JPH05301973A - Production of bonded composite body of abs resin and rubber - Google Patents

Abstract

PURPOSE:To obtain the subject composite body excellent in mechanical characteristics, electrical characteristics, adhesion, flexibility and elasticity and useful as an interior material, etc., by laminating a molding material consisting of ABS resin to a specific uncured rubber sheet and then integrally bonding the molding material to the rubber sheet by heating. CONSTITUTION:A molding material consisting of ABS resin is laminated to an uncured rubber sheet consisting of a rubber composition containing a raw material rubber component having 37-39mN/m critical surface tension gammac and then the molding material is integrally bonded to the rubber sheet by heating to provide the objective composite body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite body in which rubber is adhered and integrated with ABS resin.

[0002]

2. Description of the Related Art ABS resin is an automobile interior material, refrigerator, cooler, vacuum cleaner, because of its excellent mechanical and electrical properties.
It is used in many applications such as exterior materials for cabinets of various electric products such as televisions. Although ABS resin is more excellent in impact resistance than other resins, it has a defect that it is cracked or cracked by impact because it is hard and poor in elasticity like other plastics.

Such a defect can be solved if it is flexible and rich in elasticity and can be laminated and integrated with various general-purpose rubbers, but the ABS resin and general-purpose rubber have poor adhesiveness,
It was not possible to produce a composite that was firmly bonded and integrated. As a result of intensive studies on the adhesiveness between ABS resin and general-purpose rubber, the present inventor has found that among various general-purpose rubbers, the critical surface tension γc is 37 to 39 millinewtons / meter (hereinafter abbreviated as mN / m). ABS is a rubber composition containing a raw rubber component similar to that of ABS resin
It was found that it selectively adheres to a resin, and based on this finding, it has excellent adhesion to many general-purpose rubbers other than the above by utilizing the third intermediate medium, The present invention has been reached.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention
It is to provide a method for producing a composite body in which an S resin and a general-purpose rubber are bonded and integrated.

[0005]

The first invention of the present invention which achieves the above object is a rubber containing a molding material made of ABS resin and a raw rubber component having a critical surface tension γc of 37 to 39 mN / m. It is characterized in that an unvulcanized rubber sheet made of the composition is laminated and then heated and bonded and integrated.

[0006] Here, the critical surface tension γc means "Chemical Handbook," edited by Maruzen Co., Ltd., on August 20, 1978, II.
(Third printing), page 618, where the contact angle of a homologous series of liquid hydrocarbons and other organic liquid compounds on a solid surface is θ and the surface tension of the liquid is γ, co
The relationship between s θ and γ is almost a straight line regardless of the type of homologue. At this time, it is defined as γc corresponding to θ = 0, that is, cos θ = 1. However, the critical surface tension γc of the raw material rubber component defined in the present invention means a value similarly measured using a rubber sample obtained by flattening the rubber whose γc is to be measured by hot pressing, instead of the above solid. ..

Thus, among various rubbers, γc is 37
As a raw material rubber component having a viscosity of up to 39 mN / m, acrylonitrile-butadiene copolymer rubber (N
BR) in addition to fluororubber and epichlorohydrin rubber. Since NBR contains acrylonitrile as a copolymerization component similarly to ABS resin, it is considered that the critical surface tensions γc of both are similar to each other.
It enables adhesion of the BS resin and the unvulcanized rubber sheet by heating. The second invention is that the molding material A made of ABS resin and the critical surface tension γc are 37 to 39 mN / m.
The non-vulcanized rubber sheet made of a rubber composition containing a raw rubber component having a critical surface tension γc of 25 to 33 mN / m (hereinafter referred to as a general-purpose rubber sheet). ) B is between 37 and 3 between B and
An unvulcanized rubber sheet (hereinafter referred to as a high γc rubber sheet) a composed of a rubber composition containing 9 mN / m of raw rubber component, hydrogenated acrylonitrile-butadiene containing methacrylic acid, zinc oxide and peroxide Unvulcanized rubber sheet (hereinafter referred to as modified NBR sheet) b made of a copolymer rubber composition, unvulcanized rubber sheet made of an isobutyl-isoprene copolymer rubber (IIR) composition (hereinafter II
R sheet) c and an ultrahigh molecular weight polyethylene sheet (hereinafter referred to as an ultrahigh molecular weight PE sheet) d produced by a carving method, and A / a / b / c / d / B
It is characterized in that it is laminated in this order and then heated and bonded and integrated.

As described above, the high γc rubber sheet a containing a raw rubber component such as NBR is a hydrogenated acrylonitrile-butadiene copolymer rubber (the rubber used in the modified NBR sheet is hereinafter referred to as modified NBR). ) Also has excellent adhesiveness. Moreover, since the modified NBR has good adhesion to IIR,
By using the ultra-high molecular weight PE sheet d having excellent adhesiveness to many general-purpose rubbers such as IIR mentioned above, it is possible to adhere to the general-purpose rubber sheet B. Therefore, these NBR, modified NBR, IIR,
By combining the ultra-high molecular weight PE sheets and determining the stacking order, a composite having both characteristics of the ABS resin molding material A and the general-purpose rubber sheet B can be manufactured.

As the ABS resin used in the present invention, there is a known ABS resin composed of acrylonitrile, butadiene and styrene monomers. As this ABS resin, those having various properties can be obtained depending on the production method, but the internal dispersion structure uses a styrene-acrylonitrile copolymer as a matrix (sea), and polybutadiene rubber in which styrene and acrylonitrile are graft-polymerized in this sea. There is a resin having a sea-island structure in which particles are uniformly dispersed in an island shape and having good mechanical properties. Further, this ABS resin has a heat distortion temperature (according to ASTM D648 test) of 85 ° C to 9 ° C.
The temperature range is 0 ° C, and the monomer weight ratio of styrene / acrylonitrile constituting the ABS resin is 85/15.
To 65/35, preferably 80/20 to 70 /
A range of 30 is good.

In the present invention, NB is selected as a raw rubber component having a γc of 37 to 39 mN / m selected as a general-purpose rubber.
Although there is R, it is not limited to NBR as long as γc is within the above range, and includes fluorine rubber, epichlorohydrin rubber and the like. Such a rubber component is preferably blended in an amount of 70% by weight or more, and a vulcanizing agent such as sulfur, a reinforcing agent such as carbon black, an antiaging agent, a vulcanization accelerator, and other raw material rubber components. Various rubber chemicals required before vulcanizing can be mixed in predetermined amounts.

In the second aspect of the present invention, γc is 37
As a general-purpose rubber-containing rubber composition selected in addition to the rubber composition containing a raw material rubber component of ˜39 mN / m, it is necessary that the critical surface tension γc contains a raw material rubber component of 25 to 33 mN / m. is there. When the value of γc of the raw rubber component contained in these general-purpose rubber compositions is outside the above range,
The adhesiveness to the ultra high molecular weight PE sheet d is lowered, and the adhesive composite of the present invention cannot be manufactured. Examples of the raw rubber component having γc in the above range include IIR
(Γc = 27 mN / m), ethylene-propylene-diene copolymer rubber (EPDM, γc = 28 mN / m), natural rubber (NR, γc = 31 mN / m), styrene-butadiene copolymer rubber (SBR, γc = 33 mN / m) and the like. These may be used alone or in combination of two or more.

The modified NBR rubber composition used as an intermediate medium in the second aspect of the present invention contains 10 to 60 parts by weight of an ethylenically unsaturated nitrile unit and 3 parts of a conjugated diene unit.
20 to 60 parts by weight of methacrylic acid and 10 parts by weight of zinc oxide to 100 parts by weight of hydrogenated NBR containing 0 parts by weight or less.
.About.60 parts by weight and 0.5 to 20 parts by weight of organic peroxide.

