JP4809970B2 - Resin composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition comprising a thermoplastic resin (A), a thermoplastic elastomer (B), and an ethylene-vinyl acetate copolymer (C), and more particularly has excellent toughness and improved brittleness. The present invention relates to a so-called flexible resin composition.
[0002]
[Prior art]
Conventionally, flooring made of vinyl chloride resin has been frequently used for flooring in buildings and condominiums, and many products using chlorine-containing resin are also used for other building materials applications, but chlorine-containing resin products are Since a large amount of smoke containing harmful hydrogen chloride gas is generated at the time of a fire, there is a problem in that it adversely affects the human body and prevents evacuation and fire fighting activities. Further, since it contains a large amount of plasticizer and stabilizer, there is a problem that the plasticizer is contaminated by bleeding and the odor is strong.
[0003]
As such countermeasures, (1) JP-A-7-125145 discloses that calcium carbonate or 100 parts by weight of a base resin in which 70 to 30 parts by weight of polypropylene and 30 to 70 parts by weight of an ethylene-vinyl acetate copolymer are mixed. A flooring made of a resin composition containing a mixture of calcium carbonate and aluminum hydroxide in an amount of 120 to 300 parts by weight is disclosed in (2) JP-A-9-317142 as 30 to 70 parts by weight of polyethylene and 70 to 70 parts by weight. A flooring made of a resin composition obtained by mixing 50 to 300 parts by weight of an inorganic filler with a mixed resin of 30 parts by weight of ethylene-vinyl acetate copolymer is disclosed in (3) Japanese Patent Laid-Open No. 10-45962. 30 to 70 parts by weight of polyethylene, 70 to 30 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 71 to 90% by weight, and an inorganic filling Flooring made from the resin composition obtained by blending in a proportion of 50 to 300 parts by weight, have been proposed respectively.
[0004]
[Problems to be solved by the invention]
However, in the technology disclosed in the above publication, since the base resin such as polypropylene or polyethylene is a hard resin, an attempt is made to add flexibility by blending an ethylene-vinyl acetate copolymer. It is difficult to sufficiently satisfy the molding processability and flexibility only by blending the coalescence, and further improvement is required.
[0005]
Therefore, the present invention aims to provide a resin composition excellent in flexibility, a molded product using the resin composition, and a laminate in such a background.
[0006]
[Means for solving problems]
The present inventors have however, result of intensive research in view of the above circumstances, the thermoplastic resin (A), the thermoplastic elastomer (B) and ethylene - Ri Na contain vinyl acetate copolymer (C), The thermoplastic resin (A) is a polyolefin resin, the thermoplastic elastomer (B) is a polyester resin, and the vinyl acetate content of the ethylene-vinyl acetate copolymer (C) is 40 to 90% by weight, 1-50 parts by weight of the thermoplastic elastomer (B) of the thermoplastic resin (a) 100 parts by weight of an ethylene - vinyl acetate copolymer (C) ing by blending each 1 to 30 parts by weight of resin composition Has found that the object can be achieved, and completed the present invention.
[0007]
In the present invention, a polyester resin is used as the thermoplastic elastomer (B) in order to improve the flexibility of the thermoplastic resin (A) of a polyolefin resin such as a polyethylene resin by changing the idea from the conventional technique. As a result, the compatibility between the two was poor and the intended purpose could not be achieved, but by including an ethylene-vinyl acetate copolymer (C) having a predetermined vinyl acetate content as a compatibilizing agent, This problem is solved.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. The thermoplastic resin (A) used in the present invention, Po Li olefin resins, polyamide resins, polyester resins, polyether resins, polyurethane resins, polycarbonate resins, acrylic resins, polystyrene resins and the like Although mentioned, polyolefin-type resin is used suitably. These may be used alone or in combination of two or more.
[0009]
Examples of such polyolefin resins include high-density, medium-density, and low-density polyethylene, polypropylene, polybutene, polypentene and other homopolymers, ethylene-propylene copolymer, 1-butene and 1-hexene mainly composed of ethylene or propylene. A copolymer with an α-olefin having about 2 to 20 carbon atoms, such as an olefin-vinyl acetate copolymer having an olefin content of 90 mol% or more, such as ethylene or propylene, and an olefin- (meth) acrylate copolymer. One or two or more kinds of ionomer resins modified with polymers and metal ions, or those obtained by graft-modifying the above-mentioned polyolefin-based resins or copolymers with unsaturated carboxylic acids or the like can be arbitrarily used.
