JPH10273568A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. which is excellent in low-temp. softness, high-frequency weldability, adhesion to a base fabric, and moldability in extrusion lamination and is suitable as a lamination material or for protective safety clothing for electrical work. SOLUTION: This compsn. is prepd. by compounding 50-90 wt.% propylene polymer having a crystallization energy ▵HC of 90 J/g or lower in a crystallization peak temp. curve obtd. with a differential scanning calorimeter with 50-10 wt.% ethylene copolymer produced from ethylene and an unsatd. carboxylic acid and/or its deriv. and has a torsional rigidity modulus (at -20 deg.C, according to JIS K 6730) of 2,000 kgf/cm<2> or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition comprising a specific propylene-based polymer and an ethylene-based copolymer. More specifically, the present invention provides adhesiveness to a base fabric,
The present invention relates to a resin composition suitable for use as a tent material and a safety protective garment for electric work, which is excellent in high-frequency fusing property and flexibility in a low-temperature region and excellent in extrusion lamination moldability.

[0002]

2. Description of the Related Art Conventionally, since polyvinyl chloride resin can be fused by high frequency, industrial materials such as tents, tarpaulins, and flexible containers, waste disposal sites, pig farms, reservoirs, rooftops of residential buildings, and tunnels. Waterproof or impermeable sheets, waterproof sheets and the like have been used in various civil engineering and construction fields for construction of breakwaters and the like. Further, polyvinyl chloride resin has been used as various packaging materials. As the sealing method,
High frequency fusion processing had been applied. The high-frequency fusion is a fusion method using a principle of applying a high-frequency electric field to a dielectric to generate dielectric loss in the dielectric and generate heat. Since high-frequency fusion is internal heat generation, the thermoplastic resin is less susceptible to thermal degradation as in external heating. In the high-frequency welding, the temperature rises quickly, the rising speed can be arbitrarily selected, and uniform heating can be performed. In the case of the composite, it has a feature that it can be selectively heated by utilizing a difference in a dielectric constant or a dielectric power factor.

[0003] Generally, the high-frequency fusion property of a thermoplastic resin is as follows.
It is known that the larger the dielectric constant (ε), the dielectric loss tangent (tan δ), and the product thereof, the energy loss [(ε) × (tan δ)], the better. Among thermoplastic resins, polyolefin resins such as polyethylene and polypropylene are non-polar, and therefore have a dielectric constant (ε) and a dielectric loss tangent (t).
anδ) is small and is inferior in high-frequency fusion property. Although polyvinyl chloride resin is capable of high-frequency fusion, high-frequency fusion is sometimes insufficient due to the influence of a plasticizer or the like. Further, the polyvinyl chloride resin has a higher specific gravity than the polyolefin-based resin, so that it is difficult to handle at the time of construction, and in recent years, its use has been restricted from the viewpoint of global environmental protection.

Therefore, as a substitute for the polyvinyl chloride resin, a resin using a polyolefin-based thermoplastic elastomer has been proposed. However, there has been a problem that these materials are not only inferior in high-frequency fusing property but also cross-linked olefin elastomers are inferior in recyclability. 2. Description of the Related Art Conventionally, as a method for imparting high-frequency fusing properties to a nonpolar resin such as a polyolefin resin, a radio wave absorber such as a ferrite is blended into a film, a coated film (Japanese Patent Laid-Open No. 6-182876), a thermoplastic film, or the like. A thermoplastic resin composition comprising a high-frequency or microwave sensitizer having 3 to 30 parts by weight of a liquid polar substance adsorbed on 2 to 20 parts by weight of an inorganic porous powder per 100 parts by weight of a resin (JP-A-6-228368) Gazette) has been proposed.

[0005] Ultrahigh molecular weight polyethylene is prepared by adsorbing water and / or other volatile substances selected from the group consisting of radio frequency sensitizers consisting of zinc oxide, bentonite and aluminosilicates of alkali metals or alkaline earth metals. Of a molded article in which a mixture of an inorganic radio frequency sensitizer treated so as to remove a volatile substance and a substance suitable for improving radio frequency sensitivity is exposed to radio frequency energy (Japanese Patent Publication No. 5-4298).
No. 2: JP 193902A), N
A method for producing a thermoplastic molded article of a mixture of a radio frequency energy sensitizer comprising a composition containing 4 to 10% by weight of ethyltoluenesulfonamide and a thermoplastic polymer (Japanese Patent Application Laid-Open No. 2-182419: U.S. Pat. 4840
No. 758), a molded product obtained by mixing 20 to 200 parts by weight of an inorganic powder having water of crystallization with 100 parts by weight of a polyolefin resin (Japanese Patent Application Laid-Open No. 2-129243), a composition of sodium aluminosilicate and ultrahigh molecular weight polyethylene ( QX
Nguyen, R. Gauvin, Y. Belanger; ANTEC '91, p2245-
2247) are well known.

