JPH06136257A - Flexible resin composition having excellent moldability - Google Patents

Abstract

PURPOSE:To provide a flexible resin composition having excellent moldability, especially sheet-formability. CONSTITUTION:A flexible resin composition having excellent moldability is produced by compounding (A) 1-100 pts.wt. of a thermoplastic polyurethane with (B) 99-0 pts.wt. of a copolymer produced by copolymerizing a rubbery polymer with one or more monomers selected from an alpha,beta-unsaturated carboxylic acid alkyl ester and unsaturated monomers copolymerizable with the alkyl ester and (C) 0-70 pts.wt. of a copolymer produced by the graft- copolymerization of one or more kinds of monomers selected from an aromatic vinyl compound, a vinyl cyanide compound and monomers copolymerizable with the above compounds (the sum of A to C is 100 pts.wt.) and compounding the obtained composition with (D) 0.1-25 pts. wt. of a polyolefin compound modified with an alpha,beta-unsaturated dicarboxylic acid anhydride monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible resin composition having excellent moldability, and more particularly to a flexible resin composition having excellent sheet moldability.

[0002]

2. Description of the Related Art Conventionally, soft vinyl chloride, thermoplastic polyurethane resin and the like have been widely used for sheet materials having excellent flexibility because of their productivity and colorability. Among them, molding processing of thermoplastic polyurethane-based material, for example, when performing roll processing, in order to facilitate the moldability, resin acid lubricant, ester lubricant, alcohol lubricant, which is a general lubricant, Metal soap and polyethylene wax are often used. However, when such a lubricant is used, it is inferior in the circumference of the roll bank, the roll adhesiveness of the material becomes strong over time, it becomes difficult to continuously perform sheet forming, and a formed sheet having a uniform thickness. There were drawbacks such as not being able to obtain.

Further, when the amount of the lubricant is increased in order to eliminate the stickiness of the roll, the lubricant adheres to the surface of the processing funnel (referred to as plate-out), the lubricant remains on the surface of the molded sheet, or the time elapses. Since it also appears on the surface (called bleed-out), it causes a new problem such as not being able to obtain a sheet having a uniform surface gloss and a uniform wall thickness, and thus there is a problem that its use is limited. That is, when a composition containing a thermoplastic polyurethane is molded and processed, there are drawbacks such as an increase in roll adhesiveness and poor surface gloss due to bleed-out.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a flexible composition exhibiting excellent sheet moldability when molding a thermoplastic polyurethane type flexible composition.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a flexible composition obtained from a thermoplastic polyurethane and a rubber-based copolymer has
The present inventors have found that a resin composition excellent in molding processability can be obtained by blending a polyolefin compound modified with an α, β-unsaturated dicarboxylic acid anhydride monomer, and completed the present invention.

That is, the present invention comprises (A) 1 to 100 parts by weight of thermoplastic polyurethane, (B) a rubber-like polymer and α,
99 to 0 parts by weight of a copolymer obtained by copolymerizing a β-unsaturated carboxylic acid alkyl ester and one or more monomers selected from the group of unsaturated monomers copolymerizable therewith, and ( C) Grafting a monomer comprising one or more selected from the group of aromatic vinyl compounds, vinyl cyanide compounds and unsaturated monomers copolymerizable therewith in the presence of a rubbery polymer. A composition comprising 0 to 70 parts by weight of the copolymerized copolymer and having 100 parts by weight of each component in total was modified with (D) α, β-unsaturated dicarboxylic acid anhydride monomer. The present invention relates to a flexible resin composition having an excellent molding processability, which comprises 0.1 to 25 parts by weight of a polyolefin compound.

The present invention will be described in detail below. The thermoplastic polyurethane of the component (A) of the present invention is obtained by reacting one or more kinds selected from a diisocyanate compound, a compound containing two or more hydroxyl groups, and a compound having a functional group capable of reacting with an isocyanate group. It is a thing.

As the diisocyanate, aromatic, aliphatic and alicyclic diisocyanate compounds are used.
For example, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
4,4'-diphenyl diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, o-, m- or p
-Diisocyanates such as xylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane diisocyanate and dicyclohexylmethane diisocyanate are used.

