JP2011001506A - Flame-retardant resin composition and molding obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin material which is excellent in heat resistance, flexibility, elongation characteristics, etc., while holding excellent mechanical resin performances (abrasion resistance, whitening resistance, etc.) even when fully enhancing flame retardancy of the thermoplastic resin, of which the molding has excellent surface smoothness and appearance, and which also has high flame retardancy; and a flame-retardant molding utilizing the thermoplastic resin material.SOLUTION: The flame-retardant resin composition is obtained by blending 0-30 pts.wt. of a functional group-containing olefin polymer component (D) and 3-300 pts.wt. of a flame retardant component (E) with 100 pts.wt. of a resin component. The resin component comprises: 5-90 wt.% of a propylene-ethylene copolymer component (A) produced using a single-site catalyst; 5-90 wt.% of an ethylene copolymer component (B) selected from an ethylene-α,β-unsaturated carboxylic acid ester copolymer (B1), an ethylene-vinyl ester copolymer (B2), or an ethylene-α-olefin copolymer (B3) with density of 0.86 or more and less than 0.91 g/cm; and 5-90 wt.% of a polyethylene resin component (C) with density of 0.91-0.97 g/cm. The flame-retardant molding is obtained by using the flame-retardant resin composition.

Description

  The present invention relates to a flame retardant resin composition and a molded body comprising the same, and more specifically, excellent mechanical resin performance (abrasion resistance, heat resistance, resistance) even if the flame retardancy of a thermoplastic resin is sufficiently increased. It has excellent flexibility, elongation characteristics, etc. while possessing whitening properties, etc., and also has excellent flame retardant resin composition with excellent appearance and surface smoothness of molded products, and high flame retardancy The present invention relates to an extruded body and a molded body such as an electric wire-cable.

Since plastic materials that are heavily used as industrial materials are generally flammable, products made of molded products made from plastic materials have been strongly demanded to be flame-retardant for safety in use. ing.
Among the plastic materials, a highly versatile thermoplastic resin (and its elastomer) can be made flame retardant by categorizing the resin itself or adding a flame retardant to the resin. Among them, a method using a flame retardant that is relatively simple and can be made flame retardant is widely used.

  Examples of the flame retardant include halogen flame retardant combined with antimony oxide and halide, organic flame retardant such as phosphorus and bromine, aluminum hydroxide and magnesium hydroxide, or a combination of these and magnesium carbonate. Inorganic flame retardants are properly used according to the application and required performance. In recent years, avoiding problems such as the generation of halogen-based harmful gases in the event of a fire of halogen-based flame retardants and deterioration of appearance quality due to bleed-out of the flame retardants on the surface of molded products with organic flame retardants Therefore, importance is attached to flame retardant materials using inorganic flame retardants, particularly hydrated metal compounds.

However, any flame retardant requires an appropriate blending amount in order to impart sufficient flame retardancy, and as a result, flexibility, abrasion resistance, whitening resistance, mechanical strength (particularly, There is a drawback that various performances inherent to the resin component such as tensile elongation at break) are lowered.
On the other hand, flame retardant materials are used for insulated wires for indoor and outdoor use, for vehicles, etc., but the requirements for specifications such as wear resistance and heat resistance have become stricter, and a large amount of inorganic materials used for electric wires and cables. Ethylene copolymer such as ethylene and unsaturated carboxylic acid ester copolymer and ethylene and vinyl ester copolymer such as ethylene-ethyl acrylate copolymer, etc. Although a flame retardant resin composition using a coalescence and an inorganic flame retardant is disclosed (see Patent Document 1), the flame retardant material using these ethylene-based polymers is excellent in heat resistance, wear resistance, and the like. It has a room for improvement.

In addition, various proposals have been made for polypropylene-based resin compositions that are originally made of a polypropylene resin that is excellent in various properties such as wear resistance and heat resistance and that have been subjected to the above-described flame retardant formulation.
For example, an abrasion-resistant flame-retardant resin composition in which a propylene-ethylene block copolymer, an ethylene-vinyl acetate copolymer, and a metal hydroxide are blended has been proposed (see Patent Document 2). However, it is still not enough.
In addition, a flame-retardant and wear-resistant resin composition in which a propylene-ethylene block copolymer, a polyolefin-based elastomer, and a metal hydroxide are blended to improve the dispersibility of the flame retardant is also presented (Patent Document). 3). However, even if an improvement in wear resistance is seen, it has not been fully satisfied.

Further, as a method of using a specific resin excellent in heat resistance and wear resistance, 5 to 50 parts by weight of an ethylene-vinyl acetate copolymer (or ethylene-acrylic acid ester copolymer), 5 to 30 polypropylene resins are used. Parts by weight, 5 to 50 parts by weight of a styrene-conjugated diene block copolymer (or hydrogenated product), 5 to 40 parts by weight of rubber of ethylene-acrylate copolymer, and ethylene-propylene copolymer rubber 0 Non-halogen flame retardant containing 100 to 300 parts by weight of a metal hydrate treated with a silane coupling agent with respect to 100 parts by weight of a base polymer including -15 parts by weight and 5 to 30 parts by weight of a carboxylic acid-modified polyolefin resin A resin composition has been proposed (see Patent Document 4). Further, magnesium hydroxide (or carbonic acid carbonate) is used with respect to 100 parts by weight of a base polymer including 90 to 97 parts by weight of an ethylene-vinyl acetate copolymer (or ethylene-ethyl acrylate copolymer) and 3 to 10 parts by weight of a polypropylene-based polymer. A flame retardant resin composition containing 20 to 100 parts by weight of calcium is proposed (see Patent Document 5). Furthermore, a flame retardant resin comprising 100 parts by weight of a propylene resin, 1 to 40 parts by weight of an ethylene-vinyl acetate copolymer having a number average molecular weight of 2,000 to 4,000, and 30 to 200 parts by weight of a metal hydrate. A composition has been presented (see Patent Document 6).
However, even if these flame retardant resin compositions are all improved in abrasion resistance, they cannot be said to have sufficient heat resistance, elongation characteristics, flexibility, and surface appearance of molded products.

