JPH0444903B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a multilayer sheet or a molded product thereof, in which the outer layer is made of a flexible and scratch-resistant elastomer and the inner layer is made of a thermoplastic resin with high rigidity and toughness. More specifically, the present invention utilizes two or more extruders, one or more of which is loaded with a modified hydrogenated block copolymer elastomer, and one or more of which is loaded with a modified hydrogenated block copolymer elastomer, such as a polypropylene resin. This is a multilayer sheet obtained by adding thermoplastic resin and using a multi-manifold die, feed block die, etc. A multilayer molded product can be obtained by thermoforming, ie, vacuum forming or pressure forming, this multilayer sheet. The outer layer of the obtained molded product is flexible and has a leather-like appearance as it easily scratches, while the inner layer is a multilayer molded product with sufficient rigidity and impact resistance. (Prior Art) Conventionally, interior parts of automobiles, such as dart boards, exterior parts, furniture, etc., are often made by covering a metal core with urethane foam, and then pasting vinyl chloride leather on the outer layer. Furthermore, bags and the like are often made by pasting vinyl chloride leather onto a thermoplastic resin sheet. Furthermore, a video camera case is made of thermoplastic resin with urethane foam, polyethylene foam, or cloth pasted on the inside to protect the product. (Problems to be Solved by the Invention) When manufacturing automobile interior parts, etc., a urethane foam stock solution is injected into a molded outer shell of polyvinyl chloride resin or ABS resin using a vacuum forming method and foamed integrally. The product is manufactured, but the process is complicated and productivity is low. Also, the formulation of urethane foam is very complex. On the other hand, if the multilayer sheet of the present invention is used, only thermoforming is required, which is advantageous in terms of economy. Furthermore, when we think about car fires, as we have seen recently, urethane foam and polyvinyl chloride resin inevitably generate toxic gases, and the product of the present invention is safer. In addition, for video camera carrying cases made of thermoplastic resin, the inside of the bag is made of urethane foam,
Gluing polyethylene foam or cloth plays a role in protecting the product, but the work of gluing urethane foam or cloth is complicated and takes a lot of man-hours. In contrast, the product of the present invention can greatly simplify the number of steps. (Means and effects for solving the problems) The present invention provides (a) a polymer block A mainly composed of at least two vinyl aromatic compounds and at least one
A modified block copolymer elastomer obtained by adding maleic anhydride to a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a polymer block B mainly composed of a conjugated diene compound; ) polyolefin resin, polystyrene resin,
Provided is a multilayer sheet manufactured by coextruding a resin selected from ABS resins, or a multilayer molded product obtained by thermoforming the same. It has excellent properties and high productivity. That is, the present invention provides a multilayer sheet that has excellent moldability such as extrusion molding, does not require any special crosslinking reaction, and has excellent reworkability and can be recycled. . Furthermore, the multilayer molded product obtained from the sheet of the present invention has excellent properties shown below. 1. The outer layer is highly flexible, and the inner layer has excellent physical properties such as strength and impact resistance. 2. The outer elastomer layer has excellent scratch resistance and a leather-like appearance. 3. When the elastomer layer is used as the inner layer, it has appropriate buffering performance. 4. The outer elastomer layer and the inner thermoplastic resin layer are strongly adhered to each other. 5. Both the elastomer layer and the thermoplastic resin layer can be colored freely by mixing dyes and pigments. The modified hydrogenated block copolymer used as component (a) in the present invention comprises a polymer block A mainly composed of at least two vinyl aromatic compounds and a polymer mainly composed of at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of block B, for example, A-B-
A, B-A-B-A, (A-B) ₄ --Si, A-B-
It is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as A-B-A. This hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 50% by weight of a vinyl aromatic compound; Aromatic compound polymer block or 50% by weight of vinyl aromatic compound
It has a structure of a copolymer block of a vinyl aromatic compound containing preferably 70% by weight or more and a hydrogenated conjugated diene compound, and further mainly contains a hydrogenated conjugated diene compound. The polymer block B is a hydrogenated conjugated diene compound polymer block, or a hydrogenated conjugated diene compound containing more than 50% by weight, preferably 70% by weight or more of a hydrogenated conjugated diene compound and a vinyl aromatic compound. It has the structure of a copolymer block with a group compound. In addition, polymer block A mainly composed of these vinyl aromatic compounds and polymer block B mainly composed of hydrogenated conjugated diene compounds are composed of hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or vinyl aromatic compound may be random, tapered (monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof; When there are two or more polymer blocks mainly consisting of a compound and two or more polymer blocks mainly consisting of the hydrogenated conjugated diene compound, each polymer block may have the same structure, or may have a different structure. It may be. As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more types can be selected from, for example, styrene, α-methylstyrene, vinylkelene, p-tert-butylstyrene, etc.