Of these, polyethylene resins are preferred, and those using metallocene catalysts are useful from the viewpoint of production.
Among these, in particular, a crystalline ethylene polymer having a density of 0.910 to 0.945 g / cm ³ and a melt index (MI) of 0.5 to 50 g / 10 minutes (according to JIS K 7210). A more preferred melt index (MI) is 0.5 to 20 g / 10 min (according to JIS K 7210).
[0011]
If the melt index (MI) is less than 0.5 g / 10 minutes, the fluidity is lowered and the melt moldability is lowered, and if it exceeds 50 g / 10 minutes, the tension at the time of melting is lowered, which is not preferable.
Examples of commercially available products of such polyethylene resins include “Kernel KF270” manufactured by Nippon Polychem Co., Ltd.
[0012]
A typical example of the thermoplastic elastomer (B) used in the present invention is a polyurethane resin or a polyester resin.
Any polyurethane-based resin can be used as long as it is a condensation reaction product of polyol and polyisocyanate and exhibits elasticity.
[0013]
Examples of the polyol include 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, mannitol, arabitol, xylitol, galactitol, glycerin, poly Polyvalent alcohols such as glycerin and polytetramethylene glycol Le and, polyethylene oxide, polypropylene oxide, polyether polyols having at least one structure of a block or random copolymer of ethylene oxide / propylene oxide.
[0014]
Polyester polyol which is a condensate of polyhydric alcohol or polyether polyol and polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, caprolactone-modified polytetramethylene Examples also include caprolactone-modified polyols such as polyols, polyolefin-based polyols, and polybutadiene-based polyols such as hydrogenated polybutadiene polyol.
[0015]
The polyisocyanate is not particularly limited, and examples thereof include aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane. Diisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, etc. Diisocyanate or trimer thereof is preferably used.
As the polyurethane-based resin, those having a polyol segment of polyester polyol exhibit a remarkable effect. As a commercially available product, “Milactolan E-180FNAT” manufactured by Nippon Milactolan is useful.
[0016]
The polyester-based resin is obtained by condensing about 20 to 50% by weight of a hard segment and about 50 to 80% by weight of a soft segment, and more specifically, an aromatic dicarboxylic acid, a short-chain glycol, and carbon / oxygen. A polyester resin obtained by polycondensation of polyalkylene glycol having an atomic ratio of greater than 2.0 and 4.0 or less is preferred. As the aromatic dicarboxylic acid, terephthalic acid and its lower alkyl ester are mainly used. Others include isophthalic acid, phthalic acid, 2,5-norbornane dicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid. Acids, 4,4-oxybenzoic acid and their lower alkyl esters are exemplified, but dimethyl terephthalate is easy to obtain raw materials, has a high rate of polyesterification, and has an influence on polyether (no acid decomposition). Particularly preferred.
[0017]
Examples of such short-chain glycols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. Among them, 1,4-butanediol is preferable. The crystallinity is particularly preferred.
Furthermore, as the polyalkylene glycol having a carbon / oxygen atomic ratio of more than 2.0 and 4.0 or less, polypropylene glycol, polytetramethylene glycol or the like, or an ethylene oxide adduct thereof is used. Combination with glycol is also possible.
[0018]
Examples of thermoplastic elastomers other than polyurethane resins or polyester resins include polystyrene-polybutadiene-polystyrene copolymers, polyvinyl chloride elastomers, 1,2-polybutadiene elastomers, trans polyisoprene elastomers, fluororubber elastomers, and chlorination. Examples include polyethylene elastomer.
[0019]
The ethylene-vinyl acetate copolymer (C) used as a compatibilizing agent in the present invention has a vinyl acetate content of 40 to 90% by weight , particularly 60 to 80% by weight. If the vinyl acetate content is less than 40% by weight, the composition lacks flexibility, while if it exceeds 90% by weight, the compatibility imparting effect is poor. If the melt index (MI) of the copolymer is less than 0.05 g / 10 minutes, the fluidity is lowered, sometimes causing fish eyes, and the appearance of the molded product is deteriorated. When blended, there is stickiness and the melt tension decreases, so 0.05 to 250 g / 10 min is desirable.
[0020]
The melt index (MI) is a melt index (g / 10 minutes) measured under a load of 2160 g at 190 ° C. unless otherwise specified.