The compound containing two or more hydroxyl groups has a molecular weight of 300 to 10,000, preferably 500.
˜5,000 and containing an amount that reacts with diisocyanate. These are glycols having 2 to 8 carbon atoms, such as ethylene, trimethylene, tetramethylene, hexene, and propylene glycol, and saturated aliphatic dicarboxylic acids having 4 to 10 carbon atoms, adipic acid, succinic acid, glutaric acid, sperin. Acid, sebacic acid or the like or a condensate obtained from phthalic acid which is an aromatic dicarboxylic acid, isophthalic acid, terephthalic acid or the like, polyester glycols obtained by copolymerization of an alkylene glycol and a lactone group, for example, polylactone diol, Polycaprolactone diol, polyenanthlactone diol, etc., a condensate of alkylene oxide having 2 to 4 carbon atoms, a condensate of alkylene oxide having 2 to 4 carbon atoms and alkylene glycol, polyalkylene glycol having 2 to 4 carbon atoms, Tetrahydro Polyalkylene ether glycols obtained by such run of the ring-opening polymerization, addition, dihydroxy polyester amides, dihydroxy polyacetals, dihydroxy polyalkylene ethers, dihydroxy polycarbonates such as may be used as well. Among these, polytetramethylene ether glycol, dihydroxy polyethylene adipate, polyethylene glycol, polypropylene glycol and the like are suitable.

Further, in addition to the diol, a compound having a functional group capable of reacting with an isocyanate group, such as ethylene glycol, which is a saturated aliphatic glycol having 2 to 6 carbon atoms, as a molecular chain length regulator. 1,2-propylene glycol, 1,3-propylene glycol, butane 1,2-diol, butane 1,3-diol, butane 1,4-diol, butane 2,3-diol and butane 2,4-diol, hexane Examples thereof include diols, and aromatic glycols such as 1,4-xylylene glycol and phenylene bis- (β-hydroxyethyl ether).

In addition, for example, a small amount of trifunctional or higher functional alcohols, trimethylolpropane, glycerin,
Hexanetriol or the like may be used at the same time. The thermoplastic polyurethane is produced by a known method using the above compound.

The component (B) used in the present invention is at least one selected from the rubbery polymer (I), α, β-unsaturated carboxylic acid alkyl ester and other copolymerizable monomers. It is a copolymer obtained by copolymerizing a monomer consisting of

Examples of the rubber-like polymer (I) include diene-based copolymers such as polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, butadiene-isoprene rubber, polyisobutylene and C1-C13. Examples include polyalkyl acrylates having an alkyl, such as ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Further, polyalkylmethacrylates having alkyl having 1 to 13 carbon atoms, for example, butylmethacrylate, amylmethacrylate, hexylmethacrylate, octylmethacrylate, 2-ethylhexylmethacrylate and the like can be mentioned.

Further, within a range that does not impair the flexibility of the rubber-like polymer, ethylene glycol diacrylate,
It may be a copolymer crosslinked using a polyfunctional compound such as diethylene glycol diacrylate, propylene dimethacrylate, dicyclopentadiene acrylate, divinylbenzene, diallyl phthalate, triallyl isocyanurate or triallyl cyanurate.

Further, other graft copolymerizable ethylene-propylene rubber, ethylene-propylene diene rubber, styrene-butadiene block copolymer, hydrogenated polymer of styrene-butadiene block copolymer,
Styrene-isoprene block copolymer, styrene-
Hydrogenated polymers of isoprene-based block copolymers, silicone rubbers, etc. can also be used. These rubbery polymers can be obtained by emulsion polymerization, suspension polymerization, and a method of emulsifying the polymer with an emulsifier or the like.

Further, as the α, β-unsaturated carboxylic acid alkyl ester copolymerized with these rubber-like polymers,
An alkyl acrylate having 1 to 13 carbon atoms in the alkyl group, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, Examples thereof include methoxyethyl acrylate and ethoxyethyl acrylate.