[0006] Commercially available microwave sensitizers include:
“FREQUON: trade name” is marketed by STRUKTOL (USA). As an introduction to these products,
Polymer Digest, February 1988, p115-11
7. However, these methods have a problem that the high-frequency fusion property is still insufficient and the flexibility in a low-temperature region is poor. Further, in the method disclosed in JP-A-6-182876 in which ferrite is mixed, there is a problem that the molded product is colored. Among the polyolefin resins,
For example, it is well known that an ethylene-based copolymer having a polar group such as an ethylene-vinyl acetate copolymer or an ethylene-methyl acrylate copolymer can be subjected to high-frequency fusion. An example of such an application is a protective garment for electrical work in which a number of ethylene-vinyl acetate copolymers are laminated on a base cloth. However, the ethylene-vinyl acetate copolymer has a large specific gravity and is heavy when worn, so that a lighter one has been desired. Further, in applications such as tents, a laminate of a multifilament made of polypropylene and a base fabric is used.

Further, Japanese Patent Publication No. 8-193150 discloses a method of blending, for example, a propylene-α-olefin block copolymer with a polyamide, a vinyl polymer, a polyester or a polyurethane. However, this publication merely discloses polyamide as a preferable polymer to be used in combination, and does not specifically disclose other polymers at all. Further, this publication mentions high-frequency fusing properties, but does not mention at all extrusion extrusion laminating properties, flexibility in a low-temperature region, and usefulness as materials for tents.

[0008]

Accordingly, the present invention is excellent in adhesiveness to a base fabric, high-frequency fusing property, flexibility in a low temperature range and extrusion lamination moldability, and is particularly suitable as a material for a tent. An object is to provide a resin composition.

[0009]

According to the study of the present inventors, it has been found that the above object can be achieved by combining a specific propylene-based polymer and an ethylene-based copolymer. Based on this, the present invention has been completed. That is, the present invention provides (1) a propylene-α-olefin block copolymer 50 having a crystallization energy ΔHC of 90 (J / g) or less in a crystallization peak temperature curve by a differential scanning calorimeter (DSC). To 90% by weight, and (2) ethylene, unsaturated carboxylic acid and / or
Or an ethylene-based copolymer comprising a derivative thereof or
10% by weight and according to JIS K6730
The torsional rigidity at 20 ° C is 2,000 Kgf / cm
It is intended to provide a resin composition of ² or less.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The propylene polymer used in the present invention has a crystallization energy ΔHC of 90 (J / J) in a crystallization peak temperature curve by a differential scanning calorimeter (DSC).
g) The following are used: The number average molecular weight of such a propylene-based polymer is usually 30,000 to 2
00,000, preferably 40,000 to 180,00
0, particularly preferably 50,000 to 150,000. The crystallization energy ΔHC of the propylene-based polymer is measured according to JIS K7122. A differential scanning calorimeter (DSC) is a calorimeter used for differential scanning calorimetry.
This is a method of quantifying a thermal change that occurs when the temperature of the sample is raised and lowered at a constant speed as a thermal energy amount. The crystallization peak curve was obtained using a differential scanning calorimeter with a sample of about 3 to 5 mg.
Was melted at 230 ° C. for 5 minutes,
It is obtained by lowering the temperature to ° C.

The crystallization energy △ HC (J / g) means the total amount of the main crystallization peak area and the sub crystallization peak area in the crystallization curve. Differential scanning calorimeter (DSC)
Crystallization energy ΔH of the crystallization peak temperature curve
If C (J / g) exceeds 90 (J / g), a large amount of heat energy is required during high-frequency fusion, and high-frequency fusion is inferior and flexibility in a low-temperature region is poor, which is not preferable. The crystallization energy @ HC is preferably 80 (J / g).
Below, particularly preferably 70 (J / g) or less is appropriate. Specific examples of the propylene-based polymer include, for example, a propylene-α-olefin block copolymer, a metallocene catalyst-based polypropylene, a syndiotactic polypropylene, and a propylene random copolymer.

Above all, a propylene-α-olefin block copolymer is preferred in consideration of heat resistance, extrusion lamination moldability, compatibility with an ethylene copolymer described below, and the like. In particular, in a crystallization peak temperature curve by a differential scanning calorimeter (DSC), a main crystallization peak temperature (Tcp1) is in a range of 85 to 115 ° C., and a half width (δ) is 3 to 10 ° C. The crystallization energy is 70
The propylene-α-olefin block copolymer of (J / g) or less is excellent in extrusion laminate moldability and is preferable.
Among the propylene-α-olefin block copolymers, particularly, the soft propylene-α-olefin block copolymer described below has an energy loss [(ε) × (tan)
δ)], the crystallinity is low. Therefore, when used in combination with an ethylene copolymer described below, high-frequency fusion can be easily performed even with a small amount of heat generation.