The IIR rubber composition used in the second invention of the present invention is also not particularly limited, and contains IIR as a raw rubber component, and contains a vulcanizing agent such as sulfur, a reinforcing agent such as carbon black, and aging. A known rubber composition may be mentioned in which an inhibitor, a vulcanization accelerator, and various other rubber chemicals are mixed in predetermined amounts. In the present invention, the ultra-high molecular weight PE sheet d produced by the shaving method means that the ultra-high molecular weight polyethylene powder is sintered under heat and pressure to produce a columnar molded article, and the molded article is formed in the circumferential direction. It is cut into a sheet or film by shaving thinly. This ultra high molecular weight PE sheet d is the IIR sheet c described above.
In addition to having excellent adhesiveness to the general-purpose rubber sheet B described above, it also has excellent adhesiveness. Therefore, the ultra high molecular weight PE sheet d is the ABS resin molding material A
And indirectly bonding the general-purpose rubber sheet B.

The ultrahigh molecular weight PE sheet d used in the second invention of the present invention is preferably made of polyethylene having a molecular weight of 1,000,000 or more. When the molecular weight is 1,000,000 or more, the adhesiveness to the IIR sheet c or the general-purpose rubber sheet B can be further improved. The ultra high molecular weight PE sheet d preferably has a thickness in the range of 10 to 200 μm. By setting this thickness to 10 μm or more, the tensile strength and elastic modulus can be increased and a reinforcing effect can be imparted. On the other hand, when the thickness is 200 μm or less, the flexibility of the bonded portion can be secured.

In the first aspect of the present invention, the above A
The BS resin is appropriately molded into a molding material by means of known injection molding, extrusion molding, roll molding, etc., while the above-mentioned high γc is obtained.
Similarly, a rubber composition containing the raw material rubber component of 1 is preformed to form an unvulcanized high γc rubber sheet. High γc
The rubber sheet may be reinforced with various organic fiber cords such as steel cord, nylon, polyester and aramid. These ABS resin molding materials and high γc
The thickness of the rubber sheet is not particularly limited,
It is desirable that it is at least 0.05 mm or more.

In the first aspect of the invention, the high γc rubber sheet needs to be in an unvulcanized state, and when it is vulcanized, it can be firmly adhered to the ABS resin molding material. It becomes impossible to produce the adhesive composite of the present invention. The laminated ABS resin molding material and the high γc rubber sheet are heated so that the high γc rubber sheet can be vulcanized and simultaneously bonded to each other.

In the second aspect of the present invention, an ABS molding material A is produced in the same manner as described above, while a rubber composition containing a raw rubber component having a γc of 37 to 39 mN / m and a modified NBR rubber. Similarly, the composition, the IIR rubber composition, and the general-purpose rubber composition are preformed to prepare plate-shaped or sheet-shaped unvulcanized sheets a, b, c and general-purpose rubber sheet B. These ABS molding material A, unvulcanized sheet a,
Although the thicknesses of b and c and the general-purpose rubber sheet B are not particularly limited, they are usually preferably 0.05 mm or more. Further, the unvulcanized rubber sheets a, b, c and the general-purpose rubber sheet B can be reinforced with the above-mentioned various cords.

In the second aspect of the present invention, the high γc rubber sheet a, the modified NBR sheet b, the IIR sheet c and the general-purpose rubber sheet B each need to be in an unvulcanized state. If even one of these is vulcanized, the adhesive composite of the present invention cannot be produced. These unvulcanized rubber sheets a, b and c, the ultra high molecular weight PE sheet d and the general-purpose rubber sheet B are
It is necessary to directly stack the high γc rubber sheet a on the BS resin molding material A and then stack them in the following order of A / a / b / c / d / B. High γc for ABS resin molding material A
If the rubber sheet a is not directly laminated, the other rubber sheets cannot be firmly adhered, and the ABS resin molding material A and the general-purpose rubber sheet B are laminated by laminating in the above order.
And can be firmly bonded and integrated.

After being laminated as described above, the high γc rubber sheet a, the modified NBR sheet b, the IIR sheet c and the general-purpose rubber sheet B are vulcanized and the ultra high molecular weight P is obtained.
The E sheet d is heated under the condition that it melts. The heating condition is not particularly limited as long as it is a temperature at which the unvulcanized rubber sheets a, b, c and the general-purpose rubber sheet B are vulcanized and the ultra high molecular weight PE sheet d is melted, but it is preferable. It is preferable that the temperature is 140 to 200 ° C. and the pressure is appropriately applied.

[0020]

【Example】

Example 1 As an ABS resin molding material, a 2 mm flat plate of Clarastic-MLA manufactured by Sumitomo Nogatak Co., Ltd. was 150 mm × 50 m.
It was cut into a size of m × 2 mm. As the high γc rubber sheet, using the NBR rubber composition a having the composition shown in Table 1,
An unvulcanized NBR sheet of 150 mm × 50 mm × 0.1 mm was produced.

These ABS resin molding materials and unvulcanized NB
When laminated with an R sheet and heated at 160 ° C. for 20 minutes, a composite body in which the vulcanized NBR sheet was firmly adhered to the ABS resin molding material was obtained. Examples 2 to 4, Comparative Example 1 As the ABS resin molding material A and the high γc rubber sheet a,
In the same manner as in Example 1, an ABS resin molding material and an unvulcanized NBR sheet were produced.

As the modified NBR sheet b, ZSC-2295, 85% by weight manufactured by Zeon Corporation and ZETPOL-2020 (hydrogenated NBR) manufactured by Nippon Zeon Co., Ltd. 15% by weight.
Was added by a roll, and to 100 parts by weight of this mixture,
1.5 parts by weight of an anti-aging agent (“Now Guard” 445), as an organic peroxide, “Perkadox” 1 manufactured by Kayaku Akzo
A mixture of 5 parts by weight of 4/40 (1,3-Bister butyl peroxyisopropylbenzene) was used with a roll, and this was used with a roll of 150 mm x 50 mm x
It was formed into a 0.1 mm sheet.

As the IIR sheet c and the general-purpose rubber sheet B, the IIR rubber composition B having the composition shown in Table 1 and three kinds of general-purpose rubber compositions C-1 (raw material rubber component EPDM, γc = 2)
8 mN / m), C-2 (raw rubber component NR, γc = 31)
mN / m) and C-3 (raw rubber component SBR, γc = 3)
3mN / m), 150mm x 50mm each
An unvulcanized IIR sheet c of 0.5 mm and general-purpose rubber sheets B-1, B-2, and B-3 were molded.

As the ultra-high molecular weight PE sheet d, a molecular weight of 50 produced by the shaving method manufactured by Sakushin Kogyo Co., Ltd.
A 0.05 mm-thick film-like sheet made of 0,000 polyethylene was prepared. The ABS resin molding material A,
An unvulcanized high γc rubber sheet a, a modified NBR sheet b, an IIR sheet c, and an ultrahigh molecular weight PE sheet d are respectively placed between the general-purpose rubber sheets B-1, 2, and 3 in the same order (A / a / b / c / d / B) and then heated at 160 ° C. for 30 minutes to vulcanize the unvulcanized rubber sheets a, b, c and general-purpose rubber sheets B-1, 2, 3 respectively. At the same time, the ultra-high molecular weight PE sheet d was melted to give an adhesive composite A / a / b / c / d / B-1 (Example 2), A / a / b / c / d / B-2 (Example). 3) and A / a / b / c / d / B-3 (Example 4) were manufactured.

For comparison, a general-purpose rubber sheet B-4
As the adhesive laminate A / a / b / c /, except that the rubber sheet a made of the NBR rubber composition a was used.
d / B-4 (Comparative Example 1) was manufactured.

[0026] All the numerical values in Table 1 are parts by weight.