Alkylmethylmethacrylate having 1 to 13 carbon atoms in the alkyl group, such as methylmethacrylate, ethylmethacrylate, butylmethacrylate,
Propyl methacrylate, cyclohexyl methacrylate, amyl methacrylate, hexyl methacrylate,
Examples thereof include octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and diethylaminoethyl methacrylate. Among these, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, butyl acrylate,
2-ethylhexyl acrylate is preferred. These monomers may be used as a mixture.

Further, one or more monomers selected from unsaturated monomers copolymerizable with these may be copolymerized within a range not impairing the flexibility of the composition. Examples of these monomers include halogenated styrenes such as styrene-, α-methylstyrene, chlorinated styrene and brominated styrene, and aromatic vinyl compounds such as vinyltoluene and dimethylstyrene. Further, examples thereof include esters obtained from unsaturated carboxylic acids such as allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid and fumaric acid.

The proportion of monomers in these copolymerizations is
α, β-Unsaturated carboxylic acid alkyl ester 30 to 10
0% by weight, preferably 50 to 90% by weight, of monomers selected from the group of unsaturated monomers copolymerizable therewith, 0
-60% by weight, preferably 10-50% by weight.

The proportion of the monomer copolymerizable with the rubber-like polymer in the copolymer (B) is such that the rubber-like polymer (I) has a ratio of 5 to 5.
95 parts by weight, preferably 10 to 80 parts by weight, and the monomer to be copolymerized is 5 to 95 parts by weight, preferably 20 to 9 parts by weight.
The ratio is 0 parts by weight. When the amount of the rubber-like polymer is less than 5 parts by weight, the flexibility of the composition is poor, and when it exceeds 95 parts by weight, the tackiness of the roll is high and the roll processability is poor. If the amount of the monomer is less than 5 parts by weight, roll processability is poor and 95
If it exceeds the weight part, the flexibility is poor. These copolymerizations are
It is carried out by graft copolymerization in which the rubbery copolymer and the monomer are combined or core-shell type multiphase decoupling copolymerization, etc., and is manufactured by known bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization. It

The component (C) used in the present invention is selected from the group of aromatic vinyl compounds, vinyl cyanide compounds and unsaturated monomers copolymerizable therewith in the presence of the rubbery polymer (I). It is an aromatic vinyl copolymer obtained by graft-copolymerizing one or more kinds of monomers selected from As the rubber-like polymer (I), the same rubber-like polymer as the component (B) can be used.

As the aromatic vinyl compound, for example, halogenated styrene such as styrene, α-methylstyrene, chlorinated styrene and brominated styrene, and aromatic vinyl compound such as alkylated styrene such as vinyltoluene and dimethylstyrene. Is used. Of these, styrene and α-methylstyrene are preferable. As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile, etc. are used.

Other copolymerizable monomers include
α, β-unsaturated carboxylic acid alkyl ester, for example,
Acrylates such as methyl acrylate, cyclohexyl acrylate, benzyl acrylate, glycidyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, hydroxypropyl methacrylate, diethylamino Examples thereof include methacrylates such as ethyl methacrylate, allyl glycidyl ether, esters obtained from unsaturated carboxylic acids such as acrylic acid, methacrylic acid, hydroxyethyl methacrylate, itaconic acid and fumaric acid.
Of these, methyl acrylate, methyl methacrylate, ethyl methacrylate and glycidyl methacrylate are preferable. These monomers may be used as a mixture.

The proportion of each monomer is such that the aromatic vinyl compound is 10 to 90% by weight, preferably 30 to 70% by weight, and the vinyl cyanide compound is 10 to 50% by weight, preferably 20 to 40%. % By weight and other copolymerizable monomers are 0 to 40% by weight, and the total amount of monomers is 100% by weight.
This is the configuration. Graft copolymerization is performed by mixing these or in stages. 1 aromatic vinyl compound
If it is less than 0% by weight, the tear strength is poor, and if it exceeds 90% by weight, the flexibility is poor. 20 vinyl cyanide compounds
If it is less than wt%, the tear strength will be poor, and if it exceeds 40 wt%, the flexibility will be poor.

