JPH1034843A - Laminate and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminate having an excellent feel of touch and small stickiness and flatting by using a specific PVC-PU complex. SOLUTION: A PVC-PU complex is obtained by urethane reacting PVC, polymer polyol, isocyanate compound having three or more isocyanate groups, plasticizer and urethane reaction catalyst while heating, melting and mixing them by a shearing force. The degree of polymerization of the PVC is not particularly limited, and any can be used, but the PVC having 1000 to 4000 is preferably used. A molar ratio (NCO/OH molar ratio) of isocyanate group of the isocyanate compound to a hydroxyl group of the polymer polyol is 0.3 to 1.3 from points of excellent moldability in the case of molding the laminate and developing excellent compression permanent strain characteristics in the case of using diol as the polymer polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane (hereinafter referred to as PU) and a vinyl chloride-based polymer (hereinafter referred to as PVC) having low hardness, excellent compression set characteristics, excellent elasticity and low stickiness. -P consisting of a plasticizer
The present invention relates to a laminate including a layer composed of a U composite and its use.

[0002]

2. Description of the Related Art Conventionally, rubber laminated with hard material,
Soft PVC and thermoplastic elastomers have, for example, problems such as high hardness and poor feel, stickiness, easy adhesion of dirt due to stickiness, and poor compression set characteristics, which are easily settled during use.

In addition, rubber, soft PVC, and thermoplastic elastomer laminated with a soft material have problems such as high hardness, poor texture, inability to follow stretchability, and easy adhesion of dirt due to stickiness. was there.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an excellent feel, tackiness, and a layer comprising a layer of a PVC-PU composite which has solved the above-mentioned drawbacks in a laminate of a conventional rubber, soft PVC and thermoplastic elastomer layer. It is an object of the present invention to provide a laminate having little set and its use.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned situation, the present inventor has found that by using a specific PVC-PU composite, for example, when laminated with a hard material, it has an excellent feel and a low stickiness. The present inventors have found that a laminated body which does not sag can be obtained, and a laminated body which is excellent in texture and can follow elasticity can be obtained when laminated with a soft material, for example, and the present invention has been completed.

[0006] That is, the present invention provides a method for preparing PVC, a polymer polyol, an isocyanate compound having three or more isocyanate groups, a plasticizer, and a urethanation reaction catalyst under shearing force.
P obtained by urethane reaction while mixing under heating and melting
The present invention relates to a laminate characterized by including a layer composed of a VC-PU composite, and a use thereof.

Hereinafter, the present invention will be described in detail.

[0008] The PVC-PU composite used in the present invention comprises P
It is obtained by subjecting a VC, a polymer polyol, an isocyanate compound having three or more isocyanate groups, a plasticizer and a urethanation reaction catalyst to a urethane reaction while heating and mixing under shearing force.

In the present invention, PVC 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 a vinyl chloride copolymer obtained by random copolymerization, graft copolymerization or block copolymerization with the above, or a mixture of two or more of these polymers.

The monomers copolymerizable with the vinyl chloride monomer include, for example, ethylene, propylene, butene, pentene-1, butadiene, styrene, α-methylstyrene,
Acrylonitrile, vinylidene chloride, vinylidene cyanide, alkyl vinyl ethers such as methyl vinyl ether, carboxylic acid vinyl esters such as vinyl acetate, aryl ethers such as methoxystyrene, dialkyl maleic acids such as dimethyl maleic acid, dimethyl fumarate and the like Examples thereof include fumaric acid esters, N-vinylpyrrolidone, vinylpyridine, vinylsilanes, alkyl acrylates such as butyl acrylate, and alkyl methacrylates such as methyl methacrylate.

[0011] The degree of polymerization of PVC in the present invention is not particularly limited, and any can be used.
From the viewpoint of excellent moldability in laminating the PU composite, those having a size of 1000 or more and 4000 or less are preferably used.

Further, a PVC-PU used in the present invention described later.
When a polymer polyol and a plasticizer are impregnated in the production of the composite, the PVC is preferably obtained by a suspension polymerization method.

