JPH1120101A - Laminated body and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated body, which has excellent fusing properties to a material layer such as vinyl chloride polymer, acrylonitrile-styrene-butadiene copolymer, polycarbonate, and simplify manufacture processes of the laminated body by forming a laminated body containing vinyl chloride polymer, and dicyclohexane phthalate. SOLUTION: A layer is composed of vinyl chloride polymer composed of two or more mixtures such as vinyl chloride homopolymer, chlorinated vinyl chloride polymer, etc., and dicyclohexane phthalate composed of plasticizer for vinyl chloride polymer such as di-n-butyl phthalate, di-heptyl phthalate, etc. The vinyl chloride polymer and the dicyclohexane phthalate comprising the laminated body are heated, fused, and mixed for forming the layer. The excellent fusing properties of the layer allow easy manufacture of a laminated body in conjunction with rubber, thermoplastic elastomer, high-molecular foam, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate comprising a layer comprising a vinyl chloride polymer (hereinafter, referred to as PVC) and di-cyclohexyl phthalate (hereinafter, referred to as DCHP) and its production. It is about the method.

[0002]

2. Description of the Related Art Conventionally, general soft vinyl chloride resins obtained by blending a plasticizer with PVC include acrylonitrile-styrene-butadiene copolymer (hereinafter referred to as ABS), polycarbonate (hereinafter referred to as PC), and the like. Because of its inferior heat-fusibility with a hard resin, when manufacturing a laminate with the hard resin, the laminate has been manufactured via a primer, an adhesive or the like.

[0003]

However, the above-described method of producing a laminate through a primer, an adhesive or the like has a problem that the number of working steps is increased and the productivity of the laminate is poor. .

Accordingly, an object of the present invention is to provide a laminate which solves the above-mentioned problems and a method for producing the same.

[0005]

Means for Solving the Problems The present inventor has conducted intensive studies in view of the above-mentioned current situation, and as a result, has found that a layer composed of PVC and a specific plasticizer has excellent heat-fusibility. It was completed.

That is, the present invention relates to a laminate comprising a layer made of PVC and DCHP, and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The PVC used in the present invention is a vinyl chloride-containing polymer, for example, at least one kind of a vinyl chloride homopolymer, a chlorinated vinyl chloride polymer, and a monomer copolymerizable with a vinyl chloride monomer. And vinyl chloride copolymers obtained by random copolymerization, graft copolymerization or block copolymerization with vinyl chloride monomers, or mixtures of two or more of these polymers.

Examples of the monomer copolymerizable with the vinyl chloride monomer include ethylene, propylene, butene, pentene-1, butadiene, styrene, α-methylstyrene,
Alkyl vinyl ethers such as acrylonitrile, vinylidene chloride, vinylidene cyanide, and methyl vinyl ether; carboxylic acid vinyl esters such as vinyl acetate; aryl ethers such as methoxystyrene; dialkyl maleic acids such as dimethyl maleic acid; Fumaric acid esters; N-vinylpyrrolidone, vinylpyridine, vinylsilanes, alkyl acrylates such as butyl acrylate; and alkyl methacrylates such as methyl methacrylate.

[0010] The degree of polymerization of PVC used in the present invention is not particularly limited, and any one can be used. However, since a laminate excellent in productivity can be obtained, it is preferably 300 to 40.
Those having a value of 00 or less are preferably used.

[0011] The PVC is preferably obtained by a suspension polymerization method because it can be easily impregnated with DCHP when producing a resin composition for a laminate.

[0012] DC in the layers constituting the laminate of the present invention
The compounding amount of HP is preferably 1 to 200 parts by weight, and more preferably 1 to 90 parts by weight, based on 100 parts by weight of PVC because of excellent molding processability of the laminate.

PVC and DC constituting the laminate of the present invention
In the layer made of HP, stabilizers which are usually added to PVC to such an extent that their performance is not extremely deteriorated (for example, metal soaps such as barium stearate, organotin stabilizers such as tin laurate, tetraphenyl polypropylene glycol) Phosphite stabilizers such as diphosphite; hydrotalcite stabilizers such as perchloric acid-treated hydrotalcite; and lubricants (eg, fatty acid ester waxes such as n-butyl stearate; hydrocarbons) Waxes, metal soaps such as magnesium stearate and zinc stearate, etc.), and acrylic processing aids (e.g., methyl methacrylate-alkyl acrylate copolymers such as methyl methacrylate-butyl acrylate copolymer). .), Colorant, calcium carbonate,
Inorganic fillers such as talc, antimony trioxide,
A flame retardant represented by zinc borate and the like can be added as needed.