The proportion of the rubber-like polymer and the monomer to be graft-copolymerized in the graft copolymer (C) is such that the rubber-like polymer (I) is 5 to 95 parts by weight, preferably 10 to 80 parts by weight. The amount of the monomer to be graft-copolymerized is 5 to 95 parts by weight, preferably 20 to 90 parts by weight.
If the amount of the rubber-like polymer is less than 5 parts by weight, the flexibility of the composition will be poor, and if it exceeds 95 parts by weight, the tackiness of the roll will be high.
Roll processability is poor. Further, when the proportion of the monomer is less than 5 parts by weight, the roll adhesiveness becomes high and the roll processability becomes poor, and when it exceeds 95 parts by weight, the flexibility becomes poor. This graft copolymer (C) is produced by known bulk polymerization, emulsion polymerization, suspension polymerization, solution polymerization and the like.

The component (D) is a polyolefin compound modified with an α, β-unsaturated dicarboxylic acid anhydride monomer. As the polyolefin compound, homopolymers such as low density, medium density and high density polyethylene, polypropylene, polybutene-1 and poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer , Ethylene-hexene-1 copolymer,
Ethylene-4-methylpentene-1 copolymers and ethylene-octene-1 copolymers and other ethylene-based copolymers with other α-olefins, ethylene-propylene block copolymers and other propylene Copolymer with other α-olefin as the main component, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-
Examples thereof include methacrylic acid copolymers and ethylene-methacrylate ester copolymers. Of these, low density, medium density and high density polyethylene and polypropylene are preferred.

The α, β-unsaturated dicarboxylic acid anhydride monomer used for the modification may be maleic anhydride. The blending ratio of the polyolefin compound and the α, β-unsaturated dicarboxylic acid anhydride monomer is 80 to 99.9 parts by weight of the polyolefin compound, preferably 90 to
95 parts by weight and 0.1 to 20 parts by weight of α, β-unsaturated dicarboxylic acid anhydride monomer, preferably 5 to 10 parts by weight. If the proportion of the α, β-unsaturated dicarboxylic acid anhydride monomer is less than 0.1 part by weight, plate-out and bleed-out will occur, resulting in poor sheet moldability. If it exceeds 20 parts by weight, the lubricating effect of the composition is poor.

As the modification method of the polyolefin compound, a polyolefin compound and an α, β-unsaturated dicarboxylic acid anhydride monomer are blended or an organic peroxide is further blended, and then a Banbury mixer, a kneader, an extruder, etc. The method of heating, melting, and denaturing can be mentioned. Examples of the organic peroxide used for the modification include dicumyl peroxide (DCP), dibutyl peroxide, t-
Butyl peroxybenzoate (TBPB), t-butyl cumyl peroxide, benzoyl peroxide, etc. can be used.

The ratio of the components constituting the composition of the present invention is
1 to 100 parts by weight, preferably 10 to 70 parts by weight, of the thermoplastic polyurethane (A), 99 to 0 parts by weight, preferably 90 to 30 parts by weight, of the copolymer (B), aromatic vinyl-based graft copolymer 0 to 70 parts by weight of (C), preferably 5
.About.40 parts by weight, and a polyolefin compound (D) modified with an .alpha.,. Beta.-unsaturated dicarboxylic acid anhydride monomer,
The composition is 25 parts by weight, preferably 1 to 10 parts by weight.

If the amount of component (A) is less than 10 parts by weight, flexibility and mechanical strength are poor, and if it exceeds 70 parts by weight, sheet formability is poor. Further, the component (B) is for controlling the flexibility and the moldability, and if it is less than 30 parts by weight, the sheet moldability is poor, and if it exceeds 90 parts by weight, the flexibility is lowered.

The component (C) is blended in order to further improve the tear strength, and if it is less than 5 parts by weight, the improving effect is poor, and if it exceeds 40 parts by weight, the flexibility is lowered. The component (D) is blended in order to improve the moldability, and if it is less than 1 part by weight, the moldability is inferior, and if it exceeds 15 parts by weight, the tear strength is lowered.