[0013] Propylene-α particularly useful in the present invention
-An olefin block copolymer (hereinafter also referred to as "BPP") is a copolymer block of a polypropylene block, propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms (excluding 3 carbon atoms). And a block copolymer consisting of As the α-olefin used here, 1-butene, 3-methyl-1-butene,
3-methyl-1-pentene, 4-methyl-1-pentene, 4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane and the like. These α
-The olefin may be used alone or in combination of two or more. The propylene-α-olefin block copolymer used in the present invention is a differential scanning calorimeter (DSC).
85-115 ° C. in the crystallization peak temperature curve
In particular, those having a main crystallization peak temperature (Tcp1) in the range of, and having a half width (δ) of 3 to 10 ° C. and a crystallization energy of 70 (J / g) or less are particularly effective in improving the high-frequency fusion property. Remarkable.

The main crystallization peak temperature (Tcp1) by a differential scanning calorimeter (DSC) must be in the range of 85 to 115 ° C., and the main crystallization peak temperature (Tcp1)
However, when the temperature is lower than 85 ° C., the crystallization speed is low, the solidification at the time of molding is slow, the moldability is inferior, and the uneven flow of the solidified molded body occurs. On the other hand, when the temperature exceeds 115 ° C., flexibility and cold resistance are poor. Main crystallization peak temperature (Tcp1)
Is preferably 88 to 113 ° C, particularly 89 to 112 ° C
Is preferred. Further, the half width (δ) needs to be in the range of 3 to 10 ° C, and when the half width (δ) is less than 3 ° C,
Poor flexibility and impact resistance are not preferred. On the other hand, if it exceeds 10 ° C., transparency and moldability are poor, which is not preferable. The half width (δ) is preferably in the range of 3.5 to 8 ° C, particularly 4 to 7 ° C.
The range of ° C. is preferred.

Furthermore, the propylene-α used in the present invention
As the olefin block copolymer, those having the following properties (1) and (2) are preferable. That is, (1)
Para-xylene insoluble content at 25 ° C. is 25 to 65% by weight
(2) the content of soluble in para-xylene at 25 ° C. is (i) the average propylene content (FP) according to the two-site model is 20 to 80% by weight, and (ii) the propylene content in the two-site model is Content (P _P ) of copolymer (P _H ) formed at the active site where polymer is preferentially polymerized
There is a 60 to 90 wt%, and (iii) the proportion of P _H occupies the copolymer (P _f1) is in the range of 0.60 to 0.90. The para-xylene-insoluble content is an insoluble content when the propylene-α-olefin block copolymer is dissolved in para-xylene at a temperature of 130 ° C. at about 1% by weight and then cooled to 25 ° C. ~ 65% by weight, especially 3
0-60% by weight is preferred.

The para-xylene-soluble component is a component dissolved by the above operation, and the properties determined by a two-site model are preferably in the above range. Specifically, a component obtained by dissolving a propylene-α-olefin block copolymer in para-xylene at 25 ° C. was mixed with a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene at a polymer concentration of 10% by weight. % At 120 ° C. for dissolution. This solution was placed in a ¹⁰ mmφ glass sample tube, and ¹³
Measure the C-NMR spectrum. Here, regarding the two-site model of propylene-α-olefin, nuclear magnetic resonance (isotope carbon) of propylene-ethylene copolymer
FIG. 1 shows an example of a ( ¹³ C-NMR) spectrum. This spectrum is a chain distribution (the arrangement of ethylene and propylene)
, 10 peaks shown by i to x appear.

The name of this chain is Carman et al., Macromole.
cules 10: 536-544 (1977), and their names are shown in FIG. Such a chain can be expressed as a reaction probability (P) assuming a copolymerization reaction mechanism. When the overall peak intensity is 1, the relative intensity of each of the peaks i to x is determined using P as a parameter. It can be expressed as a probability equation by Bernoulli statistics. For example, in the case of Sαα in (i), the propylene unit is represented by the symbol p, and the ethylene unit is represented by the symbol e.
Then, the chains that can take this are [pppp], [pppp
pe] and [eppe], each of which is represented by a reaction probability (P) and added together. The remaining (ii) ~
The peak of (x) can be obtained by formulating an equation in the same manner, and optimizing P so that these ten equations and the actually measured peak intensity become the closest.

The two-site model assumes this reaction mechanism.
Model, Cheng, Jounalof Applied Polymer
Sience, 35: 1639-1650 (1988). That is, touch
Model for copolymerizing propylene and ethylene using a solvent
At the active site where propylene is preferentially polymerized
Copolymer (P_H) Propylene content (P_P) And d
Of copolymers formed at active sites that preferentially polymerize
Propylene content (P ' _P) And P_H
In the copolymer (P_f1) As a parameter
The probability equation shown in Table 1 is obtained.