The polymer polyol referred to in the present invention is a polymer polyol having two or more hydroxyl groups. Examples thereof include polyester polyol, polyether polyol, polycarbonate polyol, vinyl polyol, diene polyol, castor oil polyol, and silicone polyol. Examples thereof include polyols, polyolefin-based polyols, and copolymers thereof, and one or more of these are used.

The molecular weight of the polymer polyol is not particularly limited, and any one can be used. However, the polymer polyol itself is easy to handle, and the resulting PVC-PU composite has low hardness and good compression set, and has a number average molecular weight. It is preferable that the molecular weight is 500 or more and 8000 or less.

The polyester polyol is obtained, for example, by subjecting a dicarboxylic acid and a short-chain polyol to condensation polymerization. At this time, as the dicarboxylic acid component, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, phthalic acid, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid And the like, and one or more of these are used. On the other hand, as the short-chain polyol component, aliphatic, alicyclic, aromatic, substituted aliphatic or heterocyclic dihydroxy compounds, trihydroxy compounds or tetrahydroxy compounds, such as 1,
2-ethanediol, 1,3-propanediol, 1,
4-butanediol, butenediol, 3-methyl-
1,5-pentanediol, 1,6-hexanediol, 1,10-decamethylenediol, 2,5-dimethyl-2,5-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, -Methyl-1,8-octanediol,
1,9-nonanediol, bis (β-hydroxyethoxy) benzene, p-xylenediol, dihydroxyethyltetrahydrophthalate, trimethylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1,2, 6-hexanetriol and the like, and one or more of these are used.

As another method for obtaining a polyester polyol, β-propiolactone, bivalolactone, δ-propiolactone,
Valerolactone, β-methyl-δ-valerolactone, ε
One or more lactone compounds such as caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl-ε-caprolactone, or one or more hydroxy compounds selected from the above short-chain polyol components; It is also possible to use a method of reacting with the above.

Examples of the polyether polyol include polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol and the like, and one or more of these are used.

As the polycarbonate-based polyol,
One obtained by transesterification from one or more hydroxy compounds selected from the above-mentioned short-chain polyols and diaryl carbonate, dialkyl carbonate or ethylene carbonate is used. For example, poly (1,6-hexamethylene carbonate), poly (2,2′-bis (4-hydroxyhexyl) propane carbonate) and the like are industrially produced. As another method for obtaining a polycarbonate polyol, a so-called phosgene method can be used.

In addition, poly (1), a vinyl polyol such as an acrylic polyol obtained by copolymerizing an acrylic monomer having a hydroxy group such as β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate with an acrylate ester; , 4-butadiene) and poly (1,2-butadiene); castor oil-based polyols such as polypropylene glycol ricinoleate; silicone-based polyols; and polyolefin-based polyols.

The isocyanate compound having three or more isocyanate groups in the present invention includes, for example, isocyanurate-modified diisocyanate, 1,6,11-undecane triisocyanate, lysine ester triisocyanate, and 4-isocyanatomethyl-1,8 -Triisocyanates such as octamethyl diisocyanate or polyisocyanates such as buret modified form of diisocyanate, allophanate modified form, adduct, and polyphenylmethane polyisocyanate, and one or more of these are used. .

As the diisocyanate, for example, 2,4
-Or 2,6-tolylene diisocyanate, m- or p-phenylene diisocyanate, 1-chlorophenylene-2,4-diisocyanate, 1,5-naphthalenediisocyanate, methylenebisphenylene-4,4 '
-Diisocyanate, m- or p-xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate and the like.

The above-mentioned diisocyanates can be used in combination. However, in this case, the molar ratio of isocyanate groups of the isocyanate compound having three or more isocyanate groups to the number of moles of isocyanate groups of all the isocyanate compounds is preferably 0.25 or more from the viewpoint of exhibiting compression set characteristics.

The molar ratio (NCO / OH molar ratio) of the isocyanate group in the isocyanate compound to the hydroxyl group of the polymer polyol is excellent in moldability in molding the laminate, and exhibits excellent compression set characteristics. When using a diol as a polymer polyol from the viewpoint,
It is 0.3 or more and 1.3 or less, preferably 0.5 or more and 1.1 or less.