The compounding method of the present invention is not particularly limited, and powders and granules are mixed by a known technique such as a Henschel mixer, a tumbler, a blender and the like, and the mixture is mixed with an extruder, a kneader, a mixer or a roll. And the like, and then roll-processing or calendering the resin composition, or directly rolling or calendering powder or granules of each component. Further, in the sheet processing of the present invention, if desired, each additive component, for example, an antioxidant, an ultraviolet absorber, a flame retardant, a flame retardant aid, a plasticizer, and a light, as long as the physical properties are not impaired. Stabilizer, antistatic agent, dye,
You may mix | blend a pigment, an organic filler, an inorganic filler, etc. beforehand.

[0033]

The present invention will be described in detail with reference to the following examples, which are not intended to limit the present invention.

Reference Example 1 Copolymer (B-1) 750 parts by weight of deionized water and 3 parts by weight of an emulsifier (sodium dodecylbenzene sulfonate) were placed in a polymerization tank and heated to 70 ° C. in a nitrogen stream while stirring. The mixture is warmed and, as the first-stage polymerization, 600 parts by weight of butyl acrylate, 10 parts by weight of triallyl isocyanurate, 0.2 parts by weight of ammonium persulfate, and 0.7 parts by weight of an emulsifier (sodium dodecylbenzenesulfonate). Polymerization was carried out by adding the mixed solution over 3 hours.

Then, in the second stage polymerization, a mixed solution of 290 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, 200 parts by weight of styrene, 2 parts by weight of cumene hydroperoxide and 0.7 part by weight of t-dodecyl mercaptan. And 500 parts by weight of distilled water, 1.0 parts by weight of sodium formaldehyde sulfoxylate, ferrous sulfate (F
Polymerization was carried out by adding an aqueous solution in which 0.01 parts by weight of eSO ₄ .7H ₂ O) and 0.4 parts by weight of ethylenediamine tetraacetic acid / 2Na salt were dissolved for 6 hours. After the addition was completed, stirring was continued for another hour to complete the polymerization.
The polymerization rate was 95%. The obtained copolymer latex was coagulated and salted out, washed and dried to obtain a white solid.

Reference Example 2 Copolymer (B-2) Same as Reference Example 1 except that 470 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, and 30 parts by weight of glycidyl methacrylate were used as the second-stage polymerization. Then, polymerization was performed. The polymerization rate was 93%.

Reference Example 3 Copolymer (B-3) 1000 parts by weight of a butadiene rubber latex (40% by weight in terms of solid content) having a weight average particle diameter of 0.2 μm, an emulsifier (potassium alkenylsuccinate (alkenyl group is C _13- ). C ₁₅
2) parts by weight are charged into a polymerization tank and stirred,
The temperature was raised to 70 ° C in a nitrogen stream, and 290 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, 200 parts by weight of styrene, and cumene hydroperoxide 2 were added.
Parts by weight, 0.7 parts by weight of t-dodecyl mercaptan and 500 parts by weight of distilled water, 1.0 part by weight of sodium formaldehyde sulfoxylate, ferrous sulfate (FeSO ₄
Polymerization was carried out by adding an aqueous solution in which 0.01 parts by weight of 7H ₂ O) and 0.4 parts by weight of ethylenediaminetetraacetic acid / 2Na salt were dissolved for 6 hours. After the addition was completed, stirring was continued for another hour to complete the polymerization. The polymerization rate was 96%. The obtained copolymer latex is
After salting out with a dilute sulfuric acid aqueous solution, washing and drying were performed to obtain a white solid.

Reference Example 4 Copolymer (B-4) Monomer, 470 parts by weight of methyl methacrylate, 10 parts by weight of methyl acrylate, 3 parts of glycidyl methacrylate were used.
Polymerization was carried out in the same manner as in Reference Example 3 except that 0 part by weight was used. The polymerization rate was 93%.