[0019]

[Table 1] Table 1 Signal Establishment equation for two-site model (i) Sαα P_P ^Two× P_f1+ P '_P ^Two× (1-P_f1) (ii) Sαγ (-2P_P ^Three+ 2P_P ^Two) × P_f1+ (-2P '_P ^Three+ 2P '_P ^Two) × (1-P_f1) (iii) Sαδ (2P_P ^Three-4P_P ^Two+ 2P_P) × P_f1+ (2P '_P ^Three-4P '_P ^Two + 2P '_P) × (1-P_f1) (iv) Tδδ (P_P ^Three-2P_P ^Two+ P_P) × P_f1+ (P '_P ^Three-2P '_P ^Two+ P '_P) × (1-P_f1) (v) Sγγ + Tβδ (P_P ^Four-4P_P ^Three+ 3P_P ^Two) × P_f1+ (P '_P ^Four-4P '_P ^Three + 3P '_P ^Two) × (1-P_f1) (vi) Sγδ (-2P_P ^Four+ 6P_P ^Three-6P_P ^Two+ 2P_P) × P_f1+ × (-2P '_P ^Four + 6P '_P ^Three-6P '_P ^Two+ 2P '_P ) × (1-P_f1) (vii) Sδδ (P_P ^Four-5P_P ^Three+ 9P_P ^Two-7P_P+2) × P_f1+ × (P '_P ^Four -5P '_P ^Three+ 9P '_P ^Two-7P '_P+2) × (1-P_f1) (viii) Tββ P_P ^Three× P_f1+ P '_P ^Three× (1-P_f1) (ix) Sβδ (2P_P ^Three-4P_P ^Two+ 2P_P) × P_f1+ (2P '_P ^Three-4P '_P ^Two + 2P '_P) × (1-P_f1) (x) Sββ (-P_P ^Three+ P_P ^Two) × P_f1+ (-P '_P ^Three+ P '_P ^Two)× (1-P _f1 ) Said earlier¹³Relative intensity of C-NMR spectrum and Table 1
So that the probability equation shown in_P, P '_Pas well as
P_f1By optimizing the three parameters of
(I) Average propylene content (F
P), (ii) Prefer propylene in the two-site model
(P) _H) Pro
Pyrene content (P_P) And (iii) P_HAccounts for the copolymer
Ratio (P_f1) Is required.

The (i) average propylene content (FP) of the para-xylene soluble component of the propylene-α-olefin block copolymer of the present invention can be determined by the following equation using the above three parameters. FP = In _{P P × P f1 + P P} '× (1-P f1) ( wt%) present invention, FP obtained by the above equation 20-8
It is preferably 0% by weight, particularly preferably 30 to 70% by weight. In the present invention, (ii) _PP is
It is preferably from 60 to 90% by weight, particularly preferably from 65 to 85% by weight. Furthermore, in the present invention, (iii) P _f1 is 0.
It is preferably from 40 to 0.90, particularly preferably from 0.48 to 0.82.

The propylene-α-olefin block copolymer of the present invention is prepared by a slurry method in the presence of an inert hydrocarbon such as hexane, heptane or kerosene or a liquefied α-olefin solvent such as propylene, a solvent-free method. The temperature condition is room temperature to 130 ° C.
Preferably, it is carried out under the conditions of 50 to 90 ° C. and a pressure of ^{2 to} 50 kg / cm ² . As the reactor in the polymerization step, those usually used in the art can be appropriately used.For example, a stirred tank reactor, a fluidized bed reactor, a continuous reactor using a circulation reactor, a batchwise reactor, a batch reactor. Either method may be used. Specifically, it is obtained by using a known multi-stage polymerization method. That is,
Propylene and / or propylene-α in the first stage reactor
Is a method in which propylene and α-olefin are copolymerized in a second-stage reaction after polymerizing the olefin copolymer.
9, JP-A-3-97747, JP-A-4-9
No. 6912, JP-A-4-96907, JP-A-3-174410, JP-A-2-170803, JP-A-2-170802, JP-A-3-205
No. 439, JP-A-4-153203, JP-A-5-93024, JP-A-4-261423 and the like.

Although a method in which polypropylene and an α-olefin copolymer rubber are mixed and used in an extruder or the like may be used, it tends to be difficult to satisfy the conditions of the present invention. Examples of the propylene-α-olefin block copolymer satisfying the above conditions include, for example, “Product name: Cataloy” by Montell Corporation
And Tokuyama “trade name: PER”, Chisso Corporation “trade name: Newcon”, Idemitsu Petrochemical “trade name: TPO” and the like are commercially available as suitable ones, and these can be used. it can. The ethylene-based copolymer used in the present invention is composed of ethylene and an unsaturated carboxylic acid and / or a derivative thereof. Examples of unsaturated carboxylic acids and / or derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and monoalkyl esters of maleic acid and fumaric acid (alkyl groups having 1 to 18 carbon atoms, for example). 3 to 12 are preferable), unsaturated carboxylic acids such as maleic anhydride, etc., and methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-acrylic acid 2-
Unsaturated carboxylic acid alkyl esters such as ethylhexyl and methyl methacrylate (the carbon number of the alkyl group is 1 to
18, preferably 3 to 12), and vinyl esters such as vinyl acetate.