Among them, styrene is preferred. Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected. For example, in a polybutadiene block, the 1,2-microstructure is 20 to 50.
%, preferably 25-45%. Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above structure is 5000 to 5000.
1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and the molecular weight distribution [weight average molecular weight (w) and number average molecular weight (n)]
(w/n)] is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof. These block copolymers may be produced by any method as long as they have the above structure. For example, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798, and then, for example,
By the method described in Publication No. 8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Publication No. 133203-1983,
The hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. At that time, the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least
By hydrogenating 80% of the polymer, a polymer block mainly composed of a conjugated diene compound can be morphologically converted into an olefinic compound polymer block.
In addition, hydrogenation of aromatic double bonds based on vinyl aromatic compounds copolymerized into polymer block A mainly composed of vinyl aromatic compounds and, if necessary, polymer block B mainly composed of conjugated diene compounds. Although there is no particular restriction on the hydrogenation rate, it is preferable that the hydrogenation rate is 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like. The hydrogenated block copolymer produced as described above is added with an organic carboxylic acid such as maleic anhydride in an amount of 0.02 to
Addition of 30 parts by weight, preferably 0.05 to 20 parts by weight, yields a modified hydrogenated block copolymer. For the addition method, known means can be used. The polyolefin resins used as b) in the present invention include, for example, low-density polyethylene resins, linear low-density polyethylene resins, medium-density polyethylene resins, high-density polyethylene resins, polypropylene resins, nethylene-vinyl acetate resins, and ionomer resins. The polystyrene resin is, for example, an impact-resistant polystyrene resin containing 2 to 15% of a rubber component. Furthermore, ABS resins include, for example, 10 to 30% acrylonitrile and 5 to 45% butadiene produced by emulsion polymerization, mass suspension polymerization, and mass polymerization.
It has a composition of 50 to 85% styrene, and also includes those using α-methylstyrene instead of styrene. The resin used as b) in the present invention is not limited to a specific manufacturing method or type. For example, it can be appropriately selected from those listed below depending on the required physical properties of the final product. In other words, the resins described in "Polymer Analysis Handbook" edited by the Japan Society for Analytical Chemistry and the Polymer Analysis Research Council, Applied Edition 2, Plastics (page 225) can be used. Examples of polyolefins include 1) high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and modified polyethylene described in the section A polyethylene series, page 235 of the same, 2) listed in the section B polypropylene series, page 249 of the same. Polypropylene, copolymers with ethylene and butene, modified polypropylene, EVA described in 3) Ibid., p. 244, paragraphs 2, 2, 3, etc. are used. As the polystyrene resin, HIPS, which contains 2 to 15% of polybutadiene or styrene-butadiene rubber and is described in item (ii) on page 265 of the same publication, can be used. Furthermore, as ABS resin, various ABS and AES described in item (ii) on page 272 of the same,