It is preferable to carry out the PU production reaction in the presence of a urethanization reaction catalyst. The urethanization reaction catalyst is not particularly limited, and a known catalyst can be used. For example, amine catalysts such as triethylamine, triethylenediamine, and N-methylmorpholine; tin catalysts such as tetramethyltin, tetraoctyltin, dimethyldioctyltin, triethyltin chloride, dibutyltin diacetate, and dibutyltin dilaurate; , One or two of these
More than one species can be used, with dibutyltin dilaurate being preferred. The amount of the catalyst used depends on the activity of the catalyst used, but the amount necessary for completing the urethane reaction is good. Taking dibutyltin dilaurate as an example, the amount is preferably 1 ppm or more and 10000 ppm or less based on the total amount of PVC, polymer polyol, isocyanate compound and plasticizer from the viewpoint of excellent productivity and processability.

The PU content of the PVC-PU composite used in the present invention, that is, the total blended amount of the polymer polyol and the isocyanate compound, is preferably 30 to 100 parts by weight of PVC from the viewpoint of exhibiting good moldability and compression set. It is preferable that the amount be not less than 600 parts by weight and not more than 600 parts by weight.

Examples of the plasticizer in the present invention include di-n-butyl phthalate, di-2-ethylhexyl phthalate (hereinafter referred to as DOP), di-n-octyl phthalate, diisononyl phthalate, and diisodecyl phthalate. Phthalic acid plasticizers such as diisooctyl phthalate, octyl decyl phthalate, butyl benzyl phthalate, di-2-ethylhexyl isophthalate; di-2-ethylhexyl adipate, di-n-decyl adipate, diisodecyl adipate; Aliphatic ester plasticizers such as dibutyl sebacate and di-2-ethylhexyl sebacate; trimellitic acid plasticizers such as trioctyl trimellitate and tridecyl trimellitate; tributyl phosphate and tri-2-phosphate
Phosphate plasticizers such as ethylhexyl, 2-ethylhexyldiphenyl phosphate, tricresyl phosphate and the like;
An epoxy plasticizer such as an epoxy soybean oil; a polyester polymer plasticizer;
More than species can be used.

The amount of the plasticizer is preferably 1 to 100 parts by weight of PVC from the viewpoint of imparting flexibility and preventing bleed-out.
0 to 300 parts by weight is suitably used.

The PVC-PU composite used in the present invention contains a stabilizer (for example, a metal soap such as barium stearate, an organic soap such as tin laurate) which is usually added to PVC to such an extent that its performance is not extremely reduced. Tin-based stabilizers, phosphite-based stabilizers such as tetraphenylpolypropylene glycol diphosphite, and hydrotalcite-based stabilizers such as perchloric acid-treated hydrotalcite).
Lubricant (for example, fatty acid ester wax such as n-butyl stearate, hydrocarbon wax, metal soap such as magnesium stearate, zinc stearate, etc.), acrylic processing aid (for example, methyl methacrylate-butyl) Methyl methacrylate-alkyl acrylate copolymer such as acrylate copolymer), colorant,
Inorganic fillers such as calcium carbonate and talc, and flame retardants such as antimony trioxide and zinc borate can be added as needed.

In the PVC-PU composite used in the present invention, PU is heated and melt-mixed with a PVC, a polymer polyol, an isocyanate compound having three or more isocyanate groups, a plasticizer, and a urethanation reaction catalyst under a shearing force. For example, a Banbury mixer (manufactured by Farrell), a pressure kneader (manufactured by Moriyama Seisakusho), an internal mixer (manufactured by Kurimoto Iron Works), an intensive mixer (manufactured by Nippon Roll Manufacturing Co., Ltd.), etc. A kneading molding machine used for processing plastic or rubber, such as a mechanical press kneading machine, a roll molding machine, and an extrusion molding machine can be used. The temperature for heating and melting and mixing is 90 to 220 ° C, preferably 100 to 150 ° C. PV below 90 ° C
C is difficult to melt, and at 220 ° C. or higher, PVC may be thermally decomposed.

