JP2002114915A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellently flexible resin composition; and a molded product or a laminated product made from the same. SOLUTION: The resin composition comprises a thermoplastic resin (A), a thermoplastic elastomer (B), particularly a polyurethane resin or a polyester resin and an ethylene-vinyl acetate copolymer (C). The molded product or the laminated product can be made from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition containing a thermoplastic resin (A), a thermoplastic elastomer (B), and an ethylene-vinyl acetate copolymer (C), and more particularly to a resin composition having improved toughness. The present invention relates to a so-called highly flexible resin composition having improved brittleness.

[0002]

2. Description of the Related Art Conventionally, flooring made of vinyl chloride resin has been frequently used for flooring of buildings and condominiums,
Many other products containing chlorine-containing resin are also used for building materials, etc.However, chlorine-containing resin products generate a large amount of smoke containing harmful hydrogen chloride gas at the time of fire, which has an adverse effect on the human body. And hinder evacuation and fire fighting. In addition, since a large amount of a plasticizer or a stabilizer is contained, there is a problem in that contamination by bleeding of the plasticizer is observed and the odor is strong.

[0003] As a countermeasure, Japanese Patent Laid-Open No.
No. 45 discloses that calcium carbonate or a mixture of calcium carbonate and aluminum hydroxide is mixed with 100 parts by weight of a base resin obtained by mixing 70 to 30 parts by weight of polypropylene and 30 to 70 parts by weight of an ethylene-vinyl acetate copolymer. ~
A flooring made of a resin composition containing 300 parts by weight,
JP-A-9-317142 discloses that a mixed resin of 30 to 70 parts by weight of polyethylene and 70 to 30 parts by weight of an ethylene-vinyl acetate copolymer is mixed with 50 to 300 parts by weight of an inorganic filler. Japanese Patent Application Laid-Open No. H10-45962 discloses a flooring made of a resin composition of 30-70.
The vinyl acetate content is 71 to 9 parts by weight in polyethylene.
0 to 30% by weight of ethylene-vinyl acetate copolymer.
Floor materials made of a resin composition in which 50 parts by weight and an inorganic filler are blended in a proportion of 50 to 300 parts by weight have been proposed.

[0004]

However, in the technology disclosed in the above publication, since the base resin such as polypropylene or polyethylene is a hard resin, it is attempted to impart flexibility by blending an ethylene-vinyl acetate copolymer. However, it is difficult to sufficiently satisfy moldability and flexibility by simply blending an ethylene-vinyl acetate copolymer, and further improvement is required.

In view of the above, it is an object of the present invention to provide a resin composition having excellent flexibility, and a molded product and a laminate using the same.

[0006]

[Means for Solving the Problems]
In view of the above circumstances, as a result of intensive studies, thermoplastic resin (A), thermoplastic elastomer (B) and ethylene-
The present inventors have found that a resin composition containing a vinyl acetate copolymer (C) can achieve the object, and have completed the present invention.

In the present invention, the use of a thermoplastic elastomer (B) was attempted in order to improve the flexibility of a thermoplastic resin (A) such as a polyethylene resin by changing the idea of the conventional technology and the idea. Although the intended purpose could not be achieved due to poor compatibility of the above, this problem was solved by including an ethylene-vinyl acetate copolymer (C) as a compatibilizer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The thermoplastic resin (A) used in the present invention includes:
There is no particular limitation, and examples include polyolefin-based resins, polyamide-based resins, polyester-based resins, polyether-based resins, polyurethane-based resins, polycarbonate-based resins, acrylic-based resins, and polystyrene-based resins, with polyolefin-based resins being preferably used. . These may be used alone or in combination of two or more.

Examples of such polyolefin resins include various high-density, medium-density, and low-density homopolymers such as polyethylene, polypropylene, polybutene, and polypentene; ethylene-propylene copolymers; 2 to 2 carbon atoms such as 1-hexene
A copolymer with an α-olefin of about 0, an olefin-vinyl acetate copolymer having an olefin content of 90 mol% or more, such as ethylene or propylene, an olefin- (meth) acrylate copolymer, and a metal ion. One or two or more modified ionomer resins or the like, or those obtained by graft-modifying a homo- or copolymer of the above-mentioned polyolefin resin with an unsaturated carboxylic acid or the like can be used arbitrarily. Among them, polyethylene resins are preferable, and those using a metallocene catalyst are useful from the viewpoint of production.

[0010] Among them, particularly, the density is 0.910
It is preferably a crystalline ethylene polymer having a 0.945 g / cm ³ and a melt index (MI) of 0.5 to 50 g / 10 min (according to JIS K 7210),
More preferred melt index (MI) is 0.5 to 2
0 g / 10 minutes (according to JIS K 7210).