  In this way, from the background of the above-mentioned background technology in the flame retardancy of thermoplastic resins and the current situation, excellent mechanical resin performance (wear resistance, whitening resistance) even if the flame retardancy of thermoplastic resins is sufficiently enhanced A thermoplastic resin material that has excellent heat resistance, flexibility, elongation characteristics, etc., and also has excellent surface smoothness and appearance, and has high flame resistance. Development is sought after.

Japanese Patent Laid-Open No. 62-010151 JP 2000-86858 A JP 2000-26696 A JP 2005-314516 A JP 2004-75936 A JP 2006-348137 A

  In view of the above-mentioned problems of the prior art, the object of the present invention is to maintain excellent mechanical resin performance (wear resistance, whitening resistance, etc.) even if the flame retardancy of the thermoplastic resin is sufficiently increased. Another object of the present invention is to provide a thermoplastic resin material that is excellent in flexibility, elongation characteristics, etc., has excellent surface smoothness and appearance, and has high flame retardancy, and a flame retardant molded article using the same. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a propylene-ethylene copolymer component (A) produced with a single-site catalyst and ethylene-α, β-unsaturated carboxylic acid An ethylene copolymer component (B) selected from an ester copolymer (B1), an ethylene-vinyl ester copolymer (B2) or an ethylene-α-olefin copolymer (B3) having a specific density; When the resin component containing the polyethylene resin component (C) in a specific ratio is blended with the functional group-containing olefin polymer component (D) and the flame retardant component (E) in a specific ratio, mechanical resin performance ( Not only wear resistance, whitening resistance, etc.) but also excellent heat resistance, flexibility, elongation characteristics, etc., and also has excellent surface smoothness and appearance of molded products and high flame resistance thermoplastic resin material. The book is found Which resulted in the completion of the Akira.

That is, according to the first invention of the present invention,
5 to 90% by weight of propylene-ethylene copolymer component (A) produced with a single site catalyst,
5 to 90% by weight of at least one ethylene copolymer component (B) selected from the following (B1) to (B3)
(B1) Ethylene-α, β-unsaturated carboxylic acid ester copolymer (B2) Ethylene-vinyl ester copolymer (B3) Ethylene-α olefin copolymer having a density of 0.86 or more and less than 0.91 g / cm ³ ,
as well as,
Resin component 100 comprising 5 to 90% by weight of a polyethylene resin component (C) having a density of 0.91 to 0.97 g / cm ³ (wherein the total of components (A) to (C) is 100% by weight). Provided is a flame retardant resin composition comprising 0 to 30 parts by weight of a functional group-containing olefin polymer component (D) and 3 to 300 parts by weight of a flame retardant component (E) with respect to parts by weight. Is done.

  According to the second invention of the present invention, in the first invention, the polyethylene resin component (C) has a linear low density having a molecular weight distribution (Mw / Mn) measured by GPC of 10 or more. There is provided a flame retardant resin composition characterized by being polyethylene or high density polyethylene.

According to the third invention of the present invention, in the first or second invention, the propylene-ethylene copolymer component (A) has the following characteristics (i) to (ii): A flame retardant resin composition is provided.
(I) In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak due to the glass transition observed in the temperature range of −60 to + 20 ° C. is a single peak. Temperature is 0 ° C. or less (ii) Plot of elution amount (dwt% / dT) against temperature by temperature rising elution fractionation method (TREF) in a temperature range of −15 ° C. to 140 ° C. using o-dichlorobenzene solvent Having the following characteristics (ii-A) to (ii-C) in the TREF elution curve obtained as:
(Ii-A) In the elution curve, two peaks are observed, the peak T (A1) observed on the high temperature side is in the range of 65 to 95 ° C., and the peak T (A2) observed on the low temperature side is 45. (Ii-B) The amount W (A2) of the component (A2) eluting up to the temperature T (A3) at the midpoint between both peaks of T (A1) and T (A2) is 5 to 70% by weight. Yes, the component is a propylene-ethylene random copolymer containing 6 to 15% by weight of ethylene (ii-C) The amount W (A1) of the component (A1) eluted after elution of the component eluted by T (A3) ) Is 95 to 30% by weight, and the component is a propylene homopolymer or propylene-ethylene random copolymer containing 0 to 6% by weight of ethylene