Among them, acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate,
Vinyl acetate and the like are preferred. These monomers may be used in combination of two or more. The number average molecular weight of the ethylene copolymer used in the present invention is usually 10,000 to 1
00,000, preferably 13,000 to 80,00
0, particularly preferably 15,000 to 50,000. The content of the unsaturated carboxylic acid and / or its derivative in the ethylene-based copolymer is usually 5 to 3
0% by weight, preferably 8 to 28% by weight, particularly preferably 10 to 25% by weight is suitable. Here, the content of the unsaturated carboxylic acid and / or a derivative thereof may be, for example, a monomer of the unsaturated carboxylic acid and / or a derivative thereof such as a terpolymer such as ethylene-methyl methacrylate-maleic anhydride. When two or more are included, the total amount is referred to.

When the content of the unsaturated carboxylic acid and / or its derivative in the ethylene-based copolymer is less than 5% by weight, the high-frequency fusing property and the flexibility in the low-temperature region are unfavorably poor. On the other hand, if it exceeds 30% by weight, the compatibility with the propylene-based polymer described above is poor or the extrusion lamination moldability and heat resistance are poor, which is not preferable. As the melt flow rate (MFR) of the ethylene copolymer, various ones can be used.
The MFR in Kg is 0.5 to 50 (g / 10 minutes), preferably 1 to 40 (g / 10 minutes), particularly preferably
2 to 30 (g / 10 minutes) is appropriate. MFR is 0.5
If it is less than (g / 10 minutes), the laminate moldability is poor, which is not preferable. On the other hand, when it exceeds 50 (g / 10 minutes), the compatibility with the above-mentioned propylene-based polymer is poor, and the extrusion lamination moldability, heat resistance and mechanical strength are poor, which is not preferable.

The ethylene copolymer is usually used at a polymerization pressure of 1,000 to 3,000 kg / cm ² and a polymerization temperature of 150.
It is obtained by radical polymerization using an organic peroxide as an initiator under high pressure and high temperature of up to 300 ° C. The propylene-based polymer is used in an amount of 50 to 90% by weight, preferably 60 to 88% by weight based on the weight of the resin composition comprising the propylene-based polymer and the ethylene-based copolymer of the present invention. Is appropriate. On the other hand, the ethylene copolymer is 50 to 10% by weight based on the weight of the resin composition, preferably,
Suitably it is used in an amount of 40 to 12% by weight. If the amount of the propylene-based polymer is less than 50% by weight, extrusion lamination moldability, heat resistance, adhesiveness to the base fabric, and flexibility in a low-temperature region are unfavorably poor. On the other hand, if it exceeds 90% by weight, the high-frequency fusion property is inferior and is not preferred.

On the other hand, if the amount of the ethylene copolymer is less than 10% by weight, it is not preferable because the high-frequency fusion property is inferior.
On the other hand, if the amount exceeds 50% by weight, extrusion lamination moldability, heat resistance, generation of odor, and adhesiveness to a base fabric (particularly made of polypropylene multifilament) are unpreferable. For the resin composition of the present invention, in addition to the above components, other conventional additives such as antioxidants, weather resistance stabilizers, antistatic agents, lubricants, antiblocking agents, antifoggants In addition, dyes, pigments, oils, waxes, fillers, and the like, and other thermoplastic resins can be appropriately blended within a range that does not impair the object of the present invention. Examples of such additives include antioxidants such as 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, and 4,4′-thiobis- (6-tert-butylphenol. ), 2,2-methylene-bis (4-methyl-6-t-
Butylphenol), octadecyl 3- (3 ', 5'-
Di-t-butyl-1′-hydroxyphenyl) propionate, 4,4′-thiobis- (6-butylphenol), and as an ultraviolet absorber, for example, ethyl-2-cyano-3, 3-diphenylacrylate, 2- ( 2′-hydroxy-5-methylphenyl) benzotriazole,
2-hydroxy-4-octoxybenzophenone; as a plasticizer, for example, dimethyl phthalate, diethyl phthalate, wax, liquid paraffin, phosphate ester; as an antistatic agent, for example, pentaerythritol monostearate, sorbitan monopalmitate , Sulfated oleic acid, polyethylene oxide, carbon wax, as a lubricant, for example, ethylene bis stearamide, butyl stearate, etc., as a coloring agent, for example, carbon black,
As fillers such as phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc., such as glass fiber, asbestos, mica, wollastonite, calcium silicate, aluminum silicate, calcium carbonate, and many other high Molecular compounds can also be blended to the extent that the effects of the present invention are not inhibited. Among these, the use of a compound having a polar group such as an amino group or a hydroxyl group in the molecule is preferable because the effect of the present invention tends to be promoted. When flame retardancy is required, chlorine-based flame retardants such as chlorine paraffin, inorganic compound-based flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, and antimony pentoxide, organic bromine-based flame retardants, Furthermore, it is good to mix many phosphorus-based flame retardants.

