JP2000159938A - Heat bonding thermoplastic elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject elastomer industrially producible at a low cost, excellent in heat adhesion to resins etc., moldability and heat resistance, and good in surface gloss of a molded product by including a specific ethylenic copolymer in a specified thermoplastic elastomer in a specific proportion. SOLUTION: This elastomer is obtained by including (B) 10-80 pts.wt. of an ethylenic copolymer containing 5-80 wt.% of a monomer having epoxy group as a copolymerization component in (A) 100 pts.wt. of a thermoplastic elastomer containing (i) a crystalline olefin polymer having >=110 deg.C melting point and <=8,000 kg/cm2 modulus of elasticity and (ii) an ethylenic copolymer having <=90 degree hardness (JIS-A) without containing epoxy group in (10/90) to (80/20) weight compounding ratio of the components (i) to (ii). The component (ii) is preferably an ethylene/α-olefin copolymer, etc. The elastomer is useful as a sealing material, etc., used by bonding the sealing material, etc., to a glass etc., of an automobile.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention provides a flexible and glossy molded product which is excellent in heat adhesion to various kinds of resins, inorganic materials such as glass, metals and the like, and is excellent in moldability and heat resistance. The present invention relates to a thermo-adhesive thermoplastic elastomer which can be industrially manufactured at low cost.

[0002]

2. Description of the Related Art A thermoplastic elastomer having an intermediate property between a rubber and an olefin resin is obtained by kneading an olefin copolymer rubber such as EPDM with an olefin resin at a high shear rate and crosslinking with an organic peroxide. This olefinic thermoplastic elastomer is widely used for molding automotive parts and other products. However, since the olefin-based thermoplastic elastomer does not have a polar group, it cannot be thermally bonded to other materials, and its use has been limited.
It is known that an unsaturated epoxy monomer is added to enable the thermal bonding of the olefin-based thermoplastic elastomer (see Japanese Patent Application Laid-Open No. 64-85206).

However, the olefin-based thermoplastic elastomer to which the above-mentioned unsaturated epoxy monomer is added is a cross-linked thermoplastic elastomer using an olefin copolymer rubber such as EPDM as a soft segment, so that the moldability is low. In addition, the surface of the molded article had a pear-like shape and was poor in luster. For example, when used for a weatherstrip of a window glass of an automobile, required characteristics could not be satisfied. In addition, when used for handrailing or surface coating of a handle, there is a problem that hand grits and other dirt tend to adhere, and once adhered, it is difficult to remove.

[0004]

The present invention can be industrially manufactured at low cost, has excellent heat adhesion to resins, glass, metals, and the like, has excellent moldability and heat resistance, and can be used with other resins. Multi-color molding and composite extrusion are easy, and the molded product is flexible, glossy, hard to adhere dirt and easy to fall off, for example, glass, iron plate,
An object of the present invention is to provide a thermo-adhesive thermoplastic elastomer suitable as a sealing material, a gasket material, a packing material or the like used by bonding to a tin plate or the like, or a coating material used by bonding to a metal pipe for a handrail or a handle.

[0005]

SUMMARY OF THE INVENTION A thermoadhesive thermoplastic elastomer according to the present invention has a crystalline olefin polymer having a melting point of 110 ° C. or more and an elastic modulus of 8000 kg / cm ² or less, and a hardness (JIS-A) of 90. In a thermoplastic elastomer consisting of an ethylene-based copolymer A containing no epoxy group at a degree or less, a monomer having an epoxy group as a copolymer component,
The ethylene copolymer B having a content of 5 to 80% by weight is added. The weight ratio of the crystalline olefin polymer and the ethylene copolymer A is 10
/ 90-80 / 20, and the above-mentioned ethylene copolymer B
Is set to 10 to 80 parts by weight based on 100 parts by weight of the thermoplastic elastomer.

That is, the thermoadhesive thermoplastic elastomer of the present invention is obtained by adding an ethylene copolymer B to a thermoplastic elastomer having a crystalline olefin polymer as a hard segment and an ethylene copolymer A as a soft segment. Since it does not contain a vulcanized rubber component, it has excellent moldability, is easy to perform multicolor molding and composite extrusion with other resins, and has good surface gloss of a molded product. And
Since the ethylene copolymer A of the soft segment has good compatibility with the ethylene copolymer B having an epoxy group, the production is easy and the thermal adhesiveness of the elastomer is improved. Is easily bonded to resin, glass and metal.