[0021]
The mixing ratio of the thermoplastic resin (A), the thermoplastic elastomer (B) and the ethylene-vinyl acetate copolymer (C) is 1 to 100 parts by weight of the thermoplastic elastomer (B) with respect to 100 parts by weight of the thermoplastic resin (A). 50 parts by weight, particularly preferably 1 to 30 parts by weight, an ethylene - vinyl acetate copolymer (C) 1 to 30 parts by weight, the preferred especially is suitable from 5 to 30 parts by weight. Thermoplastic elastomer (B) is inflexible imparting effect is less than 1 part by weight, a practical problem arises in terms of strength, etc. and that too many. Ethylene - The vinyl acetate copolymer (C) is less than 1 part by weight becomes poor compatibility with the (A) and (B), tacky composition and that too many expressed.
[0022]
The mixing method of the thermoplastic resin (A), the thermoplastic elastomer (B), and the ethylene-vinyl acetate copolymer (C) is not particularly limited. For example, a pressure kneader, a mixing roll, a Banbury mixer, a Henschel mixer, and a tumbler It can be performed by mechanical shearing using an extruder or the like.
[0023]
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, which is used for scraps and various uses. It is also possible to make the above-mentioned resin composition contain scraps generated at the time, and the resin composition having the effects of the present invention is obtained. The scrap content is about 10 to 90% by weight, preferably about 10 to 50% by weight.
[0024]
When producing molded products, reinforcing materials such as glass fibers and carbon fibers, low molecular weight polyethylene, low molecular weight polypropylene, paraffin, higher fatty acid amides, metal soaps, lubricants, antioxidants, UV absorbers, Known additives such as antibacterial agents, foaming agents, inorganic / organic fillers, antistatic agents, flame retardants, and pigments may be appropriately blended.
[0025]
As the molding method, a melt molding method is usually performed, and any molding method such as calendar molding, extrusion molding method, injection molding method, compression molding method or the like can be adopted. 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 modified die extrusion method, an inflation method, and a melt span method.
[0026]
The shape of the molded product obtained from the resin composition of the present invention is arbitrary, and not only a film, a sheet, a tape, a bottle, a tube, a tank, a hose, a pipe, a filament, a modified cross-section extrudate, etc., but also the resin composition of the present invention. It is also important to form a laminate comprising at least one product, and as a counterpart resin in the case of lamination, polyolefin resin, saponified ethylene-vinyl acetate copolymer, nylon-6, nylon-6, 6, etc. 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, chlorinated polyethylene Resin, thermoplastic resin such as chlorinated polypropylene resin .
[0027]
An adhesive resin can also be used in the production of such a laminate, and a known adhesive can be used as the adhesive resin, for example, a density of 0.86 to 0 modified with an unsaturated carboxylic acid or an anhydride thereof. .95 g / cm ^{3 of} an ethylene-α-olefin copolymer is preferable, and can be obtained by copolymerizing or graft-modifying a resin similar to the above polyolefin resin with an unsaturated carboxylic acid or an anhydride thereof. Modifications also include blends of unmodified ethylene-α-olefin copolymers and unsaturated carboxylic acids or anhydrides. 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, etc. Preferably used.
[0028]
The amount of the unsaturated carboxylic acid or anhydride thereof contained in the ethylene-α-olefin copolymer at this time is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content is small, the adhesive strength is lowered. On the other hand, when the content is large, a crosslinking reaction is caused, and the moldability is deteriorated. Such an adhesive resin can be mixed in a layer to be laminated.
[0029]
The laminate of the present invention is not only in the form of a sheet or film, but also in the above-described coextrusion molding method, co-injection molding method, coextrusion inflation molding method, blow molding method, etc. It can be formed into a container or the like, and further, the laminate can be reheated to about 100 to 150 ° C. and stretched by a blow stretching method or the like.
[0030]
In addition, each layer of the laminate of the present invention (other than the resin composition layer of the present invention) has an antioxidant, a lubricant, an antistatic agent, a plasticizer, a colorant, an ultraviolet ray for improving the molding processability and physical properties. Absorbers, antibacterial agents, inorganic / organic fillers, flame retardants, pigments, and the like may be added as long as the effects of the present invention are not impaired.
[0031]
Thus, the resin composition of the present invention and a molded product or laminate using the resin composition exhibit extremely excellent effects on molding processability and flexibility, and are used for various applications. Among them, packaging materials such as films and sheets, floors, etc. It is very useful as a material, building materials such as wallpaper, and automotive interior materials.
[0032]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.
[0033]
[Thermoplastic resin (A)]
(A-1): density = 0.920 g / cm ³ , melt index (MI) = 1 g / 10 min (190 ° C., 2160 g load) polyethylene (melting point = 12.3 ° C.)