Here, the organic bromine-based flame retardant is an organic compound having a bromine atom in the molecule, and is widely used as a flame retardant in the field of resins. Representative examples are decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, tetrabromobisphenol A, hexabromocyclododecane, bistribromophenoxyethane, tribromophenol, ethylenebistetrabromophthalimide, ethylenebispentane Bromophthalimide, ethylenebispentabromodiphenyl, brominated polystyrene, TBA polycarbonate oligomer, hexabromobenzene, 1,2-bis (tribromophenoxy) ethane, tris (2,3-dibromopropyl-1)
And isocyanurate and tris (2,4,6-tribromophenoxy) isocyanurate. Among them, ethylenebistetrabromophthalimide, ethylenebispentabromophthalimide, ethylenebispentabromodiphenyl, tris (2,3-dibromopropyl-1) isocyanurate and tris (2,4,6-tribromophenoxy) isocyanurate are exemplified. preferable.

These flame retardants may be used alone or in combination of two or more. Of these, inorganic compound flame retardants and organic bromine flame retardants are preferred. About the compounding amount of the flame retardant, the propylene-based polymer used in the present invention and 100 parts by weight of the resin composition comprising the ethylene-based copolymer, the inorganic compound-based flame retardant is in a range of 20 to 300 parts by weight, The chlorine-based flame retardant, the organic bromine-based flame retardant and the phosphorus-based flame retardant are preferably used in the range of 1 to 50 parts by weight. The method of compounding the resin composition of the present invention is not particularly limited, and a known method can be used. For example, there is a method of mixing each component with a mixing roll, various mixers such as a Banbury mixer, a Henschel, a tumbler, and a ribbon blender, and then pelletizing using an extruder.

The resin composition of the present invention has a melt flow rate (MFR; 2.16 kg according to JIS K7210),
230 ° C.) is not particularly limited and is selected depending on the molding method.
R is 0.1 to 60 (g / 10 minutes), and preferably 0.2 to 60 (g / 10 minutes).
50 (g / 10 minutes), particularly preferably 0.3 to 40 (g / min).
10 minutes) is appropriate. The thus obtained resin composition of the present invention needs to have a torsional rigidity at −20 ° C. according to JIS K6730 of 2,000 Kgf / cm ² or less. For example, when used as a material for a tent, problems such as breakage and poor workability occur if the flexibility in a low temperature region is poor when used in a cold region. Preferably, the torsional rigidity at −20 ° C. is 1,800.
Those having a Kgf / cm ² or less are preferable. Particularly preferably,
It is 1,500 kgf / cm ² or less.

The resin composition of the present invention may be used as a base fabric, for example, natural fibers (cotton, hemp, etc.), regenerated fibers (viscosulation, cupra, etc.), semi-synthetic fibers (di- or triacetate fibers, etc.), Synthetic fiber (nylon-6
Fiber, nylon-66 fiber, polyester fiber, aromatic polyimide fiber, acrylic fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyvinyl fiber, polyethylene fiber, polypropylene fiber, etc.). In particular, the resin composition of the present invention is preferable because it can be laminated on polyethylene fibers and polypropylene fibers without requiring an anchor coat agent.
The fibers of these base fabrics may be in any shape such as a spun short fiber yarn, a long fiber spun yarn, a split yarn, and a tape yarn. In addition, these base fabrics are woven, knitted,
Any of a nonwoven fabric and a mixed cloth thereof may be used. Among these, a woven or knitted fabric is preferable in consideration of the strength and bending resistance of the sewn portion. The form of the fiber is a long fiber (filament) shape, and a plain woven fabric is preferable. These base fabrics are not particularly limited, and are useful for increasing the strength of the obtained laminate.

The laminated thickness of the resin composition is usually 10 to 5
00 μm, preferably 15 to 400 μm, particularly preferably 20 to 200 μm. If the laminated thickness is less than 10 μm, the high-frequency seal strength is inferior and is not preferred. On the other hand, if it exceeds 500 μm, flexibility and workability are inferior, which is not preferable. The resin composition of the present invention can be formed into a molded body using a known extrusion laminate molding method and a molding machine. In addition, other materials can be further laminated using a known dry laminating machine or the like.