The melt index (MI) is 0.5 g /
If it is less than 10 minutes, the fluidity will be reduced, and the melt moldability will be reduced. If it exceeds 50 g / 10 minutes, the tension at the time of melting will be reduced, which is not preferable. As a commercially available product of such a polyethylene resin, for example, “Kernel KF270” manufactured by Nippon Polychem Co., Ltd. and the like can be mentioned.

A typical example of the thermoplastic elastomer (B) used in the present invention is a polyurethane resin or a polyester resin. Any polyurethane resin can be used as long as it is a condensation product of a polyol and a polyisocyanate and exhibits elasticity.

As polyols, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, polyethylene glycol,
Propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-
Butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, Sorbitol,
Polyhydric alcohols such as mannitol, arabitol, xylitol, galactitol, glycerin, polyglycerin, and polytetramethylene glycol, and at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization And polyether polyols.

A polyester polyol which is a condensate of the polyhydric alcohol or polyether polyol with a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid;
Caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol; polyolefin-based polyols; and polybutadiene-based polyols such as hydrogenated polybutadiene polyol are also included.

The polyisocyanate is not particularly limited, and examples thereof include aromatic, aliphatic, cycloaliphatic and alicyclic polyisocyanates. Among them, tolylene diisocyanate, diphenylmethane diisocyanate, water Addition of diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl ) Diisocyanates such as cyclohexane and trimers thereof are preferably used. As the polyurethane-based resin, those in which the polyol segment is a polyester polyol exhibit a remarkable effect. As a commercially available product, "Milactran E-180" manufactured by Nippon Milactran Co., Ltd.
FNAT "is useful.

[0016] The polyester resin is defined as about 20 to 50% by weight of a hard segment and 50 to 50% by weight of a soft segment.
About 80% by weight of condensation, more specifically,
A polyester resin obtained by polycondensing an aromatic dicarboxylic acid, a short-chain glycol and a polyalkylene glycol having a carbon / oxygen atom ratio of more than 2.0 and 4.0 or less is preferable. As such aromatic dicarboxylic acids, terephthalic acid and its lower alkyl esters are mainly used, and others are isophthalic acid, phthalic acid, 2,5
-Norbonandicarboxylic acid, 1,4-naphthalic acid, 1,
Among them, 5-naphthalic acid, 4,4-oxybenzoic acid and their lower alkyl esters, among which dimethyl terephthalate is readily available as raw materials, has a high polyesterification rate, and has an effect on polyethers (no acid decomposition). This is particularly preferred from the viewpoint of

The short-chain glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-
Among them, hexanediol and the like can be mentioned. Among them, 1,4-butanediol is particularly preferable because it shows good crystallinity. Furthermore,
Examples of the polyalkylene glycol having a carbon / oxygen atom ratio of greater than 2.0 and 4.0 or less include polypropylene glycol, polytetramethylene glycol and the like, and ethylene oxide adducts thereof. It is also possible to use together.

Examples of the thermoplastic elastomer other than the polyurethane resin or the polyester resin include polystyrene-polybutadiene-polystyrene copolymer, polyvinyl chloride elastomer, 1,2-polybutadiene elastomer, trans polyisoprene elastomer, and fluoroelastomer. And chlorinated polyethylene elastomers.

The ethylene-vinyl acetate copolymer (C) used as a compatibilizer in the present invention preferably has a vinyl acetate content of 40 to 90% by weight. Especially 60-80% by weight
Is useful. If the vinyl acetate content is less than 40% by weight, the composition lacks flexibility, while if it exceeds 90% by weight, the effect of imparting compatibility becomes poor. If the melt index (MI) of the copolymer is less than 0.05 g / 10 minutes, the fluidity is reduced, sometimes causing fish eyes and the appearance of the molded product is deteriorated. 0.05 to 250 g / 10 min is desirable because there is stickiness when blending and the melt tension is reduced.

The above-mentioned melt index (MI) means a load of 2160 at 190 ° C. unless otherwise specified.
It is a melting index (g / 10 minutes) measured under the condition of g.

The mixing ratio of the thermoplastic resin (A), the thermoplastic elastomer (B) and the ethylene-vinyl acetate copolymer (C) is such that the thermoplastic elastomer (B) is mixed with 100 parts by weight of the thermoplastic resin (A). 1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 1 to 30 parts by weight,
1 to 100 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 100 parts by weight of the ethylene-vinyl acetate copolymer (C)
30 parts by weight are suitable. Thermoplastic elastomer (B)
Is less than 1 part by weight, there is no effect of imparting flexibility, and if it exceeds 100 parts by weight, practical problems occur in terms of strength and the like. If the amount of the ethylene-vinyl acetate copolymer (C) is less than 1 part by weight, the compatibility between (A) and (B) becomes poor, and if it exceeds 100 parts by weight, the composition exhibits tackiness.