In the present invention, the crystalline olefin polymer constituting the hard segment has a melting point of 110 ° C. or more and an elastic modulus of 8000 kg / cm ² or less;
Polypropylene copolymer, linear low-density polyethylene,
Polybutene-1 polymers and copolymers thereof are exemplified,
These representatives are readily available commercially. The above crystalline olefin polymers can be used alone or in combination of two or more. However, those having a melting point of less than 110 ° C. have reduced heat resistance, and those having an elastic modulus of more than 8000 kg / cm ² have reduced flexibility.

On the other hand, the ethylene copolymer A constituting the soft segment has a hardness (JIS-A) of not more than 90 degrees and does not contain an epoxy group, and the ethylene / α-olefin copolymer (linear Ultra-low density polyethylene), ethylene / vinyl acetate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate copolymer, etc., all of which are commercially available and have copolymer components By increasing, the hardness is set to 90 degrees or less. And these ethylene copolymers A
Can be used alone or in combination of two or more. However, when the hardness exceeds 90 degrees, the flexibility of the thermoadhesive thermoplastic elastomer is reduced, and the hardness may exceed 95 degrees, which makes it difficult to achieve the object of the present invention. In order to distinguish between the linear ultra-low density polyethylene belonging to the crystalline olefin polymer and the linear ultra-low density polyethylene belonging to the ethylene copolymer A, the former is referred to as a linear ultra-low density polyethylene in the following. Described as density polyethylene H or LLDPE-H, the latter as linear ultra-low density polyethylene S or LLDPE-S.

The compounding ratio (weight ratio) of the crystalline olefin polymer (hard segment) and the ethylene copolymer A (soft segment) of the present invention is 10/90 to 80 /.
It is set to 20. If the above mixing ratio is less than 10/90, the mechanical strength of the obtained thermoadhesive thermoplastic elastomer is insufficient, and if it is more than 80/20, the flexibility of the thermoadhesive thermoplastic elastomer decreases. 95 hardness
Results, and the purpose of the present invention is not achieved in any case.

In the present invention, the ethylene copolymer B is added to the thermoplastic elastomer comprising the hard segment and the soft segment. The ethylene-based copolymer B contains a monomer having an epoxy group as a copolymer component, and includes a copolymer of ethylene and an unsaturated epoxy monomer, and a copolymer of ethylene / vinyl acetate and an unsaturated epoxy monomer. Copolymers of ethylene / methyl methacrylate and unsaturated epoxy monomers, and the like. Examples of the unsaturated epoxy monomers include glycidyl acrylate and glycidyl methacrylate. The ones are commercially available. However, the content of these monomers is limited to 5 to 80% by weight, and if it is less than 5% by weight, the adhesive strength of the composition is insufficient, and if it exceeds 80% by weight, gelation easily occurs.

The amount of the ethylene-based copolymer B is 1 to 100 parts by weight of the thermoplastic elastomer comprising the crystalline olefin polymer and the ethylene-based copolymer A.
It is set to 0 to 80 parts by weight. If the amount is less than 10 parts by weight, the adhesive strength will be insufficient, and if it exceeds 80 parts by weight, gelation will easily occur.

In the present invention, a paraffinic, naphthenic or aromatic process oil is added as a softening agent, if necessary, in addition to the ethylene copolymer B, and the hardness of the heat-adhesive thermoplastic elastomer (JIS) -A) from 50 to 9
It can be set to 5 degrees. The addition amount is preferably 80 parts by weight or less with respect to 100 parts by weight of the thermoplastic elastomer comprising the crystalline olefin polymer and the ethylene-based copolymer A, and if it exceeds 80 parts by weight, the desired thermal adhesiveness is obtained. Can not be obtained. If the hardness is less than 50 degrees,
When the mechanical strength of the obtained heat-adhesive thermoplastic elastomer is insufficient, when it exceeds 95 degrees, the flexibility is insufficient.
The heat-adhesive thermoplastic elastomers of Embodiments 1 to 7 described below have a hardness of 7 without adding process oil.
Although a degree of 5 to 85 degrees is obtained and the thermal adhesion is excellent, the addition of the above process oil makes it possible to adjust the hardness in a wide range.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiment 1 A polypropylene copolymer is prepared as a crystalline olefin polymer having a melting point of 110 ° C. or more and an elastic modulus of 8000 kg / cm ² or less. A linear low-density polyethylene S is prepared as an ethylene copolymer A having a hardness (JIS-A) of 90 degrees or less and containing no epoxy group. Further, a monomer having an epoxy group is used as a copolymer component, and its content is 5 to 5.
80% by weight of ethylene copolymer B is ethylene /
Vinyl acetate / glycidyl methacrylate copolymer (EV
AGMA) is prepared.