[0032]

The present invention will be described below in more detail with reference to examples. The methods for measuring various physical properties used in the present invention are described below. Measurement of para-xylene insoluble content and soluble content At 130 ° C., the polymer was temporarily dissolved in para-xylene so as to have a concentration of about 1% by weight, and then cooled to 25 ° C. This was taken as a para-xylene soluble matter, and its weight ratio was determined. The para-xylene solubles were used for the next measurement of the ¹³ C-NMR spectrum. ¹³ C-NMR spectrum measurement Measuring machine: JNM-GSX manufactured by JEOL Ltd.
400 Measurement mode: Proton decoupling method Pulse width: 8.0 μs Pulse repetition time: 5.0 μs Number of integrations: 20000 Solvent: Mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene (75/25 volume) %) Internal standard: Hexamethyldisiloxane Sample concentration: 300 mg / 3.0 ml Solvent Measurement temperature: 120 ° C. Main crystallization peak temperature by differential scanning calorimeter (DSC)
(Tcp1), secondary crystallization peak temperature (Tcp2), and
Measurement device of half width (δ) and area ratio (R) : DSC7 type manufactured by PERKIN-ELMER Sample weight: about 3 to 5 mg Measurement method: After heating the sample to 0 ° C. to 230 ° C. and holding for 5 minutes The temperature was lowered to 0 ° C. at a rate of 20 ° C./min to obtain a crystallization temperature curve. The main crystallization peak temperature (Tcp), half width (δ), and peak area were determined from the obtained crystallization temperature curve. MFR Measurement Based on JIS K7210, MFR was measured using a melt indexer manufactured by Takara. Measurement of torsional rigidity 230 ° C. for each resin composition using a press molding machine
A sample having a thickness of 1.5 mm was prepared by using the automatic flexibility tester model TM602 manufactured by Kamishima Seisakusho in accordance with JIS.
According to K7122, the torsional rigidity at a temperature of 0 ° C. and −20 ° C. was measured. Measurement of high-frequency seal strength A sample obtained by high-frequency fusion by a method described later was 15 mm in width.
And Orientec tensile tester (RTA)
-100 type), the 180-degree peel strength was determined under the condition of a tensile speed of 300 mm / min.

Examples 1-4, Comparative Example 1 Propylene-α-olefin block copolymer BPP1: A propylene-α-olefin block copolymer of Cataloy KS357P manufactured by Montell Corporation was used.
The characteristics of the propylene-α-olefin block copolymer are as follows. (1) Elastomer block content 65% by weight (2) Main crystallization peak temperature by DSC (Tcp1)
92.8 ° C (3) Width at half maximum (σ) 5.5 (4) Crystallization energy 25.3 (J / g) (5) Paraxylene insolubles 41% by weight (6) Paraxylene solubles FP 74. 9 wt%, _{P P} 83.4 weight%, P _f1 is 0.7
9. MFR 9g / 1 with temperature 230 ° C and load 2.16Kg
0 minutes (7) Number average molecular weight 61,200 FIG. 3 shows a crystallization curve of this propylene-α-olefin block copolymer by a differential scanning calorimeter (DSC). BPP2: Propylene-α-olefin block copolymer having the following properties (1) Elastomer block content 20% by weight (2) Main crystallization peak temperature by DSC (Tcp1)
109.1 ° C (3) Width at half maximum (σ) 3.8 (4) Crystallization energy 78.8 (J / g) (5) Paraxylene insoluble content 85.6% by weight (6) Paraxylene soluble content FP 54.2 weight%, _{P P} 81.7 weight%, P _f1 0.3
7. MFR at a temperature of 230 ° C and a load of 2.16 kg 12.5 g / 1
0 minutes (7) Number average molecular weight 50,300

Ethylene copolymer E-1: MFR of 20 (g) at 190 ° C. under a load of 2.16 kg
/ 10 min), an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% by weight (number average molecular weight: 19,00
0) E-2: MFR at 190 ° C. under a load of 2.16 kg is 6 (g / g).
10 minutes), an ethylene-methyl acrylate copolymer having a methyl acrylate content of 20% by weight (number average molecular weight:
E-3: 190 ° C., 2.16 kg MFR of 7 (g / g)
10 minutes), the content of n-butyl acrylate is 13% by weight,
Ethylene terpolymer having a maleic anhydride content of 1% by weight (number average molecular weight: 23,000) [Kneading treatment] The above propylene-α-olefin block copolymer and ethylene copolymer are prepared in predetermined amounts. Formulated with
After mixing with a tumbler, the mixture was pelletized at a temperature of 190 to 210 ° C. using a twin screw extruder (Model KTX37) manufactured by Kobe Steel Ltd. [Extrusion lamination molding] The above-mentioned pellets are caliber 50m
m extruder, using an extrusion laminator manufactured by Modern Machinery Co., Ltd. with a die width of 500 mm, a resin composition using an ethylene-vinyl acetate copolymer at a die temperature of 220 ° C., and the other at a die temperature of 260 ° C. and 680 denier. Polypropylene multifilament base cloth (20 ×
50/75 μm on both sides of 20 / inch ² )
And 100 μm. The extrusion laminate formability was evaluated by the following method. (Drawdown property) The rotation speed of the screw was kept constant at 75 rpm, and the take-up speed when surging, film breakage and close contact with the cooling roll occurred was determined. (Neck-in) When the thickness of 50 μm is laminated on both sides of the base fabric,
The difference in the width of the actually formed product was determined from the die width. [High-frequency fusion property] The laminates laminated as described above were combined with a Yamamoto Vinita YVT-700 type high-frequency sealing machine (rated power consumption 13 KVA, rated high-frequency output 7 KW,
Using a frequency of 41.14 MHz, high frequency welding was performed under the conditions of a welding time of 3 seconds and a cooling time of 2 seconds. Next, the high frequency welding strength was determined according to the method described above.