The method of mixing the thermoplastic resin (A), the thermoplastic elastomer (B) and the ethylene-vinyl acetate copolymer (C) is not particularly limited, and includes, for example, a pressure kneader, a mixing roll, a Banbury mixer, a Henschel. It can be performed by mechanical shearing with a mixer, tumbler, extruder or the like.

In the present invention, the resin composition comprising the thermoplastic resin (A), the thermoplastic elastomer (B) and the ethylene-vinyl acetate copolymer (C) is formed into a molded product, and the scrap and various applications generated at that time are formed. The scrap generated when subjected to the above can be contained in the above resin composition, and a resin composition having the effects of the present invention can be obtained. The content ratio of the scrap is 10 to 90% by weight, preferably about 10 to 50% by weight.

When producing molded articles, if necessary, reinforcing materials such as glass fiber and carbon fiber, lubricants such as low molecular weight polyethylene, low molecular weight polypropylene, paraffin, higher fatty acid amides, metal soaps, antioxidants, ultraviolet rays Known additives such as an absorbent, an antibacterial agent, a foaming agent, an inorganic / organic filler, an antistatic agent, a flame retardant, and a pigment may be appropriately compounded.

As a molding method, usually, a melt molding method is performed,
Arbitrary molding methods such as calender molding, extrusion molding, injection molding, and compression molding can be employed. Among these, examples of the extrusion molding method include a T-die method, a hollow molding method, a pipe extrusion method, a linear extrusion method, a profile die extrusion method, an inflation method, and a melt spun method.

The shape of the molded product obtained from the resin composition of the present invention is arbitrary, and not limited to films, sheets, tapes, bottles, tubes, tanks, hoses, pipes, filaments, extruded products with irregular cross-sections, etc. It is also important to form a laminate having at least one layer of the resin composition of the present invention. In the case of lamination, the mating resin is a polyolefin resin, a saponified ethylene-vinyl acetate copolymer, nylon-6, nylon-6, or the like. 6, polyamide resin, vinylidene chloride resin, polystyrene resin, polyester resin, polycarbonate resin, polyvinyl chloride resin, acrylic resin, vinyl ester resin, polyester resin elastomer, polyurethane resin elastomer, chlorine Thermoplastic resin such as chlorinated polyethylene resin and chlorinated polypropylene resin And the like.

In producing such a laminate, an adhesive resin can be used. As the adhesive resin, a known adhesive can be used. For example, a density of 0.1% modified with an unsaturated carboxylic acid or its anhydride can be used. 86 to 0.95 g /
cm ^{3 of} an ethylene-α-olefin copolymer is preferable, and can be obtained by copolymerizing or graft-modifying the same resin as the above polyolefin-based resin with an unsaturated carboxylic acid or an anhydride thereof. And a blend of an unmodified ethylene-α-olefin copolymer and an unsaturated carboxylic acid or anhydride thereof. Examples of the unsaturated carboxylic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride and the like. It is preferably used.

At this time, the amount of unsaturated carboxylic acid or anhydride contained in the ethylene-α-olefin copolymer is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. is there. If the content is small, the adhesive strength is reduced, and if it is too large, a crosslinking reaction is caused and moldability is deteriorated, which is not preferable. Such an adhesive resin can be mixed into a layer to be laminated.

The laminate of the present invention can be produced not only in the form of a sheet or a film, but also in the form of a pipe or tube or a tank or the like by the above-mentioned coextrusion molding method, coinjection molding method, coextrusion inflation molding method or blow molding method. The laminate can be formed into a container such as a bottle, and the laminate can be heated again to about 100 to 150 ° C. and stretched by a blow stretching method or the like.

Each layer of the laminate of the present invention (other than the resin composition layer of the present invention) is provided with an antioxidant, a lubricant, an antistatic agent, a plasticizer, and a coloring agent in order to improve moldability and physical properties. An agent, an ultraviolet absorber, an antibacterial agent, an inorganic / organic filler, a flame retardant, a pigment, and the like can be added as long as the effects of the present invention are not impaired.

Thus, the resin composition of the present invention and molded articles and laminates using the same exhibit extremely excellent moldability and flexibility, and are used for various applications, especially for packaging of films and sheets. It is very useful for applications such as materials, flooring materials, building materials such as wallpaper, and interior materials for automobiles.

[0032]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” mean on a weight basis unless otherwise specified.