The mixing ratio of the above polypropylene copolymer and linear low density polyethylene S is 10/90 to 80.
/ 20 and weighed into a kneader, and weighed 10 to 80 parts by weight of ethylene / vinyl acetate / glycidyl methacrylate copolymer per 100 parts by weight of the total, and charged the mixture into the kneader. Is kneaded at a temperature of 160 to 200 ° C. for 5 to 15 minutes, and the obtained thermoadhesive thermoplastic elastomer is extruded, cut and pelletized. Since this elastomer uses a polypropylene copolymer having a high melting point, it has excellent heat resistance.

The obtained thermoadhesive thermoplastic elastomer in the form of pellets is melted in a required amount at a temperature of 170 to 210 ° C., and formed into a desired shape by injection molding or extrusion or any other method. And other resin as needed,
It is laminated on a substrate made of glass, metal or the like by thermal bonding. For example, 150 to 250
Preheat to about ° C, and coat a molten resin on it. Also,
The sheet-shaped molded product is pressed by a hot roll. In the injection molding, a gap is formed on the injection port side of the cavity by mounting the pre-molded substrate in the cavity of the flat plate mold, and by injecting the thermoadhesive thermoplastic elastomer into the gap, A laminate comprising the above-mentioned substrate and a cushion layer of a thermo-adhesive thermoplastic elastomer firmly bonded to its surface is obtained.

Embodiment 2 The melting point is 1 instead of the polypropylene copolymer of Embodiment 1.
A linear low-density polyethylene H having an elastic modulus of 10 ° C. or more and an elastic modulus of 8000 kg / cm ² or less is used in the same manner as in Embodiment 1, except that the linear low-density polyethylene H A thermoadhesive thermoplastic elastomer comprising polyethylene S and an ethylene / vinyl acetate / glycidyl methacrylate copolymer is produced.

Embodiment 3 In place of the polypropylene copolymer of Embodiment 1, the melting point is 1
Butene having an elastic modulus of not less than 10 ° C. and not more than 8000 kg / cm ^2.
One polymer is used for the hard segment, and the other conditions are the same as those in Embodiment 1, except that the thermal adhesive heat of butene-1 polymer, linear low-density polyethylene S and ethylene / vinyl acetate / glycidyl methacrylate copolymer is used. Produce a plastic elastomer.

Embodiment 4 In Embodiment 2, in place of linear low-density polyethylene S, an ethylene / vinyl acetate copolymer having a hardness (JIS-A) of 90 ° or less is used, and otherwise the same as Embodiment 2 To produce a thermoadhesive thermoplastic elastomer comprising linear low density polyethylene H, ethylene / vinyl acetate copolymer and ethylene / vinyl acetate / glycidyl methacrylate copolymer.

Embodiment 5 In Embodiment 2, a linear low-density polyethylene S having a hardness (JIS-A) of 90 ° or less and an ethylene / methyl methacrylate copolymer (EMMA) are used in combination as the ethylene copolymer A, Otherwise, in the same manner as in Embodiment 2, a heat-bonding heat composed of linear low-density polyethylene H, linear low-density polyethylene S, ethylene / methyl methacrylate copolymer and ethylene / vinyl acetate / glycidyl methacrylate copolymer Produce a plastic elastomer. In this case, the ethylene / vinyl acetate / glycidyl methacrylate copolymer forms a soft segment and has a polar group (acryl), so that compatibility with a metal, a resin, or the like is improved.