Table 2 shows the above evaluation results.

[0036]

[Table 2] Table 2 Example and Composition MFR of Resin Composition Torsional Rigidity Comparative Example No. (1) Component (2) Component 230 ° C. (Kgf / cm ² ) Kind Compounding amount Kind Compounding amount Load 2.16 kg 0 ° C. -20 ° C. (g / 10 Min) Example 1 BPP1 80 E-2 20 8.9 284 319 Example 2 BPP1 70 E-2 30 9.4 225 285 Example 3 BPP1 80 E-1 20 11.8 372 448 Example 4 BPP1 70 E-1 30 13.4 295 376 Example 5 BPP1 80 E-3 20 9.5 564 652 Example 6 BPP1 65 E-3 35 9.8 762 865 Comparative Example 1 BPP1 100 − − 9.0 342 538 Comparative Example 2 BPP2 100 − − 12.5 8,600 10,390 Comparative Example 3 BPP2 70 E -2 30 9.5 6,170 7,560 Comparative Example 4 BPP2 80 E-3 20 15.6 6,830 8,610 Comparative Example 5--E-2 100 9.0 196 458

[0037]

[Table 3] Table 2 (continued) Example and high frequency seal Extrusion lamination Comparative example number Strength formability (g / 15 mm width) Drawdown property Neck-in 50 μm 75 μm 100 μm (m / min) (mm) Example 1 1,290 1,460 2,460 110 116 Example 2 990 1,030 2,690 100 112 Example 3 1,240 1,480 1,910 80 138 Example 4 820 890 2,280 70 156 Example 5 1,050 1,340 2,780 100 128 Example 6 1,380 1,560 2,980 90 135 Comparative Example 1 0 0 0 70 105 Comparative Example 2 0 0 0 60 168 Comparison Example 3 <50 <50 <50 60 226 Comparative Example 4 <50 <50 <50 50 283 Comparative Example 5 1,350 1,480 1,810 50 245

[0038]

Industrial Applicability The resin composition of the present invention is more excellent in adhesiveness to a base fabric, high-frequency fusion property, flexibility in a low-temperature region, and extruded laminate moldability than conventional ones. It is effective as various construction fields, vehicle parts such as automobiles, various packaging materials, electric parts such as home appliances, various industrial materials, and the like. In particular, it is useful as a tent material and a safety protection garment for electric work.

[Brief description of the drawings]

FIG. 1 is a diagram showing a nuclear magnetic resonance spectrum of isotope carbon of an ethylene-propylene copolymer.

FIG. 2 is a diagram showing names of carbons derived from a chain distribution in a polyolefin.

FIG. 3 is a view showing a DSC crystallization curve of a propylene-α-olefin block copolymer used in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 53/00 C08L 53/00

Claims (5)

[Claims] (1) In a crystallization peak temperature curve by a differential scanning calorimeter, a crystallization energy ΔHC is 90%.
(J / g) not more than 50 to 90 propylene-based polymer
50% by weight, and (2) an ethylene copolymer comprising ethylene and an unsaturated carboxylic acid and / or a derivative thereof.
And a torsional rigidity of 2,000 kgf at a temperature of -20 ° C according to JIS K6730.
/ Cm ² or less. 2. The propylene-based polymer comprises: (1) a polypropylene block, (2) propylene, and 2 to 2 carbon atoms.
A propylene-α-olefin block copolymer comprising 12 (excluding 3) copolymer elastomer blocks with α-olefin, wherein the copolymer elastomer block is the propylene-α-olefin block copolymer. The resin composition according to claim 1, wherein the proportion of the resin composition is 30 to 70% by weight. 3. The propylene-α-olefin block copolymer has a main crystallization peak temperature in the range of 85 to 115 ° C. in a crystallization peak temperature curve by a differential scanning calorimeter, and has a crystallization energy of The thermoplastic resin composition according to any one of claims 1 to 2, wherein the thermoplastic resin composition is 70 (J / g) or less. 4. The resin composition according to claim 1, wherein the propylene-α-olefin block copolymer has the following physical properties (1) and (2). (1) Paraxylene insoluble content at a temperature of 25 ° C. is 25 to
65% by weight. (2) The component soluble in para-xylene at a temperature of 25 ° C. has (i) an average propylene content (FP) of 20 to 80% by weight according to a two-site model, and (ii) propylene preferentially in a two-site model. The propylene content (P _P ) of the copolymer (P _H ) formed at the active site where the polymerization proceeds to 6 is 6
(Iii) the proportion of P _H in the copolymer (P _f1 ) is 0.60 to 0.90. 5. A tent or a safety protective garment for electrical work, wherein the resin composition according to claim 1 is laminated on a polypropylene multifilament base fabric.