Reference Example 5 Copolymer (C-1) 1000 parts by weight of a butadiene rubber latex having a weight average particle diameter of 0.3 μm (40% by weight in terms of solid content) and 2 parts by weight of an emulsifier (disproportionated potassium rosinate). It was charged in a polymerization tank and heated to 70 ° C. in a nitrogen stream while stirring, to which 150 parts by weight of acrylonitrile, 350 parts by weight of styrene,
A mixture of 2 parts by weight of cumene hydroperoxide and 0.5 parts by weight of t-dodecyl mercaptan, and 500 parts by weight of distilled water were added to 1.0 part of sodium formaldehyde sulfoxylate.
Parts, ferrous sulfate _{(FeSO 4 · 7H 2 O)} 0.01
Polymerization was carried out by adding an aqueous solution in which 0.3 part by weight of ethylenediaminetetraacetic acid / 2 Na salt was dissolved for 6 hours. After the addition was completed, stirring was continued for another hour to complete the polymerization. The polymerization rate was 95%. The obtained copolymer latex was washed with water after coagulating and salting out.
Drying gave a white solid.

Reference Example 6 Copolymer (C-2) Polymerization was carried out in the same manner as in Reference Example 1 except that 150 parts by weight of acrylonitrile and 350 parts by weight of styrene were used as the second-stage polymerization. The polymerization rate was 93%.

Reference Example 7 Modified polyolefin (D-1) 100 parts by weight of polypropylene (average molecular weight 15,000), 1 part by weight of maleic anhydride and 0.2 part by weight of t-butylperoxybenzoate were mixed in a Henschel mixer. After that, modification was performed with an extruder in which the cylinder temperature was 200 to 220 ° C.

Reference Example 8 Modified polyolefin (D-2) 100 parts by weight of polypropylene (average molecular weight of 5,000), 1 part by weight of maleic anhydride and 0.3 part by weight of dicumyl peroxide were mixed in a Henschel mixer,
The modification was performed with an extruder having a cylinder temperature of 200 to 220 ° C.

Reference Example 9 Modified Polyolefin (D-3) 100 parts by weight of polyethylene (average molecular weight 4,000), 2 parts by weight of maleic anhydride and 0.5 part by weight of dicumyl peroxide were mixed in a Henschel mixer, and then mixed. With an extruder with a cylinder temperature of 200-220 ° C,
Made a metamorphosis.

Example 1 Thermoplastic polyurethane (diphenylmethane-4,4'-
Thermoplastic polyurethane derived from polyester glycol obtained from diisocyanate (MDI), butanediol and adipic acid; JIS hardness A 85) (A-
1) 80 parts by weight of the graft copolymer (B
-1) 20 parts by weight and modified polypropylene (D-1) 10
Parts by weight were blended and premixed with a Henschel mixer.
Next, using an extruder, they were melt mixed and pelletized.
The pellets were kneaded with a two-roll kneading roll heated to 180 ° C. to form a sheet. This sheet was pressed with a press machine at 170 ° C. to form a sheet having a thickness of 1 mm, and the sheet physical properties were measured.

The characteristics shown in the following examples and comparative examples were measured by the following methods. (1) Roll processability (1-1) Initial processability It heated at 170 degreeC. Put the pellets in the roll gap,
A 0.5 mm thick sheet was taken out. The appearance was observed, the smoothness of the sheet surface was observed, and the judgment was made according to the following judgment criteria. ○: Initially, it takes a short time to wind around the roll and is easy to process. In addition, the thickness of the sheet is uniform and the thickness is uniform. Δ: Initially, the sheet is wrapped around a roll and can be processed, but the sheet has uneven thickness and becomes uneven. X: Those that are difficult to process because they stick to the roll at the initial stage. Sheet forming is difficult. XX: A material to which a processing aid adheres on the roll (plates out) and is unsuitable for processing.

(1-2) Sustainable workability In the same manner as in (1-1), it was wound on a roll to
A sheet of 0.5 mm was taken out by the same operation for 60 minutes at intervals of 0 minutes. The appearance was observed, the smoothness of the sheet surface was observed, and the judgment was made according to the following judgment criteria. Good: A sheet can be processed without sticking to the roll even after 40 minutes or more. In addition, the thickness of the sheet is uniform and the thickness is uniform. Δ: Roll adhesiveness in the range of 10 to 30 minutes, but sheet processing is possible. However, the sheet will have uneven thickness and become uneven. X: The product is difficult to process because it sticks to the roll within 10 minutes. Sheet forming is difficult.