According to a fourth aspect of the present invention, in any one of the first to third aspects, the propylene-ethylene copolymer component (A) further has the following characteristic (iii): A flame retardant resin composition is provided.
(Iii) 95-30 wt% of a crystalline propylene homopolymer or crystalline propylene-ethylene random copolymer component (A1) having an ethylene content of 0-6 wt% in the first step using a single-site catalyst, It is obtained by sequentially polymerizing 5 to 70% by weight of a low crystalline propylene-ethylene random copolymer component (A2) having an ethylene content of 6 to 15% by weight in the second step.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the propylene-ethylene copolymer component (A) further has the following characteristic (iv): A flame retardant resin composition is provided.
(Iv) In a TREF elution curve obtained as a plot of elution amount (dwt% / dT) against temperature by a temperature rising elution fractionation method (TREF) in a temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent, having the following characteristics (iv-a) ~ (iv-D) (iv-a) 2 peaks in the elution curve is observed, a peak is observed in the high temperature side T (A1) is in the range of sixty-five to eighty-eight ° C. There, a peak is observed in the low temperature side T (A2) is in the 45 ° C. or less (iv-B) T (A1) and T (A2) temperature T (A3) component elutes to the midpoint of both peaks ( the amount of A2) W (A2) is 30 to 70 wt%, propylene said component comprises 8-14 wt% of ethylene - eluting before ethylene random copolymer (iv-C) T (A3) Elute after elution of components The amount of component (A1) W (A1) is 70 to 30 wt%, the component is propylene containing 1-5 wt% of ethylene - ethylene random copolymer (iv-D) 99% by weight is eluted The temperature T (A4) is 90 ° C. or less, and the temperature difference ΔT (T (A4) −T (A1)) from the peak T (A1) to T (A4) is 5 ° C. or less.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the ethylene copolymer component (B) is an ethylene- (meth) acrylic acid alkyl ester copolymer or ethylene- There is provided a flame retardant resin composition characterized by being a vinyl acetate copolymer.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the component (A), the component (B), and the component (C) are added to the total amount of 100 parts by weight of the component ( D) 1-30 weight part and inorganic flame retardant component (E) 20-300 weight part are mix | blended, The flame-retardant resin composition characterized by the above-mentioned is provided.

  According to the eighth invention of the present invention, in the seventh invention, the functional group-containing olefin polymer component (D) is an acid anhydride group-containing olefin copolymer or a metal salt thereof, or a modified polyolefin system. Provided is a flame retardant resin composition, which is a component selected from resins.

  According to a ninth aspect of the present invention, there is provided the flame retardant resin composition according to the seventh or eighth aspect, wherein the inorganic flame retardant is aluminum hydroxide and / or magnesium hydroxide. The

  Furthermore, according to the 10th invention of this invention, the molded object formed by shape | molding the flame-retardant resin composition which concerns on any one of the 1st-9th invention is provided.

  According to an eleventh aspect of the present invention, in the tenth aspect, there is provided a molded body that is an electric wire-cable.

  According to the present invention, even if the flame retardancy of a thermoplastic resin is sufficiently increased, excellent mechanical resin performance (abrasion resistance, heat resistance, whitening resistance, etc.) is maintained and excellent in flexibility and elongation characteristics. In addition, it is possible to provide a thermoplastic resin material for molded articles which is excellent in surface smoothness and appearance of molded articles and has high flame retardancy, and a flame retardant molded article thereby.

In the present invention, as described above, the propylene-ethylene copolymer component (A) produced with a single-site catalyst (hereinafter sometimes abbreviated as “component (A)”) is 5 to 90% by weight. , Ethylene-α, β-unsaturated carboxylic acid ester copolymer (B1), ethylene-vinyl ester copolymer (B2), or ethylene-α-olefin copolymer having a density of 0.86 or more and less than 0.91 g / cm ³ At least one ethylene-based copolymer component (B) selected from (B3) (hereinafter sometimes abbreviated as “component (B)”) in an amount of 5 to 90% by weight and a density of 0.91 to 0 .97 g / cm ³ of a polyethylene resin component (C) (hereinafter, also abbreviated as “component (C)”). Olefin polymer component (D) , Sometimes abbreviated as “component (D)”) 0 to 30 parts by weight, and flame retardant component (E) (hereinafter also abbreviated as “component (E)”) 3 to 300 parts by weight. A flame retardant resin composition, a molded product obtained by molding the resin composition, or an extruded molded product, and an electric wire-cable.
Hereinafter, basic characteristics, constituent components, molded articles, molding methods, and the like of the flame-retardant resin composition of the present invention will be described in detail.

1. About flame retardancy Generally, plastic materials, especially thermoplastic resin molded articles, are generally flammable, and therefore flame retardant has been strongly demanded for safety in the use of molded articles.
Conventionally, in polypropylene resins, a large amount of inorganic flame retardants must be blended to provide sufficient flame retardancy, and satisfy mechanical properties, particularly tensile elongation properties and flame retardant properties. It was difficult to do.

In the present invention, a case where the oxygen index in JIS K7201 is less than 21 is referred to as flammability, a case where the oxygen index is 21 or more is referred to as flame retardancy, and when flame retardancy is high, self-extinguishing ( Self-extinguishing). The oxygen index (OI) is defined below.
At a temperature of 180 ° C., a 3 mm sheet was prepared by compression (press) molding, a test piece having a width of 6.5 mm × a length of 150 mm was cut, and the obtained test piece was in accordance with the method of JIS K-7201. Measure the oxygen index.