AAS that uses α-methylstyrene instead of styrene is also used. The coextrusion method uses two or more extruders, and the coextrusion die includes a multi-manifold die, a combining die, an adapter die, and a multi-loft die. The weight ratio per unit area of each layer a) and b) in the multilayer sheet of the present invention is appropriately selected depending on the required characteristics of the final product, but it is generally preferable that a) layer 10 to 90%, b) ) layers are selected in the range of 90-10%. Desirable ranges are a) 15-85%, b) 85-15
%, more desirable ranges are a) 20 to 80%, b) 80 to
It is 20%. If necessary, inorganic fillers and plasticizers can be added to the modified hydrogenated block copolymer to adjust hardness and plasticity. Inorganic fillers used include titanium oxide, calcium carbonate, clay, talc, mica, bentonite, and the like. Plasticizers used include paraffin oil, naphthenic oil, dibutyl phthalate, di(2-ethylhexyl) phthalate, di-(2-ethylhexyl) adipate, diethylene glycol dibenzoate, butyl stearate, butyl epoxy stearate, and tristyrene. −
(2-ethylhexyl) phosphate and the like. Stabilizers, pigments, etc., which are general additives added to thermoplastic resin materials, can be appropriately added in the case of the present invention as well as conventional polymer resins. (Effects of the Invention) As detailed above, the multilayer molded product of the present invention has flexibility, weather resistance, scratch resistance, and cushioning properties due to the outer layer elastomer, and strength, modulus, and cushioning properties due to the inner layer thermoplastic resin. It provides impact resistance, and both are bonded with high adhesive strength. For this purpose, we produce automotive interior parts, exterior parts, furniture parts, home appliances,
Used for OA equipment carrying cases. (Examples) The present invention will be specifically described below with reference to Examples and Reference Examples, but the scope of the present invention is not limited thereto. Reference Example Synthesis Reference Example of Modified Hydrogenated Block Copolymer 1 Modified hydrogenated block copolymer (A) Has the structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene, and the amount of bound styrene is 18 weight %, the amount of 1,2-vinyl bonds in the polybutadiene part before hydrogenation is 40%, the number average molecular weight is 56000, the molecular weight distribution is 1.04,
A hydrogenated block copolymer with a hydrogenation rate of 98% was published in 1983-
Synthesized using a Ti-based hydrogenation catalyst described in Publication No. 133203. Per 100 parts by weight of this hydrogenated block copolymer,
1 part by weight of maleic anhydride, 2,5-dimethyl-
2,5-di(tert-butylperoxy)hexane
0.1 part by weight was mixed and a modification reaction was carried out in a 50 mm diameter twin screw extruder set at 250°C. The obtained modified hydrogenated block copolymer contained 0.75 parts by weight of maleic anhydride. Reference Example 2 Modified hydrogenated block copolymer (B) Next, (polystyrene-hydrogenated polybutadiene) has a structure of ₄ --Si and the amount of bound styrene
30% by weight, 1 of the polybutadiene part before hydrogenation
2-vinyl bond amount is 60%, number average molecular weight is 93000,
A hydrogenated block copolymer with a molecular weight distribution of 1.48 and a hydrogenation rate of 97% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203. This hydrogen block copolymer
Per 100 parts by weight, 0.5 parts by weight of maleic anhydride, 0.1 parts by weight of dicumyl peroxide, and 0.2 parts by weight of magnesium hydroxide were mixed, and the mixture was heated to 230 parts by weight using a 40 mm diameter single screw extruder.