[Thermoplastic resin (A)] (A-1): Density = 0.920 g / cm ³ , Melt index (MI) = 1 g / 10 min (190 ° C., 2160
g load) (melting point = 122.3 ° C) (A-2): Polyethylene “Kernel KF270” manufactured by Nippon Polychem (using a metallocene catalyst, average molecular weight 35)
000)

[Thermoplastic Elastomer (B)] (B-1): Polyurethane-based polyurethane resin “Miractran E-180FNAT” manufactured by Nippon Miractran Co.
(Average molecular weight: 150,000) (B-2): a polyester polyol having a molecular weight of 2,000 obtained from a condensate of adipic acid and 1,4-butanediol / neopentyl glycol (molar ratio: 9/1);
Polyurethane reacted with tolylene diisocyanate (B-3): 34.4 parts of dimethyl phthalate, 63.8 polytetramethylene glycol having an average molecular weight of 2,000
Part, polyester resin obtained by reacting 24.0 parts of 1,4-butanediol (B-4): polyester resin “Nichigo Polyester SP-176” manufactured by Nippon Synthetic Chemical Company

[Ethylene-vinyl acetate copolymer (C)] (C-1): vinyl acetate content = 67%, melt index (MI) = 52 g / 10 min, average molecular weight = 300
000 ethylene-vinyl acetate copolymer (C-2): vinyl acetate content = 60%, melt index (MI) = 152 g / 10 min, average molecular weight = 23
Ethylene-vinyl acetate copolymer of 0000 (C-3): vinyl acetate content = 55%, melt index (MI) = 180 g / 10 min, average molecular weight = 24
0000 ethylene-vinyl acetate copolymer

Examples 1 to 5 The above thermoplastic resin (A) and thermoplastic elastomer (B)
And the ethylene-vinyl acetate copolymer (C) were mixed at a mixing weight of 200 ° C. and a Banbury mixer manufactured by Nippon Roll Co., Ltd. at 40 rpm for 25 minutes as shown in Table 1 to obtain a resin composition. Was.

[Table 1] Thermoplastic Thermoplastic Eras Ethylene-Acetate Biresin (A) Tomer (B) Nyl Copolymer (C) Example 1 (A-1) 100 (B-1) 20 (C-1) ) 10〃2 (A-1) 100 (B-2) 35 (C-1) 10〃3 (A-2) 100 (B-1) 40 (C-2) 15〃4 (A-2) 100 (B-3) 50 (C-3) 20 ５5 (A-2) 100 (B-4) 20 (C-3) 15

In the resin composition obtained above, a polyethylene wax (manufactured by Mitsui Chemicals, Inc., "H
w-220P ") in an amount of 0.2 to 100 parts of the resin composition.
The mixture was mixed at 140 ° C. for 7 minutes with two rolls having a diameter of 8 inches to form a sheet.

The sheet was pressed at 145 ° C.
A No. 3 test piece was prepared according to SK6301, and 20
Tensile strength and elongation were measured at a tensile speed of 100 mm / min in an atmosphere of 65 ° C. and 65% RH. Table 2 shows the measurement results.

[Table 2] Tensile strength (Kg / cm ² ) Elongation (%) Example 1 230 310 〃2 240 320 ３3 245 330 〃4 250 335 ５5 235 320

[0041]

The resin composition of the present invention comprises a thermoplastic resin (A), a thermoplastic elastomer (B) and an ethylene-vinyl acetate copolymer (C), and comprises an ethylene-vinyl acetate copolymer. Since (C) acts as a compatibilizer between the thermoplastic resin (A) and the thermoplastic elastomer (B), it exhibits excellent effects on moldability and flexibility, and can be used for various applications. Packaging materials such as sheets,
It is very useful for building materials such as flooring and wallpaper, interior materials for automobiles, and laminates.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 67/00 C08L 67/00 75/04 75/04 (72) Inventor Tatsuaki Hani 2-8 Yaesu, Chuo-ku, Tokyo No. 1 Japan Synthetic Chemical Industry Co., Ltd. Tokyo branch office (72) Inventor Minoru Fujita 2-3-1, Muroyama, Ibaraki-shi, Osaka F-term in Central Research Laboratory of Nippon Kasei Chemical Industry Co., Ltd. 4J002 AA01W AA01X AC00X BB03W BB05W BB063 BF033 CF09X CK02X CK04X

Claims (5)

[Claims] 1. A resin composition comprising a thermoplastic resin (A), a thermoplastic elastomer (B) and an ethylene-vinyl acetate copolymer (C). 2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyethylene resin. 3. The resin composition according to claim 1, wherein the thermoplastic elastomer (B) is a polyurethane resin or a polyester resin. 4. The resin composition according to claim 1, wherein the ethylene-vinyl acetate copolymer (C) has a vinyl acetate content of 40 to 90% by weight. 5. A thermoplastic elastomer (B) is blended in an amount of 1 to 100 parts by weight and an ethylene-vinyl acetate copolymer (C) in an amount of 1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin (A). The resin composition according to claim 1, wherein: