ionically crosslinked by neutralizing the copolymer with monovalent metal ions such as sodium and potassium, or divalent metal ions such as calcium, magnesium, and zinc, and acrylic acid that can be copolymerized with other components than the above. ester, methacrylate ester,
Copolymers containing components such as vinyl acetate, polyethylene,
Polypropylene, polyisobutylene, copolymers such as ethylene-propylene copolymers, etc., which are made by grafting unsaturated carboxylic acids such as acrylic acid and maleic anhydride, unsaturated carboxylic acid anhydrides, etc. to non-olefin polymers or English polymers, etc. is included. The content of carboxylic acid constituting the above copolymer can be obtained over a wide range, but is usually 0.2 to 10
It is mole%. The carbonate compound or oxide compound added to the above resin is a compound represented by the general formula or (in the formula, R, R2, R3, and R4 represent a hydrogen atom or an alkyl group), and examples of carbonate compounds include ethylene carbon Examples of oxide compounds include ethylene oxide, propylene oxide, butylene oxide, Q
-Olefin oxides (5 to 30 carbon atoms) and the like are included.

In the case of an oxide compound, an oxide compound having a relatively high boiling point (high molecular weight) is preferably used in view of the ease of the addition method. The amount of these added is 0.2 to 1 part by weight, preferably 0.3 to 7 parts by weight, per 100 parts by weight of the resin. If it is less than 0.2 parts by weight, the improvement in the adhesiveness of the resin will be insufficient, and if it exceeds 1 part by weight, not only can no further improvement in adhesiveness be expected, but the performance of the resin itself, especially gelation and This is not preferable because it causes a decrease in mechanical strength.

The modification method is to knead the resin and a carbonate compound or oxide compound for an appropriate time using a kneader, a Banbury mixer, a mixing roll, etc. usually set at 150 to 300, or knead with an extruder and form pellets. However, 150 to 300q of the dry blend of both
It may be molded and modified using an extruder, injection molding machine, etc. at a temperature range of

A particularly effective adhesive for the resin molded article made of the modified copolymer of the present invention is a urethane adhesive, and by using this as an intermediary, the resin molded article and other materials, such as plastics and metals, can be bonded together. , leather, paper, woven fabric, glass, ceramics, etc. can be firmly bonded to form a laminate. In addition, by pre-treating the resin molded article with an isocyanate compound or urethane-based anchor coating agent, other adhesives such as synthetic rubber adhesives such as chloroprene-based, styrene-butadiene-based, and nitrile rubber-based adhesives, epoxy-based adhesives, etc. Adhesives such as vinyl acetate, polyester, and phenol will also be put to practical use. The resin molded product made of the modified copolymer used in the present invention has extremely good adhesion with polyurethane paint, and can be treated with other general coatings by treating the resin surface with an isocyanate-based or urethane-based anchor coating agent. Paints such as alkyd resin, acrylic resin, vinyl acetate resin,
Good adhesion to paints such as epoxy resins and polyester resins can be obtained, and peeling of paints can be prevented. In the present invention, adhesive performance of a molded article made of a modified copolymer obtained by adding a small amount of a carbonate compound or oxide compound to an olefin copolymer having a carboxylic acid group in the side chain and kneading the resin in a molten state Although the reason for the improvement is not necessarily clear, looking from the infrared absorption spectrum of the added mixture, carboxylic acid groups,
It is presumed that this is due to the reaction between the carboxylic acid anhydride or the carboxylic acid metal salt and the above-mentioned compound to introduce some hydroxyl groups into the polymer chain.

In particular, it has high reactivity with ionomer resins containing carboxylic acid metal salts of monovalent metals, such as sodium carponate, and is particularly effective in the present invention. In the present invention, the resin may be used alone before or after modification, but compositions in which other resins such as polyethylene, polypropylene, ethylene-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer are blended are used. It is also effective to use it as

In this case, the ratio of the resin is usually preferably 30% or more. Further, there is no problem with adding ordinary additives such as colorants, anti-aging agents, ultraviolet light inhibitors, etc. to the resin.

The adhesive performance of resin molded products made from the modified copolymer of the present invention is significantly improved, and as a result of the improved adhesion to paints, it can be widely applied as a laminate with other base materials in the form of a film or sheet. .

In particular, it is useful for improving the adhesion of ionomer resins to the upper skin when used as soles of various types of shoes, and can be used as a laminate by adhesion with metals to replace various rubber products, golf ball covers, bumper guards, etc. It can also have a remarkable effect. The present invention will be explained below with reference to Examples. Example 1 Ethylene component 82. prepared according to the method described in Japanese Patent Publication No. 49-31556. Round weight%, methacrylic brewing ingredient 1
Ionomer resin (M
II. 2) 1.2 parts by weight of ethylene carbonate per 100 parts by weight was kneaded for 5 minutes in a kneader set at 190q0, and then pressed at 180°C to form a sheet with a thickness of 2 sails.