The denaturation reaction was carried out under temperature conditions of °C. The obtained modified hydrogenated block copolymer had 0.16 parts by weight of maleic anhydride added thereto. Reference Example 3 Modified block copolymer (C) Furthermore, it has a structure of polystyrene-hydrogenated polybutadiene-polystyrene, the amount of bound styrene is 30%, and the amount of 1,2-vinyl bonds in the polybutadiene part before hydrogenation is 32 %, number average molecular weight
A hydrogenated block copolymer having a molecular weight distribution of 1.05 and a hydrogenation rate of 99% was synthesized using a hydrogenation catalyst described in JP-A-59-133203. This hydrogenated block copolymer
Per 100 parts by weight, 3.0 parts by weight of maleic anhydride, n-
0.3 parts by weight of butyl 4,4-bis(tert-butylperoxy)valerate was mixed, and a modification reaction was carried out at 260° C. in a 30 mm diameter twin screw extruder. The obtained modified hydrogenated block copolymer had 2.1 parts by weight of maleic anhydride added thereto. Example 1 A 90 m/m extruder manufactured by Toshiba Machine Co., Ltd., a 65 m/m extruder equipped with an adapter, a multi-manifold die, a take-up machine and a winder, and a 90 m/m extruder hopper. Asahi Kasei Polypropylene
Introducing M7200 (MFI1.5g/10MIN.), 65m/
The modified hydrogenated block copolymer (A) described above was charged into the hopper of an extruder to produce a multilayer sheet. The thickness of the polypropylene layer was 3.6 m/m, and the thickness of the modified hydrogenated block copolymer layer was 2.4 m/m. This sheet was molded into a video camera carrying case using a vacuum forming machine manufactured by Asano Laboratory. The modified hydrogenated block copolymer layer was placed on the inside of the case and had appropriate cushioning properties. Example 2 Using the multilayer sheet equipment of Example 1, a multilayer sheet of modified hydrogenated block copolymer (B) (a) and ABS resin (Cycolac GSE manufactured by Ube Cycon Co., Ltd.) (b) was created. The attachment case was molded using the Asano Laboratory's vacuum forming machine. In this case, the modified hydrogenated block copolymer layer was used as the outer layer. If the outer layer is a modified hydrogenated block copolymer layer, it will be a single layer molded product (made of ABS resin).
It had better scratch resistance, better weather resistance, and a softer appearance. Example 3 Using the multilayer sheet equipment of Example 1, modified hydrogenated block copolymer (C)(a) and Asahi Kasei Polypro M7200 were prepared.
(MFI1.5g/10MIN.) Create a multilayer sheet of (b),
Parts for a vehicle dash board were molded using a vacuum forming machine at the Kojino Research Institute. In this case, the modified hydrogenated block copolymer layer was used as the outer layer. Since the outer layer is a modified hydrogenated block copolymer layer, compared to a single layer polypropylene resin molded product,
It has good scratch resistance, good weather resistance, and
It had a soft appearance. Example 4 Using the multilayer sheet equipment of Example 1, modified hydrogenated block copolymer (B) (a) and Asahi Kasei Polypro M7200 were prepared.
(MFI1.5g/10MIN.) Create a multilayer sheet of (b),
A side protector for a car was molded using an air pressure molding machine manufactured by Iritsupi. Since the modified hydrogenated block copolymer layer was the outer layer, the molded product had better weather resistance, scratch resistance, impact resistance, and paintability than a single-layer polypropylene resin molded product. The physical properties of Examples 1 to 4 are listed in Table 1.

[Table] FIG. 1 shows the molded product of Example 1. 1 is a polypropylene resin, and 2 is a modified hydrogenated block copolymer. FIG. 2 shows Example 2. 3 represents a modified hydrogenated block copolymer, and 4 represents an ABS resin. FIG. 3 shows Example 3. 5 represents a modified hydrogenated block copolymer, and 6 represents a polypropylene resin. FIG. 4 shows Example 4. 7 represents a modified hydrogenated block copolymer, and 8 represents a polypropylene resin.

[Brief explanation of drawings]

FIG. 1 shows the molded product of Example 1, FIG. 2 shows the molded product of Example 2, FIG. 3 shows the molded product of Example 3, and FIG. 4 shows the molded product of Example 4.

Claims (1)

[Claims] 1 a Hydrogenation of a block copolymer consisting of a polymer block A mainly composed of at least two vinyl aromatic compounds and a polymer block B mainly composed of at least one conjugated diene compound. a modified hydrogenated block copolymer elastomer obtained by adding maleic anhydride to a hydrogenated block copolymer obtained by b) polyolefin resin, polystyrene resin,
A multilayer sheet manufactured by coextruding ABS resin with a selected resin.