Using an oxygen measuring device, the oxygen index (OI) is measured by measuring the minimum oxygen flow rate necessary for the burning time of the test piece to continue for 3 minutes or more, or for the combustion length after flame to continue to burn to 50 mm or more. Ask for.
OI (%) = {[O ₂ ] / ([O ₂ ] + [N ₂ ])} × 100
[O ₂ ]: Flow rate of oxygen L / min [N ₂ ]: Flow rate of nitrogen L / min

2. Regarding the composition of the resin composition of the present invention (1) Basic structure A specific resin composition that is employed in the present invention is a polypropylene-based resin material that has excellent flexibility, heat resistance, rigidity, etc., and excellent moldability. Propylene-ethylene copolymer has excellent compatibility between resin components, and good flexibility is maintained even when a large amount of inorganic flame retardant is blended. If used, the stress at the time of strain is reduced, so that the stress applied to the interface between the resin component and the flame retardant can be suppressed, and the mechanical strength (particularly, tensile elongation) can be prevented from being reduced. The surface smoothness of the product is good and the whitening resistance is further improved.

The flame retardant resin composition of the present invention comprises a specific propylene-ethylene copolymer component (A), an ethylene-α, β-unsaturated carboxylic acid ester copolymer (B1), an ethylene-vinyl ester copolymer. It comprises at least one ethylene copolymer component (B) selected from a coalescence (B2) or a specific density ethylene-α olefin copolymer (B3), and a specific density polyethylene resin component (C). It consists of a resin component, a functional group-containing olefin polymer component (D), and a flame retardant component (E), and additional components can be added within a range that does not impair the efficacy (action effect) of the present invention. Each component must meet various requirements to solve problems.
The detailed description of each component is added below.

(2) Propylene-ethylene copolymer component (A)
(I) Basic features In conventional polypropylene resins, in order to improve the tensile elongation at break of a relatively high crystallinity component mainly composed of propylene, an ethylene elastomer is blended as a low crystallinity component. The technique of using a so-called block copolymer produced by sequential polymerization of low-crystalline components containing ethylene is widely known to those skilled in the art, but these low-crystalline components are components mainly composed of propylene. Because of their low compatibility with each other, they are phase-separated and each has a phase-separated structure that becomes a separate phase.
When a flame retardant for imparting flame retardancy is added to the resin having such a structure, uneven distribution of the flame retardant occurs due to different compatibility with the softening temperature and the flame retardant in each phase, Since breakage is likely to occur at a portion where the flame retardant concentration is high, the effect of improving the tensile elongation at break cannot be sufficiently exhibited. In addition, when an external force is applied to the molded product, peeling occurs not only between the flame retardant and the resin but also at the interface of each phase of the resin component, which causes a problem that bending whitening is extremely deteriorated.

  The propylene-ethylene copolymer component (A) in the present invention is produced by a single site catalyst, unlike a propylene resin material using a multi-site catalyst such as the conventional Ziegler-Natta catalyst. . The single site catalyst refers to a catalyst having the same active site (single site), and specifically includes a metallocene catalyst. The propylene-ethylene random copolymer obtained by such a single-site catalyst is more flexible than a propylene-ethylene block copolymer obtained by a conventional Ziegler catalyst, and a large amount of inorganic flame retardant. Even if is blended, flexibility can be maintained. Moreover, melting | fusing point is also high compared with an ethylene-type copolymer, and can improve the heat resistance of a flame-retardant resin composition.

The propylene-ethylene copolymer component (A) of the present invention preferably has an ethylene content of 0.1 to 20% by weight, more preferably 0.2 to 15% by weight. The melt flow rate MFR of the propylene-ethylene copolymer component (A) is preferably from 0.1 to 100 g / 10 minutes, more preferably from 0.5 to 50 g / 10 minutes.
In particular, the propylene-ethylene copolymer component (A) in the present invention is defined by the following characteristics that are different in ethylene content and crystallinity to improve the balance of physical properties, as will be described in detail below. However, a propylene-ethylene copolymer consisting mainly of two components (A1) and (A2) is preferred.

(Ii) Identification by Solid Viscoelasticity Measurement (DMA) The preferred propylene-ethylene copolymer component (A) includes a low crystalline component (A2) for improving the tensile elongation (tensile elongation at break). However, those having a phase separation structure with the relatively high crystallinity component (A1) mainly composed of propylene are preferable.

The absence of the phase separation structure is identified by the fact that the tan δ curve has a single peak between −60 and + 20 ° C. in the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA). It becomes.
This is because, in solid viscoelasticity measurement, the glass transition temperature of a propylene-ethylene copolymer resin is usually observed between -60 and + 20 ° C. as the peak of the tan δ curve. While only the glass transition temperature is observed, the phase separation structure is based on showing a plurality of peaks because the glass transition temperature of each phase is observed separately.

Here, the solid viscoelasticity measurement (DMA) is specifically performed by applying a sine distortion of a specific frequency to a strip-shaped sample piece and detecting the generated stress.
That is, the frequency is 1 Hz, and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus and the loss elastic modulus are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by the ratio thereof is plotted against the temperature. In general, the peak of loss tangent (tan δ) at 0 ° C. or less is for observing the glass transition of the amorphous part, and here, this peak temperature is defined as the glass transition temperature Tg (° C.). The peak temperature due to glass transition is preferably −5 ° C. or lower, more preferably −20 to −10 ° C.
In addition, in the whole measurement temperature range, another relaxation peak may appear at about 20 to 120 ° C., which is based on crystal relaxation called α relaxation, and is the glass transition targeted in the present invention. It is distinguished from

(Iii) Temperature rising elution fractionation method (TREF)
The low crystalline propylene-ethylene random copolymer component (A2) preferably contained in the propylene-ethylene copolymer component (A) used in the present invention does not have a phase separation structure with the component (A1), And, in order to have a sufficient effect of improving the tensile elongation at break, it is preferable to sufficiently reduce the crystallinity by increasing the ethylene content, and the compatibility decreases as the ethylene content increases. it is suppressed to within the range of.
Further, the propylene-ethylene random copolymer component (A1), which is preferably contained in the propylene-ethylene copolymer component (A), has a low crystallinity distribution on the high crystal side. Since the crystallinity distribution is narrow, the tensile break elongation is improved by taking a more uniform and fine crystal structure.