* 1 is N-phenyl-N'-isopropyl-p-phenylenediamine * 2 is Nt-butyl-2-benzothiazolesulfenamide * 3 is tetramethylthiuram disulfide * 4 is 2-mercapto Benzothiazole * 5 is tetramethyl thiuram monosulfide * 6 is benzothiazyl disulfide.

The adhesive composites of Examples 2 to 4 were all AB
S resin molding material A and general-purpose rubber sheets B-1, B-2, B
-3 was firmly bonded and integrated through the rubber sheets a, b and c and the ultra high molecular weight PE sheet d, respectively. However, the adhesive composite of Comparative Example 1 had low adhesiveness between the rubber sheet B-4 and the ultrahigh molecular weight PE sheet d and was easily peeled off. Example 5, Comparative Example 2 In Example 2, the general-purpose rubber sheet B-1 was vulcanized, and the vulcanized rubber sheet B-1 ′ was laminated to form an adhesive composite A.
/ A / b / c / d / B-1 '(Example 5) and general-purpose rubber sheet B-3 were vulcanized, and this vulcanized rubber sheet B-
3'laminated adhesive composite A / a / b / c / d / B-
3 '(Comparative Example 2) was manufactured.

In the adhesive composite of Example 5, the ABS resin molding material A and the general-purpose rubber sheet B-1 'are the rubber sheet a,
It was firmly bonded via b and c and the ultra high molecular weight PE sheet d. On the other hand, in the adhesive composite of Comparative Example 2, the adhesiveness between the general-purpose rubber sheet B-3 ′ and the ultrahigh molecular weight PE sheet d was low and was easily peeled off. Comparative Examples 3 and 4 An adhesive composite A / b / a / c / d / B-1 (Comparative Example 3) was produced in the same manner as in Example 2 except that the stacking order was changed. However, in this adhesive laminate, the ABS resin molding material A and the modified NBR sheet b were not adhered.

[0030]

According to the first invention of the present invention, 37 to 3
Like NBR, the rubber component having a high γc of 9 mN / m contains acrylonitrile as a copolymerization component like the ABS resin, and therefore it is considered that the critical surface tensions γc of both are similar. Therefore, when the ABS resin and the unvulcanized high γc rubber sheet are laminated and heated, it is possible to manufacture an adhesive composite of the ABS resin and the rubber that is firmly adhered and integrated by the selective adhesiveness of the both. It will be possible.

According to the second aspect of the present invention, a high γ that selectively adheres to the ABS resin molding material A described above is used.
c rubber sheet a is directly laminated, and this high γc rubber sheet a
Sequentially, modified N with good adhesiveness to each other
The BR sheet b, the IIR sheet c, the ultra-high molecular weight PE sheet d, and the general-purpose rubber sheet B are laminated in the order of A / a / b / c / d / B and then heated to be bonded and integrated, It is possible to produce an adhesive composite having both properties of ABS resin and general-purpose rubber.

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Claims (2)

[Claims] 1. A molding material made of ABS resin and an unvulcanized rubber sheet made of a rubber composition containing a raw rubber component having a critical surface tension γc of 37 to 39 millinewtons / meter are laminated and then heated and bonded. A method for producing an integrated adhesive composite of ABS resin and rubber. 2. Between a molding material A made of ABS resin and an unvulcanized rubber sheet B made of a rubber composition containing a raw rubber component having a critical surface tension γc of 25 to 33 millinewtons / meter, 37 To 39 millinewtons / meter of an unvulcanized rubber sheet a composed of a rubber composition containing a raw rubber component, and a hydrogenated acrylonitrile-butadiene copolymer rubber composition containing methacrylic acid, zinc oxide and peroxide A non-vulcanized rubber sheet b, a non-vulcanized rubber sheet c made of an isobutyl-isoprene copolymer rubber composition, and an ultrahigh molecular weight polyethylene sheet d produced by a shaving method are interposed, and A / a / b / c / d / B
A method for producing an adhesive composite of an ABS resin and rubber, which is laminated in this order and then heated and adhesively integrated.