The layer comprising PVC and DCHP constituting the laminate of the present invention comprises di-n-butyl phthalate (hereinafter referred to as DBP) used as a plasticizer for PVC and di-heptyl phthalate. (Hereinafter referred to as DHP), di-2-ethylhexyl phthalate (hereinafter referred to as DO)
Say P. ), Di-n-octyl phthalate, di-isononyl phthalate, di-isodecyl phthalate, di-phthalic acid
Phthalic acid-based plasticizers such as isooctyl, octyldecyl phthalate, butylbenzyl phthalate (hereinafter referred to as BBP), di-methylcyclohexyl phthalate, and di-2-ethylhexyl isophthalate; di-2-ethylhexyl adipate ( Hereinafter, referred to as DOA.), Di-n-adipate
Aliphatic plasticizers such as decyl, diisodecyl adipate, dibutyl sebacate and di-2-ethylhexyl sebacate; trimellitic acid plasticizers such as trioctyl trimellitate and tridecyl trimellitate; tributyl phosphate and phosphorus Tri-2-ethylhexyl acid, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, tri-xylenyl phosphate (hereinafter referred to as TXP)
A plasticizer such as an epoxy plasticizer such as an epoxy soybean oil and a plasticizer such as a polyester polymer plasticizer may be added without departing from the object of the present invention.

PVC and DC constituting the laminate of the present invention
In order to manufacture a layer composed of HP, PVC and DCH
It is preferable that P is melted and mixed by heating to prepare a resin composition for a laminate.

As the method of heating and melting and mixing, any method may be used. For example, a Banbury mixer (manufactured by Farrell), a pressure kneader (manufactured by Moriyama Seisakusho), an internal mixer (manufactured by Kurimoto Iron Works), intensive, etc. Using a kneading and molding machine used for processing plastics or rubber, such as a mechanical press kneader such as a mixer (manufactured by Nippon Roll Manufacturing Co., Ltd.), a roll molding machine, an extrusion molding machine, etc.
The HP is kneaded at a kneading temperature of 90 to 220 ° C, preferably 100 to 1
A method of heating and melting at 80 ° C. is exemplified. In this case, it is preferable to use a powdery mixture in which DCHP is impregnated with PVC in advance, and to heat and mix. Here, in order to impregnate the PVC with DCHP in advance, for example, a mixer such as a ribbon blender with a jacket, a Henschel mixer (manufactured by Mitsui Miike Seisakusho) or a super mixer (manufactured by Kawada Seisakusho) may be used. When such a mixer is used, PVC is charged into the mixer, and then D.
By adding CHP and continuing the mixing until the resin temperature becomes 90 to 150 ° C., the DCHP is impregnated with the PVC powder to obtain a fluid powdery mixture.

PVC and DC constituting the laminate of the present invention
Because of the excellent fusibility of the layer made of HP, it is possible to easily produce a laminate with, for example, rubber, thermoplastic elastomer, thermoplastic resin, thermosetting resin, or polymer foam.

Examples of the rubber include butadiene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber,
Isoprene rubber, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber, acrylic rubber, ethylene propylene rubber, butyl rubber, silicone rubber,
Fluoro rubber, chloroprene, chlorinated polyethylene rubber,
Examples include epichlorohydrin rubber, chlorosulfonated polyethylene rubber, urethane rubber, natural rubber, or mixtures thereof.

Examples of the thermoplastic elastomer include styrene-butadiene-based thermoplastic elastomer, styrene-isoprene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, PVC-based thermoplastic elastomer, urethane-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer. Examples thereof include a thermoplastic elastomer, a fluorine-based thermoplastic elastomer, a silicone-based thermoplastic elastomer, and the like, or a mixture thereof.

Examples of the thermoplastic resin include acrylic resin, acetal resin, fluororesin, polyamide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene chloride, PVC, polypropylene, polyethylene, and polyolefin such as ethylene-vinyl acetate copolymer. , PC, polystyrene, polyphenylene sulfide, liquid crystal polymer, ABS, ABS / PC
Alloys, hard PVC, soft PVC, and the like, or a mixture thereof, may be used.

Examples of the thermosetting resin include aniline resin, urea resin, melamine resin, epoxy resin, phenol resin, unsaturated polyester resin, alkyd resin, allyl resin and the like, or a mixture thereof.

Examples of the polymer foam include those using PVC, polyurethane, polystyrene, polyolefin and the like.