The crystallinity, crystallinity distribution, and ratio of these components are specified by a temperature rising elution fractionation method (TREF).
The technique for evaluating the crystallinity distribution of a propylene-ethylene copolymer by TREF is well known to those skilled in the art. For example, detailed measurement methods are shown in the following documents.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)
In TREF measurement, the lower the crystallinity, the lower the elution, and the higher the crystallinity, the higher the elution. .
The components (A1) and (A2), which are preferable components of the propylene-ethylene copolymer component (A), are greatly different in crystallinity, and both components can be accurately separated by TREF. .

In the present invention, the TREF measurement is specifically measured as follows.
A sample is dissolved in 140 ° C. o-dichlorobenzene (containing 0.5 mg / mL BHT) to form a solution. After this is introduced into a 140 ° C. TREF column, it is cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, subsequently cooled to −15 ° C. at a temperature lowering rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene as a solvent (containing 0.5 mg / mL BHT) is allowed to flow through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. in the TREF column. Elution is performed for 10 minutes, and then the column is linearly heated to 140 ° C. at a temperature increase rate of 100 ° C./hour to obtain an elution curve along the temperature increase.
The elution curve is a TREF elution curve obtained as a plot of elution amount (dwt% / dT) against temperature by the temperature rising elution fractionation method (TREF) in the temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent. It is.

[Specification by TREF peak temperature of each preferred propylene-ethylene copolymer component (A), each elution amount, etc.]
The preferred propylene-ethylene copolymer component (A) is roughly composed of two components having different crystallinity so that two peaks are observed, and as a result, sufficient improvement in elongation is obtained. From this, in the preferable propylene-ethylene copolymer component (A), two peaks are observed in the elution curve in the range of −15 ° C. to 140 ° C.

In TREF measurement, the higher the elution temperature, the higher the crystallinity, and the lower the component, the lower the crystallinity. The propylene-ethylene random copolymer component (A1), which is preferably contained in the propylene-ethylene copolymer component (A), has a relatively high crystallinity. Therefore, the crystallinity should not be lowered excessively, and the peak temperature T (A1) is preferably 65 ° C. or higher. On the other hand, if the crystallinity becomes too high, the tensile elongation at break decreases, so that T (A1) is preferably 95 ° C. or lower.
On the other hand, the low crystalline propylene-ethylene random copolymer component (A2) contained in the preferred propylene-ethylene copolymer component (A) is improved in tensile elongation at break if the crystallinity is not sufficiently lowered. Since the effect cannot be exhibited, the peak temperature T (A2) is desirably 45 ° C. or lower.

The propylene-ethylene random copolymer component (A1) having a relatively high crystallinity and the low crystallinity propylene-ethylene random copolymer component (A2) contained in the preferred propylene-ethylene copolymer component (A) are: , Almost at the temperature T (A3) between the peaks of both components observed in the TREF elution curve.
Here, when the intermediate temperature T (A3) is accurately expressed by a mathematical formula,
T (A3) = {T (A1) + T (A2)} / 2.
At this time, the component eluted by T (A3) is a low crystalline propylene-ethylene random copolymer component (A2), and the amount W (A2) is preferably 5 to 70% by weight. In accordance with this, the component after removing the component eluted by T (A3) (after dissolution) is a propylene-ethylene random copolymer component (A1) having relatively high crystallinity, and its amount W (A1) is 95 to 30% by weight.

W (A2) is necessary for improving the tensile elongation at break, and when W (A2) is less than 5% by weight, it is difficult to obtain a sufficient improvement effect, so W (A2) is at least 5% by weight. In order to exhibit a sufficient improvement effect, it is more preferably 30% by weight or more, and further preferably 40% by weight or more. That is, W (A1) is preferably 95% by weight or less, more preferably 70% by weight or less, and particularly 60% by weight or less.
On the other hand, if there is too much W (A2), that is, if the amount of the component having relatively high crystallinity is too small, problems such as deterioration of moldability and heat resistance are likely to occur. % Or less, and more preferably 60% by weight or less. That is, W (A1) is preferably 30% by weight or more, and more preferably 40% by weight or more.

  The components separated at this time are taken out and analyzed for each component, whereby the ethylene content in each component can be measured. Here, the low crystalline propylene-ethylene random copolymer component (A2) eluting up to the temperature T (A3) can exhibit an effect of improving the tensile elongation at break if the crystallinity is not sufficiently lowered. Since it is difficult to perform, the peak temperature T (A2) is more preferably 45 ° C. or less, further 10 to 40 ° C., and particularly preferably 20 to 30 ° C. At this time, since the crystallinity of the propylene-ethylene random copolymer tends to decrease as the ethylene content increases, the propylene-ethylene random copolymer preferably contains 6 wt% or more, more preferably 8 wt% or more of ethylene. On the other hand, if the ethylene content is excessively large, a phase separation structure is easily obtained, and therefore, it is preferable to suppress it to a range in which phase separation does not occur, and at most 15 wt%, more preferably 14 wt% or less.