(A-2): Polyethylene “Kernel KF270” manufactured by Nippon Polychem Co., Ltd. (using metallocene catalyst, average molecular weight 35000)
[0034]
[Thermoplastic elastomer (B)]
(B-1): Polyester polyurethane resin “miractran E-180FNAT” manufactured by Japan Miractolan (average molecular weight: 150,000)
(B-2): Polyurethane obtained by reacting tolylene diisocyanate with a 2000-molecular weight polyester polyol obtained from a condensate of adipic acid and 1,4-butanediol / neopentyl glycol (molar ratio 9/1) (B-3): Polyester resin (B-4) obtained by reacting 34.4 parts of dimethyl phthalate, 63.8 parts of polytetramethylene glycol having an average molecular weight of 2000, and 24.0 parts of 1,4-butanediol : Nippon Synthetic Chemical Co., Ltd. polyester resin “Nichigo Polyester SP-176”
[0035]
[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 = 230,000 ethylene-vinyl acetate copolymer (C-3): vinyl acetate content = 55%, melt index (MI) = 180 g / 10 min, average Ethylene-vinyl acetate copolymer having a molecular weight of 240,000
Examples 1-2, Reference Examples 1-3
Using the above-mentioned thermoplastic resin (A), thermoplastic elastomer (B) and ethylene-vinyl acetate copolymer (C), a Banbury manufactured by Nippon Roll Co., Ltd. at a mixing weight part as shown in Table 1 and a mixing temperature of 200 ° C. The mixture was mixed with a mixer at 40 rpm for 25 minutes to obtain a resin composition.
[0037]
[Table 1]
Thermoplastic thermoplastic elastomer Ethylene-vinyl acetate
Resin (A) Tomer (B) Nyl Copolymer (C)
Example 1 (A-2) 100 (B-3) 50 (C-3) 20
〃 2 (A-2) 100 (B-4) 20 (C-3) 15
Reference Example 1 (A-1) 100 (B-1) 20 (C-1) 10
〃 2 (A-1) 100 (B-2) 35 (C-1) 10
３ 3 (A-2) 100 (B-1) 40 (C-2) 15
[0038]
In the resin composition obtained above, polyethylene wax ("Hw-220P", manufactured by Mitsui Chemicals, Inc.) as a lubricant is further added in an amount of 0.2 part to 100 parts of the resin composition, and the two rolls having a diameter of 8 inches are added. Were mixed at 140 ° C. for 7 minutes to form a sheet.
[0039]
This sheet was pressed at 145 ° C. to prepare No. 3 test piece according to JIS K 6301, and the tensile strength and elongation were measured at 20 ° C. and 65% RH atmosphere at a tensile speed of 100 mm / min.
The measurement results are shown in Table 2.
[0040]
[Table 2]
Tensile strength (Kg / cm ² ) Elongation (%)
Example 1 250 335
〃 2 235 320
Reference Example 1 230 310
〃 2 240 320
〃 3 245 330
[0041]
【The invention's effect】
The resin composition of the present invention contains a thermoplastic resin (A), a thermoplastic elastomer (B) and an ethylene-vinyl acetate copolymer (C), and the thermoplastic resin (A) is a polyolefin resin. The thermoplastic elastomer (B) is a polyester resin, the vinyl acetate content of the ethylene-vinyl acetate copolymer (C) is 40 to 90% by weight, and is 100 parts by weight of the thermoplastic resin (A). 1 to 50 parts by weight of the thermoplastic elastomer (B) and 1 to 30 parts by weight of the ethylene-vinyl acetate copolymer (C) are blended, and the ethylene-vinyl acetate copolymer (C) is a thermoplastic resin ( A) acts as a compatibilizer between the thermoplastic elastomer (B), and thus exhibits excellent effects in molding processability and flexibility, and can be used for various applications. Flooring, building materials such as wallpaper, automotive interior materials, it is very useful for applications of the laminate or the like.

Claims (2)

Thermoplastic resin (A), the thermoplastic elastomer (B) and ethylene - Ri Na contain vinyl acetate copolymer (C), the thermoplastic resin (A) is a polyolefin resin, a thermoplastic elastomer (B) Is a polyester resin, the vinyl acetate content of the ethylene-vinyl acetate copolymer (C) is 40 to 90% by weight, and the thermoplastic elastomer (B) is added to 100 parts by weight of the thermoplastic resin (A). 1-50 parts by weight, an ethylene - vinyl acetate copolymer (C) a resin composition characterized Rukoto such blended respectively 30 parts by weight.   The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyethylene resin.