At this time, it is preferable to carry out heat melting and mixing under a shearing force using a powdery mixture in which a plasticizer has been impregnated with PVC in advance, since the surface smoothness during extrusion molding is good.

The urethane-forming reaction catalyst may or may not be impregnated with PVC in advance together with a plasticizer.
It is preferable to impregnate in handling.

Further, when the liquid component is large, when the mixture is heated and melted under a shearing force using a powder mixture in which a polymer polyol and a plasticizer have been impregnated in PVC in advance, the surface smoothness during extrusion molding is good. It is preferable because productivity is improved as well.

To impregnate the PVC with a plasticizer, a polymer polyol, a urethanization reaction catalyst or the like in advance, 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) is used. It may be used. When such a mixer is used, after adding PVC to the mixer, a predetermined amount of a plasticizer, a polymer polyol, a urethanization reaction catalyst, etc. are added thereto with stirring, and mixed until the resin temperature reaches 90 to 150 ° C. , A plasticizer, a polymer polyol, a urethanization reaction catalyst, and the like are impregnated in the PVC powder to obtain a fluid powdery mixture. Resin temperature is 90 ° C
If it is less than 150 ° C., the powder fluidity is poor, and if it exceeds 150 ° C., fish eyes may be formed.

When impregnating two or more of a plasticizer, a polymer polyol and a urethanization reaction catalyst, they may be mixed in advance and then charged into a mixer such as the above-mentioned Henschel mixer, or may be charged separately. .

PU is made of PVC, polymer polyol, isocyanate compound having three or more isocyanate groups,
An example of producing a plasticizer and a urethanization reaction catalyst by heating and melt-mixing them under a shearing force is PVC and three or more isocyanate groups previously impregnated with a polymer polyol, a plasticizer and a urethanization reaction catalyst in this way. Is introduced into the above-mentioned kneading and molding machine, followed by heating and melt-mixing under shearing force after the isocyanate compound having the formula (I) and the polymer polyol not impregnated in PVC are mixed.

In the present invention, by forming a laminate including a layer composed of the above-mentioned PVC-PU composite, a laminate having excellent feel, less stickiness and non-stickiness is obtained. And the layer which comprises the laminated body of this invention is this PVC-PU
Other than the layer composed of the composite, a layer composed of any material may be used.For example, cloth, nonwoven fabric, synthetic fiber, artificial leather, synthetic leather, fur, leather, metal, rubber, thermoplastic elastomer, thermoplastic resin, heat Curable resin, polymer foam, paper, wood, glass, stone, ceramics, etc., may be used alone or in combination of two or more,
Further, a layer composed of these may have a multilayer structure.

Examples of the cloth include silk, cotton, hemp, tetron and the like.

As the nonwoven fabric, for example, cotton, rayon, acetate, nylon, polyester and the like are used alone or in combination.

As the synthetic fiber, for example, polyester,
Nylon, acrylic, etc. are used alone or in combination.

As artificial leather and synthetic leather, for example, P
U, PVC and the like are used.

As fur and leather, for example, mink, fox,
Rabbit, tongue, cow, horse, sheep, kangaroo, pig, crocodile, snake and the like are used.

As the metal, for example, iron, copper, stainless steel, titanium steel, aluminum, nickel, brass, nichrome, manganese steel, and other non-ferrous metal materials are used.

Examples of the rubber include butadiene rubber, styrene butadiene rubber (including hydrogenated products), isoprene rubber, acrylonitrile butadiene rubber (including hydrogenated products), acrylic rubber, ethylene propylene rubber, butyl rubber, silicone rubber, and fluoro rubber Chloroprene, chlorinated polyethylene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene rubber, urethane rubber, natural rubber and the like are used alone or in combination.

Examples of the thermoplastic elastomer include styrene-butadiene-based thermoplastic elastomer, styrene-isoprene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, PVC-based thermoplastic elastomer, PU
Thermoplastic elastomers, ester thermoplastic elastomers, amide thermoplastic elastomers, fluorine thermoplastic elastomers, silicone thermoplastic elastomers, etc. are used alone or in combination.

Examples of the thermoplastic resin include acrylic resin, acetal resin, fluororesin, polyamide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyvinylidene chloride, PVC, polypropylene, polyethylene, ethylene-vinyl acetate copolymer and other polyolefins. , Polycarbonate, polystyrene,
Polyphenylene sulfide, liquid crystal polymer, acrylonitrile-butadiene-styrene resin and the like are used alone or in combination.

As the thermosetting resin, for example, an aniline resin, a urea resin, a melamine resin, an epoxy resin, a phenol resin, an unsaturated polyester resin, an alkyd resin, an allyl resin or the like is used alone or in combination.

As the polymer foam, for example, PVC,
Those using PU, polystyrene, polyolefin or the like are used alone or in combination as a foam.

As the paper, for example, wrapping paper such as kraft paper, insulating paper such as laminated paper and condenser paper, construction paper, crepe paper, printing paper, sanitary paper, decorative paper, colored paper, Japanese paper and the like can be used.

As the wood, for example, hardwoods such as beechwood and birchwood; softwoods such as cedar and pine; pulpwood can be used.

As the glass, for example, silicate glass such as E glass and alkali silicate glass, quartz glass, decorative glass, phosphate glass, tempered glass, and sheet glass such as laminated glass can be used.

As the stone material, for example, marble, artificial stone and the like can be used.

Examples of the ceramic include cements such as alumina cement and mixed cement; alumina refractories;
Refractories such as basic refractories; ceramics such as porcelain, stoneware and earthenware; refractory bricks such as dolomite bricks; bricks such as decorative bricks can be used.

The laminate including a layer composed of the PVC-PU composite according to the present invention has a structure of two or more layers, and there is no particular limitation on the structure and order.

In order to produce a laminate including a layer comprising the PVC-PU composite according to the present invention, for example, multilayer extrusion molding, multilayer injection molding, extrusion lamination, hot melt lamination, dry lamination, wet lamination, etc. Molding methods such as molding, multilayer inflation molding, and multilayer blow molding.

Further, a layer comprising a PVC-PU composite and cloth, nonwoven fabric, synthetic fiber, artificial leather, synthetic leather, fur, leather, metal, rubber, thermoplastic elastomer, thermoplastic resin, thermosetting resin, paper, One or more layers selected from the group consisting of wood, glass, stone, and ceramic are laminated with an adhesive, a pressure-sensitive adhesive, hot melt, etc.
High frequency welder, heat seal, impulse seal,
Thermal bonding may be performed by ultrasonic bonding or the like.

The PVC, polymer polyol, isocyanate compound having three or more isocyanate groups, a plasticizer, and a urethanization reaction catalyst according to the present invention are subjected to shearing force.
P obtained by urethane reaction while mixing under heating and melting
The laminate including the layer composed of the VC-PU composite includes, for example, a conveyor belt, a resin conveyor belt, a steeply inclined conveyor,
Conveying conveyor belts such as cylindrical conveyor belts; power transmission belts such as V belts and toothed belts; braided hoses, cloth wound hoses, high pressure hoses, suction hoses,
Duct hoses, spray hoses, hoses for water supply and drainage, pressure-resistant reinforcing hoses, antistatic hoses, etc .; anti-vibration rubbers for automobiles, railways, industrial machines, construction and civil engineering, fenders; printing rolls Industrial rolls such as papermaking rolls, spinning rolls, ironmaking rolls, and dyed fiber rolls; rolls for various machines such as office machine rolls, OA machine rolls, and rolls for automated machines; agricultural machines such as milling machines Rolls; Sheets such as linings, decorative sheets, antistatic sheets, roofing sheets, etc. of various materials including metals; Packing laminates such as mobile phone cases, remote control cases for electric appliances, etc .; Sealing materials, waterproofing materials , Oil seals, mechanical seals, molded seals, dynamic seals such as gland packings; O-rings, seals for fixing gaskets, etc., for capacitors Mouth, sponge product, stopper, catheter, dropper, gasket for syringe, mask, sack, gloves, condom, water pillow, nipple for baby, cap container, rainwear, airbag, diaphragm, rubber dam, gas septum, oil fence, Balls such as flexible containers, golf balls and soccer balls;
Sports floors, cushioning rubber for fences, chains, pavement blocks, automotive boots, weather strips, construction gaskets, seismic isolation rubber, handrails, non-slip, airtight, spacers, laminated glass, waterproof boards, telescopic joints , Thread rubber, rubber cord, hand rail, 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,
Grip parts for golf clubs, tennis rackets, ski poles, etc .; toys, masks, shoes, rubber feet, tubes, packing for electric appliances, industrial parts, etc .; sealants, sheets, electric parts, electronic parts, semiconductive films, antistatic films Films such as pharmaceutical films; can be used for tires, precision equipment, vibration-absorbing materials for precision processing equipment, sporting goods, daily goods, seats, etc.

[0057]

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

Example 1 100 parts by weight of an ethylene-vinyl chloride copolymer (manufactured by Taiyo Vinyl Co., Ltd., trade name: TE-2800) obtained by a suspension polymerization method in a Henschel mixer having an internal volume of 20 liters, magnesium stearate 1 part by weight (hereinafter referred to as Mg stearate), microwax (manufactured by Nippon Seiro Co., Ltd.,
5 parts by weight of LUVAX 2191), 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: BP-
331) 1.5 parts by weight were charged and stirred at a rotation speed of 950 rpm for 1 minute. Separately, a polymer polyol (manufactured by Nippon Polyurethane Co., Ltd., trade name Nipporan 4)
067, number average molecular weight 2000) 50 parts by weight, DOP1
A mixture prepared by mixing 00 parts by weight with 0.15 parts by weight of dibutyltin dilaurate (a urethanization reaction catalyst) for 1 minute was prepared. This 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.

257.65 parts by weight of the obtained powder was added in a volume of 1
The mixture was charged into a Banbury mixer of 700 cc at a set temperature of 110 ° C., and stirred at a constant rotation speed. Apart from this,
Hexamethylene diisocyanate modified isocyanurate (Coronate H, manufactured by Nippon Polyurethane Co., Ltd.)
X) 34 parts by weight of a polymer polyol heated to 80 ° C. (Nipporan 406, manufactured by Nippon Polyurethane Co., Ltd.)
7, 216 parts by weight (NCO / O)
(H molar ratio = 0.65) and mixed for 1 minute to prepare a mixture, and the mixture was poured from a Banbury mixer inlet. The content was 1540 g in total. The mixture was heated and melted under a shearing force, and was discharged when the temperature of the melted mixture reached 175 ° C.

The hardness of the obtained PVC-PU composite (JI
SK6301, type A) was 22.

The obtained PVC-PU composite is granulated,
Extrusion was performed using a 0 mm single screw extruder (trade name: Labo Plast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.), and the outer diameter was 2 mm.
Form a roll of 2mm, inner diameter 10mm, length 20cm
Cut into pieces.

[0062] A stainless steel roll having a diameter of 11 mm was inserted into the roll, and a roll as a laminate was prepared as a metal.

The obtained roll had a low hardness, had no stickiness, and had little adhesion of dirt.

Example 2 In the same manner as in Example 1, a PVC-PU composite was obtained.

The PVC-PU composite was rolled into a 200 micron thick film on an 8 inch roll. The roll temperature was 165 ° C.

The obtained film was cut into a 10 cm square, and sandwiched between glass sheets to obtain a three-layer laminate of glass / PVC-PU composite / glass.

The obtained laminated glass had a good texture without oozing out of the liquid component which causes stickiness.

Example 3 In the same manner as in Example 2, a PVC-PU composite film was obtained.

The obtained film was cut into 15 cm squares and bonded with cotton by hot pressing to obtain a laminate of a PVC-PU composite / cotton.

The obtained cross lamination has a good touch and PV
The C-PU composite followed the deformation of the cotton and had less adhesion of dirt due to stickiness.

Example 4 100 parts by weight of an ethylene-vinyl chloride copolymer (manufactured by Taiyo Vinyl Co., Ltd., trade name: TE-2800) obtained by a suspension polymerization method in a Henschel mixer having an internal volume of 20 liters, and methyl methacrylate- Alkyl acrylate copolymer (trade name: Metablen P531, manufactured by Mitsubishi Rayon Co., Ltd.)
3 parts by weight, 2 parts by weight of barium stearate as a stabilizer, and 1.5 parts by weight of perchloric acid-treated hydrotalcite (trade name: BP-331, manufactured by Nissan Ferro-Organic Chemical Co., Ltd.) were charged at a rotation speed of 950 rpm. Stirred for minutes. Also,
Separately, a mixture of 50 parts by weight of DOP and 0.01467 parts by weight of dibutyltin dilaurate (catalyst for urethanization reaction) was prepared. This was added to the above-mentioned Henschel mixer, and the mixture (4 kg in total) was stirred and mixed until the temperature of the mixture reached 120 ° C. The mixture became a powdery mixture that could easily flow.

156.551467 parts by weight of the obtained powder was charged into a Banbury type mixer (manufactured by Minami-Senju Seisakusho Co., Ltd.) having an internal volume of 1.7 liters and a set temperature of 110.degree.
Stirred at pm. The temperature of the powder at the time of charging was 110 ° C. Separately, 50 parts by weight of heated DOP (di-2-ethylhexyl phthalate) and 16.3 parts by weight of a modified isocyanurate of hexamethylene diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) After mixing for 1 minute, further heated 1,4-butanediol and adipic acid are subjected to condensation polymerization to obtain a polymer polyol (Nipporan 4010, trade name, manufactured by Nippon Polyurethane Co., Ltd., number average molecular weight 2000) 77. One part by weight (NCO / OH molar ratio = 1.1) was added and mixed for 1 minute to prepare a mixture. Subsequently, the mixed solution was poured from the inlet of the Banbury-type mixer, and was heated and melt-mixed under a shearing force at 100 rpm, and was discharged when the temperature of the molten mixture reached 175 ° C.

Further, the obtained PVC-PU composite is granulated, and the PVC-PU composite is put into a 40 mm single screw extruder, and a vinyl chloride polymer (manufactured by Taiyo PVC Co., Ltd.) is placed in a 30 mm single screw extruder. Hard-PVC made by mixing 1 part by weight of tribasic lead sulfate, 1.5 parts by weight of lead stearate, and 0.5 parts by weight of calcium stearate with respect to 100 parts by weight, and used for doors. Two-color extrusion molding of packing (packing laminate) was performed. The obtained packing laminate is placed on a rigid PVC portion (thickness 1 mm, width 8 mm).
C-PU composite (1mm thick, 4mm outer diameter semicircular)
Was fused.

The obtained door packings (hard PVC and PV
The laminate of the C-PU composite) had little set and was soft, had good sealing properties, and had little sticking of dirt due to stickiness.

[0075]

The laminate and the molded article obtained therefrom according to the present invention are low in hardness, excellent in compression set characteristics, excellent in elasticity, less sticky, and therefore have less adhesion of dirt.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 75/04 NGH C08L 75/04 NGH

Claims (6)

[Claims] 1. A vinyl chloride polymer obtained by subjecting a vinyl chloride polymer, a polymer polyol, an isocyanate compound having three or more isocyanate groups, a plasticizer, and a urethanation reaction catalyst to a urethane reaction while heating and mixing under shearing force. A laminate comprising a layer comprising a polymer-polyurethane composite. 2. A cloth, non-woven fabric, synthetic fiber, artificial leather, synthetic leather, fur, leather, metal, rubber, thermoplastic elastomer,
The laminate according to claim 1, comprising one or more layers selected from the group consisting of a thermoplastic resin, a thermosetting resin, a polymer foam, paper, wood, glass, stone, and ceramic. 3. The laminate according to claim 1, comprising a metal layer, a cloth, a nonwoven fabric, a layer made of synthetic fibers, and a layer made of a thermoplastic resin. 4. A roll comprising the laminate according to claim 1. 5. A cross-laminate comprising the laminate according to any one of claims 1 to 3. 6. A packing comprising the laminate according to claim 1.