On the other hand, the propylene-ethylene random copolymer component (A1) having a relatively high crystallinity after removing the components eluted by T (A3) (after elution) is to maintain moldability and heat resistance. The peak T (A1) is preferably in the range of 65 to 95 ° C, more preferably 69 to 88 ° C, particularly 73 to 83 ° C. If the crystallinity of the component (A1) is too high, the compatibility of the resin component tends to be lowered. At this time, the ethylene content is preferably 0 to 6% by weight, more preferably 1 to 5% by weight, particularly 2 to 4% by weight. % Range.
Here, if the crystallinity of the component (A1) is high, even if the compatibility is improved by the component (A2), it is preferable to add as much inorganic filler as possible to improve the flame retardancy. Sometimes the tensile elongation at break is insufficient. In order to further improve this, it is preferable that the crystallinity of the component (A1) is also in a specific range.
That is, the crystallinity of the component (A1) itself is lowered within a range in which heat resistance and moldability can be maintained, and by selecting one having a narrow crystallinity distribution, the crystal structure is refined and the tensile elongation at break is improved. For this purpose, the ethylene content in the preferred component (A1) is preferably 1% by weight or more, and the peak temperature T (A1) in the TREF elution curve, which is a measure of crystallinity, is preferably 88 ° C. or less. . At this time, even if T (A1) decreases, the crystallinity distribution is widened, and if there are many highly crystalline components, the improvement effect tends to be reduced, so the temperature T (A4) at which 99% by weight elutes is reduced. It is preferably 90 ° C. or lower, and more preferably 85 ° C. or lower. And it is also preferable that temperature difference (DELTA) T (T (A4) -T (A1)) from peak T (A1) to T (A4) is 5 degrees C or less, and it is more preferable that it is 4 degrees C or less.

(Iv) Method for measuring ethylene content a. Separation of components (A1) and (A2) Based on T (A3) obtained by the previous TREF measurement, a component of T (A3) soluble component (A2) was obtained by a temperature rising column fractionation method using a preparative fractionator. ) And T (A3) insoluble component (A1), and the ethylene content of each component is determined by NMR.
The temperature rising column fractionation method refers to a measurement method disclosed in, for example, Macromolecules; 21, 314 to 319 (1988).

B. Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of a sample o-dichlorobenzene (ODCB) solution (10 mg / mL) dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (A3) at a heating rate of 10 ° C./hour and held for 1 hour. The accuracy of column temperature control through a series of operations is ± 1 ° C.
Next, 800 mL of o-dichlorobenzene is allowed to flow at a flow rate of 20 mL / min while maintaining the column temperature at T (A3), thereby eluting and recovering components soluble in T (A3) present in the column.
Next, the column temperature is increased to 140 ° C. at a rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 mL of a 140 ° C. solvent (ODCB) is allowed to flow at a flow rate of 20 mL / min to obtain T (A3 ) To elute and collect insoluble components.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is collected by filtration and dried overnight in a vacuum dryer.

C. Measurement by NMR The ethylene content of each of the components (A1) and (A2) obtained by the above fractionation is analyzed by analyzing a ¹³ C-NMR spectrum measured according to the following conditions by the proton complete decoupling method. Ask.
Model: GSX-400 (or equivalent device) manufactured by JEOL Ltd.
Carbon nuclear resonance frequency of 100 MHz or more Solvent: o-dichlorobenzene: heavy benzene = 4: 1 (volume ratio) concentration: 100 mg / mL
Temperature: 130 ° C Pulse angle: 90 ° Pulse interval: 15 seconds Integration count: 5,000 times or more

The spectrum may be assigned with reference to Macromolecules; 17, 1950 (1984), for example. The attribution of spectra measured under the above conditions is as shown in Table 1 below. Symbols such as S _{alpha alpha} in the table, Carman other; accordance notation (Macromolecules 10,536 (1977)), P represents methyl carbon, S is methylene carbon, T is a methine carbon, respectively.

In the following, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. . As described in Macromolecules; 15, 1150 (1982), the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads.

Therefore, the total of the six triads is 1 as shown in the following formula (7).
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1
Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .
By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
In addition, the preferable propylene random copolymer in the present invention described above includes a small amount of propylene heterogeneous bond (2,1-bond and / or 1,3-bond), and is described in Table 2 below. Resulting in a small peak.

  In order to obtain an accurate ethylene content, it is necessary to include peaks derived from these heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from the heterogeneous bonds. Therefore, the ethylene content of the present invention is the same as in the analysis of the copolymer produced with the Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. It is determined using an expression.