Embodiment 6 In Embodiment 1, the polypropylene copolymer of Embodiment 1 and the linear low-density polyethylene H of Embodiment 2 are used in combination as the crystalline olefin polymer. To produce a thermoadhesive thermoplastic elastomer comprising a polypropylene copolymer, a linear low-density polyethylene H, a linear low-density polyethylene S and an ethylene / vinyl acetate / glycidyl methacrylate copolymer. In this case, the use of the polypropylene copolymer improves the heat resistance and increases the hardness, but the combined use of the linear low-density polyethylene H suppresses the increase in the hardness, and achieves both heat resistance and flexibility. Will be possible.

Embodiment 7 In the sixth embodiment, a linear low-density polyethylene S and an ethylene / methyl methacrylate copolymer are used in combination as the ethylene copolymer A of the soft segment. A thermoadhesive thermoplastic elastomer comprising a copolymer, linear low density polyethylene H, linear low density polyethylene S, ethylene / methyl methacrylate copolymer and ethylene / vinyl acetate / glycidyl methacrylate copolymer is produced.

[0022]

EXAMPLE The melting point is 110 ° C. or more and the elastic modulus is 8000 kg /.
The following were prepared as crystalline olefin polymers of cm ² or less. (1) PP copolymer a: "Nobrene S1" manufactured by Sumitomo Chemical Co., Ltd.
31 ", melting point 134 ° C, elastic modulus 6900 kg / cm ² (2) PP copolymer b:" Soft polyolefin KS37G-1 "manufactured by Sumitomo Chemical Co., Ltd., melting point 138 ° C, elastic modulus 3400 kg
/ Cm ² (3) LLDPE-Ha: “MORETECH 01” manufactured by Idemitsu Chemical Co., Ltd.
28 ", melting point 110 ° C. or higher, elastic modulus 3000 kg / cm ² (4) LLDPE-Hb: Sumikasen Hi manufactured by Sumitomo Chemical Co., Ltd.
−α ”, melting point 118 ° C., elastic modulus 1400 kg / cm ² (5) LLDPE-Hc:“ Excellen VL ”manufactured by Sumitomo Chemical Co., Ltd.
−100 ”, melting point 117 ° C., modulus of elasticity 900 kg / cm ² (6) Polybutene-1:“ P-4000 ”manufactured by Mitsui Chemicals, Inc.
Melting point 123 ° C, elastic modulus 4300 kg / cm ²

The following ethylene copolymer A having a hardness (JIS-A) of 90 degrees or less and containing no epoxy group was prepared. (1) LLDPE-Sa: “Engage, EG8180” manufactured by DuPont Dow Chemical Company, hardness (JIS-A) 6
6 degrees (2) LLDPE-Sb: "Esprene SP" manufactured by Sumitomo Chemical Co., Ltd.
ONO394 ", hardness (JIS-A) 85 degrees (3) EVA:" Evaflex EV-250 "manufactured by Dupont Mitsui Polychemicals, hardness (JIS-A) 76 degrees (4) EMMA:" Sumitomo Chemical " ACLIFT CM-40
13 ", hardness (JIS-A) 63 degrees The following hydrogenated NBR was prepared for comparison. (5) Hydrogenated NBR: “Dynalon 132” manufactured by Nippon Synthetic Rubber Co., Ltd.
0P ", hardness (JIS-A) 40 degrees

The following was prepared as an ethylene copolymer B having a monomer having an epoxy group as a copolymer component and having a content of 10 to 80% by weight. 1. 1. EVAGMA-a: “Bond First 2B” manufactured by Sumitomo Chemical Co., Ltd., epoxy content: 12 wt% EVAGMA-b: "Elvaloy PT" manufactured by Dupont Mitsui Polychemicals Inc., epoxy content: 5 wt% or more For comparison, the following epoxy-modified styrene-based elastomer and maleic anhydride-modified olefin were prepared. 3. Epoxy-modified styrene elastomer: "Epoblend A1020" manufactured by Daicel Chemical Industries, Ltd., epoxy content 2
0 wt% 4. Maleic anhydride-modified olefin: "Bondane AX8390" manufactured by Sumitomo Chemical Co., Ltd., epoxy content 0 wt%