After buffing the surfaces of two strip-shaped samples cut out from this sheet with a diameter of 2.5 arcs and a length of 10 arcs using sandpaper, we applied a polyurethane adhesive (Nogawa Chemical Co., Ltd. Diapond DA-1o09, polyol and curing agent). ratio 100
:3) was applied to each of them to a thickness of approximately 0.2, and after drying for 30 minutes, the two were adhered for 3 minutes at a pressure of 5k9/ground, and the adhesive strength was measured after 2 hours. For comparison, a sheet to which ethylene carbonate was not added was also adhered using the same formulation, and the adhesive strength was measured, and the results are shown in Table 1.

From the above results, it is clear that the effects of the present invention are extremely large. Table I Measurement conditions: T-type foil key <Description speed 200 items/min Example 2 The surface of the sheet sample of the ethylene carbonate-added ionomer resin used in Example 1 was buffed with sandpaper, and then washed with trichlene. The 1-thickness aluminum plate, the galvanized steel plate, and the 2-thickness natural leather sheet were each bonded using the polyurethane adhesive of Example 1 under exactly the same conditions, and the adhesion strength was measured.

Further, for comparison, similar measurements were performed on sheets to which ethylene carbonate was not added, and the results are shown in Table 2. These results demonstrate that the product of the present invention has high adhesive strength. Table 2 Measurement conditions Aluminum plate, galvanized steel plate 1800 peels 200 ribs/min vs. natural leather T peel 200 peels/min Example 3 Ethylene component 81. The weight of an ionomer resin (skin 2.3) consisting of 9.1% by weight of methyl methacrylate component and 9.0% by weight of methacrylate component, of which 48% of the methacrylic component was neutralized by magnesium ions (2.3% by weight) Q consisting of a mixture of 16 and 18 carbon atoms per part
-Olefin epoxide (manufactured by Adeka Argus Co., Ltd. 168
) was kneaded into pellets using an extruder with a cylinder temperature of 200°C.

This material was pressed at 80° C. to form a sheet with a thickness of 2, and a sample with a thickness of 2.5 and a length of 10 skin was prepared. The surface of this product was buffed with sand vapor, and a 20% solution of triphenylmethane triisocyanate in methylene dichloride (Bayer Co., Ltd. Dismodor R) was applied. After leaving it for 24 hours, a chloroprene-based adhesive (Nogawa Chemical Co., Ltd. Diabond) was applied. No. 888) was bonded to natural leather having a thickness of 1.5 ribs under the same conditions as in Example 1. The adhesive peel strength was 12.8 kg/2.5 skin, and the peeling was based on the destruction of the natural leather. For comparison, a similar adhesion test was conducted on an ionomer resin sheet to which no Q-olefin epoxide was added, and the adhesion strength was 5.2k9/cm, with no peeling between the ionomer resin layer and the isocyanate layer. occured. Example 4 The surface of the ethylene carbonate-added ionomer resin sheet of Example 1 was buffed with sand vapor, and 10 parts by weight of a polyester polyol for polyurethane paint (Nippon Polyurethane Kogyo Desmophen 800) was added.
A urethane paint made by mixing 118 parts by weight of a curing agent for polyurethane (Japan Polyurethane Kogyo Coronate L), 10 parts by weight of ethyl acetate, and 40 parts by weight of titanium dioxide was mixed with 0.1 parts by weight.
It was applied at a thickness of ~0.2 sail and dried for 2 hours at 50 qo.

Next, using a knife, score the pieces vertically and horizontally at intervals of one rib to create a grid of 10 pieces. When cellophane tape was applied on top of this and the adhesion between the resin and urethane paint was determined by telling the number of grid points that remained when the cellophane tape was peeled off, all 100 pieces remained without peeling, indicating good adhesion. showed his sexuality. For comparison, a similar test was conducted on an ionomer resin sheet to which no ethylene carbonate was added, and it was found that the number of remaining grid lines was 17, indicating that the sheets did not adhere sufficiently. Example 5 The amount of ethylene carbonate added was 0.1, 0.5, 2,
An adhesion test was conducted in the same manner as in Example 1 except that the weight parts were changed to 5 and 1 parts by weight, and the results shown in Table 3 were obtained.

Table 3 As is clear from the table, ethylene carbonate added in an amount of 0.1 parts by weight has little effect, and adding 10 parts by weight or more does not contribute to the improvement of adhesion.

Example 6 An ethylene-acrylic acid copolymer (M15.
6) Propylene carbonate to 10 parts by weight 2.
Dry blend 5 parts by weight and cylinder temperature 240oo
, under the conditions of nozzle temperature 220 oo, mold temperature 25 pm,
A flat plate sample with a thickness of 3 willows was molded by injection molding.

Claims (1)

[Scope of Claims] 1 A copolymer whose main component is ethylene or α-olefin having 3 to 8 carbon atoms and whose side chain contains a carboxylic acid group, or whose carboxylic acid group is ionically cross-linked with metal ions. 100 parts by weight of the copolymer has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ or ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2, R_3 and R_4 each represent a hydrogen atom or an alkyl group. 0.2 to 10 parts by weight of a carbonate compound or oxide compound represented by A laminate made by bonding together materials selected from the group consisting of , metal, leather, paper, woven fabric, glass, and ceramics.