Moreover, conversion from mol% of ethylene content to weight% is performed using the following formula | equation.
Ethylene content (wt%) =
(28 * X / 100) / {28 * X / 100 + 42 * (1-X / 100)} * 100
Here, X is the ethylene content in mol%.
The ethylene content of the entire copolymer is calculated from the component (A1) and component (A2) measured from the above, the respective ethylene contents (% by weight) [E] A1, [E] A2, and TREF. From the weight ratios W (A) and W (B) [wt%] of each component, the following formula is used.
[E] W = [E] A1 × W (A) / 100 + [E] A2 × W (B) / 100 (% by weight)

(V) Production Method of Propylene-Ethylene Copolymer Component (A) As described above, the propylene-ethylene copolymer component (A) used particularly preferably in the present invention is propylene having relatively high crystallinity. An ethylene random copolymer component (A1) and a low crystalline propylene-ethylene random copolymer component (A2), which are roughly composed of two types of propylene-ethylene random copolymers having different crystallinity. .
As described above, since the component (A1) and the component (A2) are different in crystallinity, the melting temperature is also greatly different. When each component is melted and kneaded separately, the component (A2) melts at an extremely early stage, After that, since the temperature further rises, the component (A1) is melted, so that the inorganic flame retardant concentrates in the previously melted component (A2), and dispersion failure tends to occur. Therefore, the component (A1) and the component (A2) are most preferably produced by sequential polymerization.

(I) Polymerization method (i) Sequential polymerization of component (A1) and component (A2) A preferred propylene-ethylene copolymer component (A) is produced from component (A1) and component (A2). In this case, it is preferable to sequentially polymerize the component (A1) and the component (A2).
At this time, since component (A2) is a copolymer having a high ethylene content and easily sticky alone, in order to prevent problems such as adhesion to the reactor, component (A2) is polymerized after component (A1) is polymerized. ) Is preferably used.

When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity. In the case of the batch method, it is also possible to polymerize the component (A1) and the component (A2) individually using a single reactor by changing the polymerization conditions with time. In this case, a plurality of reactors may be connected in parallel.
In the case of a continuous process, since it is necessary to polymerize component (A1) and component (A2) separately, it is necessary to use a production facility in which two or more polymerization reactors are connected in series. A plurality of reactors may be connected in series and / or in parallel for each of component (A1) and component (A2) as long as they are not inhibited.

  In the present invention, not only the propylene-ethylene copolymer component (A) but also the propylene-ethylene copolymer component (A) having the characteristics (i) to (ii) and the propylene having the characteristic (iv) -To preferably produce the ethylene copolymer component (A), a single-site catalyst is used, and a crystalline propylene homopolymer or crystalline propylene-ethylene random copolymer having an ethylene content of 0 to 6 wt% in the first step is used. Sequential polymerization of 95 to 30% by weight of polymer component (A1) and 5 to 70% by weight of low crystalline propylene-ethylene random copolymer component (A2) having an ethylene content of 6 to 15% by weight in the second step Can be obtained.

(B) Polymerization process As the polymerization process, any polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. Here, since the component (A2) having a high ethylene content is easily dissolved in an organic solvent such as hydrocarbon or liquefied propylene, it is desirable to use a gas phase method for the production of the component (A2).
In addition, there is no particular problem in using any process for the production of the crystalline propylene-ethylene random copolymer component (A1), but when producing the component (A1) having relatively low crystallinity, It is desirable to use a vapor phase method to avoid problems such as adhesion.
Therefore, using the continuous method, first, the component (A1) is polymerized by the bulk method or the gas phase method, and then the component (A2) is polymerized by the gas phase method, the characteristics (i), (ii) And (iv) is the most desirable method for obtaining the propylene-ethylene copolymer component (A).

(C) Other polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 to 200 ° C, more preferably 40 to 100 ° C can be used.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, more preferably 0.1 to 50 MPa can be used. In that case, inert gas, such as nitrogen, can also coexist.
When the sequential polymerization of the component (A1) in the first step and the component (A2) in the second step is performed, it is desirable to add a polymerization inhibitor into the system in the second step. When a polymerization inhibitor is added to the reactor in which ethylene-propylene random copolymerization in the second step is performed, product quality such as particle properties (fluidity, etc.) and gel of the resulting powder can be improved. Various technical studies have been made on this method, and examples thereof include Japanese Patent Publication No. 63-54296, Japanese Patent Application Laid-Open No. 7-25960, Japanese Patent Application Laid-Open No. 2003-2939, and the like. It is desirable to apply the method to the present invention.

(D) Polymerization catalyst Since each component (A1) and (A2) needs to have a narrow crystallinity distribution, that is, a composition distribution, a single-site catalyst is used for the production thereof.
The type of the single site catalyst is not particularly limited as long as a copolymer having the performance of the present invention can be produced. In order to satisfy the requirements of the present invention, for example, the following components ( It is preferable to use a single-site catalyst comprising a) and component (b), and further component (c) used as necessary.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) Component (b): Selected from the following (b-1) to (b-4) At least one solid component (b-1) particulate carrier on which an organoaluminoxy compound is supported (b-2) ionicity capable of reacting with component (a) to convert component (a) into a cation (B-3) Solid acid fine particles (b-4) Ion exchange layered silicate Component (c): Organoaluminum compound

(A) Component (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) can be used.
^{_{Q (C 5 H 4-a}} -aR 1) (C 5 H 4-b -bR 2) MeXY (1)
[Wherein, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, or hafnium, and X and Y represent hydrogen atoms. Atom, halogen atom, hydrocarbon group, alkoxy group, amino group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group, X and Y are each independently, that is, the same or different. Also good. R ¹ and R ² represent hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group or phosphorus-containing hydrocarbon group. . a and b are the number of substituents. ]

Specifically, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands. For example, a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a hydrocarbon group as a substituent. Examples thereof include a silylene group or an oligosilylene group, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred are a divalent hydrocarbon group and a silylene group having a hydrocarbon group as a substituent.
X and Y each represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. And chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group and the like.