(2) Tensile Strength and Elongation A JIS No. 1 dumbbell was prepared from the sheet and JIS K
It measured according to 6301. (3) Tear strength A JIS B test piece was prepared from the sheet, and JIS K63
It measured according to 01. (4) Hardness Measured according to JIS K6301 (JIS A).

Examples 2 to 10 Pellets having the composition ratios shown in Tables 1 and 2 were used as pellets, and the following operations were performed in the same manner as in Example 1 to evaluate the respective physical properties, and the results are shown in Tables 1 and 2. The resins shown below were used as the blending resin. (A) Thermoplastic polyurethane (A-2) Thermoplastic polyurethane derived from MDI and polycaprolactone diol (JIS hardness A 8
0) (A-3) Thermoplastic polyurethane derived from polyester glycol obtained from MDI, ethylene glycol and adipic acid (JIS hardness A 65)

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Comparative Examples 1 to 8] Pellets having the composition ratios shown in Tables 3 and 4 were used as pellets, and the following operations were performed in the same manner as in Example 1 to evaluate the respective physical properties. It was shown to. In Comparative Example 6, 1 part by weight of calcium stearate was used as a processing aid, and in Comparative Examples 7 and 8, 1 part by weight and 3 parts by weight of polyethylene wax were used.

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

From the comprehensive table of Table 5, it can be seen that the composition of the present invention has excellent roll processability and flexibility (hardness (JIS A) and 10% modulus). In addition,
The symbols of the evaluation items in Table 5 have the following meanings.

Evaluation of Roll Workability (Initial) ◯: Initially, the time required to wind the roll is short and the work is easy. The thickness of the sheet is uniform and the thickness is uniform. Δ: Initially, the sheet can be wrapped around the roll, but the sheet has uneven thickness and is uneven. X: It is difficult to process because it sticks to the roll in the initial stage. XX: Processing aid adheres to the roll (plate-out) and processing is unsuitable.

Evaluation of roll processability (sustained) A: A sheet can be processed without sticking to a roll even after 40 minutes or more. Further, the thickness of the sheet is uniform and the thickness is uniform. (Triangle | delta): It is roll adhesiveness within the range of 10 to 30 minutes, but a sheet can be processed However, the sheet has uneven thickness and becomes non-uniform. X: The product sticks to the roll within 10 minutes and is difficult to process.

Sheet processing is difficult.

Evaluation of hardness O: Less than 95. X: 95 or more. 50% modulus ◯: less than 100. X: 100 or more. Evaluation of tear strength ○: 35 or more.

X: Less than 35

[0061]

INDUSTRIAL APPLICABILITY The present invention provides a resin composition containing a thermoplastic polyurethane, a copolymer and a graft copolymer, and a polyolefin modified with an α, β-unsaturated dicarboxylic acid anhydride monomer. By compounding the compound, there is an effect that a flexible resin composition having excellent moldability can be obtained.

Claims (3)

[Claims] 1. (A) Thermoplastic polyurethane 1 to 100
Parts by weight, (B) a rubber-like polymer, an α, β-unsaturated carboxylic acid alkyl ester, and a monomer composed of at least one member selected from the group of unsaturated monomers copolymerizable therewith. Among the group of aromatic vinyl compounds, vinyl cyanide compounds and unsaturated monomers copolymerizable therewith in the presence of 99 to 0 parts by weight of copolymerized copolymer and (C) rubbery polymer. (D) α, for a composition comprising 0 to 70 parts by weight of a copolymer obtained by graft-copolymerizing one or more monomers selected from (D) α,
A flexible resin composition having an excellent molding processability, which comprises 0.1 to 25 parts by weight of a polyolefin compound modified with a β-unsaturated dicarboxylic acid anhydride monomer. 2. The resin composition according to claim 1, wherein the polyolefin compound (D) is polypropylene or polyethylene. 3. The resin composition according to claim 1 or 2, wherein the α, β-unsaturated carboxylic acid anhydride monomer is maleic anhydride.