The above various resin materials are blended at various ratios, and a kneading machine ("Laboplant Mill R-50" manufactured by Toyo Seiki Co., Ltd.) is used.
0), kneading at 180 ° C. for 30 minutes, forming a sheet with a roll, adhesive strength, hardness Hs (JIS-A), tensile strength Tb, tensile elongation Eb and 100% modulus M
₁₀₀ measurement samples were made and tested. Adhesion strength is 18
Bonded to a glass plate and a tin plate (zinc-plated iron plate) with a hot press at 0 ° C, and tested by a 180 ° peeling method (sample width: 10 mm). Δ, 0.5 or more and less than 1.0 kg were indicated by ○, and 1.0 kg or more were indicated by ◎. The bonding strength between glass and glass was defined as bonding strength a, and the bonding strength between tin and glass was defined as bonding strength b. Also, Tb, Eb
And M ₁₀₀ were tested according to JIS K-6251. The test results are shown in Tables 1 and 2 below together with the mixing ratio (% by weight). However, "Example" is changed to "Real"
"Comparative Example" was abbreviated as "ratio".

Table 1

Table 2

As shown in Tables 1 and 2 above, Examples 1 to
Sample No. 9 was excellent in adhesion to glass and tinplate, and had good surface gloss. Comparative Example 1 In contrast, as a third component other than the hard and soft segments, due to the use of epoxy-modified styrene-based elastomer instead of the ethylene copolymer B, M ₁₀₀ is at elevated, pair glass And the adhesion strength to tinplate decreased. In Comparative Example 2, hydrogenated NBR was used in place of ethylene copolymer A, and ethylene copolymer B was used.
In place of the above, a maleic anhydride-modified olefin having no epoxy group was used, so that the adhesive strength between glass and tinplate was low. In Comparative Example 3, since the maleic anhydride-modified olefin was used in the same manner as in Comparative Example 2 instead of the ethylene-based copolymer B, the adhesive strength between glass and tinplate was low. In Comparative Example 4, the ethylene copolymer B (ethylene / vinyl acetate / glycidyl methacrylate was used, but the amount of the copolymer was small and 4% by weight of the total amount of the composition. Has a low adhesive strength.

[0029]

As described above, the thermoadhesive thermoplastic elastomer of the present invention uses a crystalline olefin polymer as a hard segment and a low-hardness ethylene-based copolymer A containing no epoxy group as a soft segment. Since it is obtained by adding an ethylene-based copolymer B containing an epoxy group, a commercially available material can be easily produced simply by kneading with a single-screw extruder, which is inexpensive. It has the properties of an elastomer, has good moldability and surface gloss, and has excellent thermal adhesion to glass, iron and the like. Therefore, it is suitable as a sealing material, a gasket material, a packing material, and the like used by bonding to glass, an iron plate, a tin plate and the like in the field of automobiles and building materials, and a coating material used by bonding to a metal pipe for handrails and handles. Particularly, in the invention described in claim 2, since the hardness of the ethylene-based copolymer A is easily adjusted, the production is further facilitated.

Continuing from the front page (72) Inventor Atsushi Jinno 255 Kannonji-cho, Tsu-shi, Mie Prefecture, Kurehaera Stomer Co., Ltd. (72) Inventor Noriichi Kodera 255 Kannonji-cho, Tsu-shi, Mie Kurehaera Stomer Co., Ltd. F Term (reference) 4J002 BB00W BB04X BB05X BB06X BB07X BB08X BB10Y CD19Y GF00

Claims (2)

[Claims] 1. A melting point of 110 ° C. or more and an elastic modulus of 8000.
kg / cm ² or less crystalline olefin polymer and hardness (J
IS-A) is a thermoplastic elastomer comprising an ethylene-based copolymer A having an epoxy group-free content of 90 ° or less, a monomer having an epoxy group as a copolymer component, and a content of 5 to 80% by weight. The ethylene-based copolymer B is added, the weight ratio of the crystalline olefin polymer and the ethylene-based copolymer A is 10/90 to 80/20, and the blending amount of the ethylene-based copolymer B is A heat-adhesive thermoplastic elastomer, which is used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the thermoplastic elastomer. 2. An ethylene-based copolymer A comprising ethylene / α-
Olefin copolymer, ethylene / vinyl acetate copolymer,
2. The heat-adhesive thermoplastic elastomer according to claim 1, comprising one or more copolymers selected from ethylene / methyl methacrylate copolymer and ethylene / ethyl acrylate copolymer.