In producing a laminate comprising a layer comprising PVC and DCHP of the present invention, for example, multilayer extrusion molding, multilayer injection molding (multicolor injection molding, insert molding), extrusion lamination, hot melt lamination, dry lamination Various molding processing methods such as multilayer lamination molding such as lamination and wet lamination, multilayer inflation molding, and multilayer blow molding are exemplified, and among them, a method by injection molding in which the effect of the present invention is particularly remarkable is preferably used.

In order to produce the laminate of the present invention, at least one layer selected from the group consisting of rubber, thermoplastic elastomer, thermoplastic resin, thermosetting resin, polymer foam, etc. Heat welding may be performed by a method such as pressing, high-frequency welding, heat sealing, impulse sealing, or ultrasonic bonding.

The laminate of the present invention comprising a layer composed of PVC and DCHP can be used for transporting conveyor belts such as a conveyor belt, a resin conveyor belt, a steeply inclined conveyor, a cylindrical conveyor belt, and the like, such as a power belt such as a V belt and a toothed belt. Transmission belts; braided hoses, cloth-wound hoses, high-pressure hoses, suction hoses, duct hoses, spray hoses, hoses for water supply and drainage, pressure-resistant reinforcement hoses, antistatic hoses, etc .; automobiles, railways, industrial machines, Anti-vibration rubber for architectural civil engineering; fenders, printing rolls, papermaking rolls, spinning rolls, steelmaking rolls, dyeing fiber rolls, etc .; industrial rolls; office machine rolls, OA equipment rolls, automation Rolls for various machines such as machine rolls; Rolls for agricultural machines such as milling machines; Lining of various materials including metals; Makeup Sheets such as sheets, antistatic sheets, roofing sheets, etc .; packing laminates for mobile phone cases, remote control cases for electric appliances, etc., sealing materials, waterproof materials, oil seals, mechanical seals, molded packings, gland packings, etc. Seal for movement; sealing for fixing O-rings, gaskets, etc .; sealing for capacitors;
Sponge products, stoppers, catheters, droppers, gaskets for syringes, masks, sacks, gloves, condoms, water pillows, nipples for baby bottles, cap containers, rainwear, airbags, diaphragms, rubber dams, gas envelopes, oil fences, flexible containers , Golf balls, soccer balls and other balls, sports floors, cushioning rubber for fences, chains, paving blocks, automotive boots,
Weather strips, architectural gaskets, seismic isolation rubber, handrails, non-slip, airtight, spacers, laminated glass, waterstops, elastic joints, thread rubber, rubber cords,
Handrail, plastic magnet, rubber magnet, electric wire, cord, caster, bearing, coupling, cushion, bush, boots, grommet, insulator, stopper, wiper blade, joint, vibration damping rubber,
Rubber switches, sockets, toys, masks, shoes, foot rubber,
Tubes, packing for electric appliances, industrial parts, etc., grips for golf clubs, tennis rackets, ski poles, etc., sealants, sheets, electric parts, electronic parts, semiconductive films, antistatic films, films such as pharmaceutical films, tires, It can be used for precision equipment, vibration absorbers for precision processing machines, sports equipment, daily goods, seats, etc.

[0026]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The laminates obtained in Examples and Comparative Examples were evaluated by the following methods.

-Peel strength-According to the peel strength test of cloth and vulcanized rubber according to JIS K 6256, a strip-shaped test piece was used. However, the peel length was 70 mm or less.

Example 1 100 parts by weight of an ethylene-vinyl chloride copolymer (manufactured by Taiyo Vinyl Co., Ltd., trade name: TE-1050) obtained by a suspension polymerization method in a Henschel mixer having an internal volume of 20 liters, as a stabilizer 2 parts by weight of barium stearate, hydrochlorite treated with perchloric acid (manufactured by Nissan Ferro-Organic Chemical Co., Ltd.
BP-331) 1.5 parts by weight and 950 rp
The mixture was stirred at a rotation speed of m for 1 minute. Subsequently, 90 parts by weight of DCHP (trade name: DCHP, manufactured by Osaka Organic Chemical Co., Ltd.) was added to the Henschel mixer, and the mixture was stirred and mixed until the temperature of the mixture reached 110 ° C. The content was 4000 g in total. The mixture became a powdery mixture that could easily flow.

The obtained powdery mixture was heated and melt-mixed with a twin-screw extruder under shearing force to granulate a fusible resin composition (hereinafter, referred to as composition 1).

On the other hand, using a 50-ton injection molding machine separately, a rigid PVC (trade name 4 manufactured by Plus Tech Co., Ltd.) was used.
250) was formed into a 70 mm × 70 mm × 2 mm plate.

The obtained rigid PVC plate is 70 mm × 7
Insert into a mold cavity of 0 mm x 3 mm,
The laminated body composed of the rigid PVC-composition 1 was obtained by subjecting the composition 1 to injection molding (cylinder temperature: 170 ° C, nozzle temperature: 180 ° C) using an injection molding machine.

The peel strength of the obtained laminate was evaluated. Table 1 shows the results.

The composition 1 of the laminate obtained and the rigid PVC were excellent in fusing property.

Example 2 A laminate was produced and evaluated in the same manner as in Example 1, except that PC (manufactured by Teijin Limited, trade name: Panlite L1225) was used instead of rigid PVC.

Table 1 shows the results.

The fusion property between the composition 1 of the obtained laminate and PC was excellent.

Example 3 A laminate was manufactured and evaluated in the same manner as in Example 1 except that ABS (Styrac 200, trade name, manufactured by Asahi Kasei Corporation) was used instead of rigid PVC.

Table 1 shows the results.

The fusion property between the composition 1 and the ABS of the obtained laminate was excellent.

Example 4 A vinyl chloride copolymer obtained from a Henschel mixer having an inner volume of 20 liters by a suspension polymerization method (Taiyo PVC Co., Ltd.)
100 parts by weight, trade name TH-1000), 2 parts by weight of barium stearate as a stabilizer, hydrotalcite treated with perchloric acid (manufactured by Nissan Ferro-Organic Chemical Co., Ltd., trade name B)
P-331) 1.5 parts by weight were charged and stirred at a rotation speed of 950 rpm for 1 minute. Subsequently, 50 parts by weight of DCHP (trade name: DCHP, manufactured by Osaka Organic Chemical Co., Ltd.) was added to the Henschel mixer, and the mixture was stirred and mixed until the temperature of the mixture reached 110 ° C. The content was 4000 g in total.
The mixture became a powdery mixture that could easily flow.

The resulting powdery mixture was heated and melt-mixed with a twin-screw extruder under shearing force to granulate a fusible resin composition (hereinafter referred to as composition 2).

On the other hand, using a 50-ton injection molding machine separately, rigid PVC (trade name: 4 manufactured by Plus Tech Co., Ltd.) was used.
250) was formed into a 70 mm × 70 mm × 2 mm plate.

The obtained rigid PVC plate is 70 mm × 7
Insert into a mold cavity of 0 mm x 3 mm,
The composition 2 was injection-molded using an injection molding machine to obtain a laminate composed of the rigid PVC-composition 2.

The peel strength of the obtained laminate was evaluated. Table 1 shows the results.

The composition 2 of the obtained laminate was excellent in the fusing property between the rigid PVC.

Comparative Example 1 A laminate was produced and evaluated in the same manner as in Example 1 except that DOP was used as a plasticizer instead of DCHP.

Table 1 shows the results.

The fusibility between the composition of the obtained laminate and the rigid PVC was low.

Comparative Examples 2 to 6 Laminates were produced and evaluated in the same manner as in Example 1 except that the plasticizers shown in Table 1 were used instead of DCHP.

Table 1 shows the results.

The compositions of the laminates obtained in Comparative Examples 2 to 6 and the rigid PVC had low fusing properties.

Bleed was observed in the composition of the laminate obtained in Comparative Example 5.

Comparative Example 7 DOP in place of DCHP and AB in place of rigid PVC
A laminate was manufactured and evaluated in the same manner as in Example 1 except that S was used.

Table 1 shows the results.

The fusibility between the composition of the obtained laminate and ABS was low.

[0057]

[Table 1]

[0058]

The laminate of the present invention comprising a layer composed of PVC and DCHP is excellent in fusing property with material layers such as PVC, ABS and PC, and simplifies the production process when producing the laminate. Can be achieved.

[0059]

Claims (4)

[Claims] 1. A laminate comprising a layer comprising a vinyl chloride polymer and di-cyclohexyl phthalate. 2. The laminate according to claim 1, further comprising a layer made of a thermoplastic resin. 3. A method according to claim 1, wherein the vinyl chloride polymer is 100 parts by weight.
3. The laminate according to claim 1, comprising a layer comprising 1 to 90 parts by weight of di-cyclohexyl phthalate. 4. The method for producing a laminate according to claim 1, wherein an injection molding method is used.