R ¹ and R ² represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group or phosphorus-containing hydrocarbon group include methoxy group, ethoxy group, phenoxy group, trimethylsilyl group. Typical examples include a group, a diethylamino group, a diphenylamino group, a pyrazolyl group, an indolyl group, a dimethylphosphino group, a diphenylphosphino group, a diphenylboron group, and a dimethoxyboron group. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable.
By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

  Among the components (a) described above, the preferable propylene-ethylene copolymer component (A) in the present invention is preferably a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a bridged substituted cyclopentadienyl group, substituted indenyl group, substituted fluorenyl group, substituted azulenyl group, and particularly preferably a silylene group or a germylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a bridged 2,4-position substituted indenyl group and 2,4-position substituted azulenyl group.

Specific examples include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methylbenzoindenyl). Zirconium dichloride, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethylsilylenebis (2 -Methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylenebis (2-ethyl) 4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium dichloride, dimethyl Examples include silylene bis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} zirconium dichloride, and the like. It is done.
A compound in which the silylene group of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound.

(B) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used. Each of these components is known and can be used by appropriately selecting from known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, and the like.
Here, as the particulate carrier used for the component (b-1) and the component (b-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include porous organic carriers such as inorganic halides such as aluminum and lanthanum chloride.

As a specific example of the component (b), as the component (b-1), a fine particle carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl or the like is supported is used. 2) As triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluoro) The fine particle carrier on which phenyl) borate or the like is supported is composed of, as component (b-3), alumina, silica alumina, magnesium chloride, etc., and as component (b-4), montmorillonite, zakonite, beidellite, nontronite, saponite. , Kutoraito, stevensite, bentonite, smectite group such as taeniolite, vermiculite, and the like mica group. These may form a mixed phase.
Among the components (b), in order to obtain the preferred propylene-ethylene copolymer component (A) in the present invention, the preferred one is the ion-exchange layered silicate of the component (b-4), and A preferable material is an ion-exchange layered silicate that has been subjected to chemical treatment such as acid treatment, alkali treatment, salt treatment, or organic matter treatment.

(C) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a X _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3), trimethylaluminum, triethylaluminum, tripropylaluminum, Trialkylaluminum such as triisobutylaluminum or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

(D) Formation of catalyst Component (a) and component (b) are further brought into contact with component (c) as necessary to form a catalyst. The contacting method is not particularly limited, and this contacting may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of olefin polymerization.
The amount of the components (a) and (b) and (c) used is, for example, the amount of the component (a) used relative to the component (b) is preferably 0.1 μmol to 1 g of the component (b). 1,000 μmol, particularly preferably in the range of 0.5 μmol to 500 μmol. The amount of component (c) used relative to component (b) is preferably such that the amount of aluminum metal is 0.001 to 100 mmol, particularly preferably 0.005 to 50 mmol, relative to 1 g of component (b). Therefore, the amount of component (c) to component (a) is preferably in the range of 10 ⁻³ to 10 ⁶ , particularly preferably 10 ⁻² to 10 ⁵ , in terms of the molar ratio of the metal.

(E) Prepolymerization treatment In obtaining the preferred propylene-ethylene copolymer component (A) in the present invention, the catalyst may be subjected to a prepolymerization treatment consisting of preliminarily contacting an olefin and polymerized in a small amount. preferable. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and the like are used. In particular, it is preferable to use propylene.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively.
The prepolymerization amount is preferably 0.01 to 100 parts, more preferably 0.1 to 50 parts, based on the component (b).
After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.

(3) Ethylene copolymer component (B)
The ethylene-based copolymer component (B) used in the present invention comprises an ethylene-α, β-unsaturated carboxylic acid ester copolymer (B1), an ethylene-vinyl ester copolymer (B2) and a density described below. The ethylene-α olefin copolymer (B3) is selected from at least 0.86 and less than 0.91 g / cm ³ .

{Ethylene-α, β-unsaturated carboxylic acid ester copolymer (B1)}
Representative copolymers of ethylene and α, β-unsaturated carboxylic acid ester include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate. Copolymers, ethylene- (meth) acrylic acid alkyl ester copolymers such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer; ethylene-maleic anhydride-vinyl acetate copolymer, ethylene- Examples thereof include binary or multi-component copolymers such as maleic anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-ethyl acrylate copolymer, or metal salts thereof.
That is, as comonomer with ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylate-n-butyl, methacrylic acid -N-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate and the like can be mentioned. Among these, particularly preferred are (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and the preferred copolymerization content is from 3 to 35% by weight. Preferably it is the range of 5-30 weight%.
Moreover, K, Na, Li, Ca, Zn, Mg, Al etc. are mentioned as a metal of the said metal salt.

{Ethylene-vinyl ester copolymer (B2)}
The ethylene-vinyl ester copolymer is produced by a high-pressure radical polymerization method. Ethylene and vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, trifluoro It is a copolymer with a vinyl ester monomer such as vinyl acetate. Among these, vinyl acetate is particularly preferable.
The copolymer composition of the copolymer is preferably 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers. Furthermore, the vinyl ester content is preferably selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

{Ethylene-α olefin copolymer (B3)}
Component (B3) has a density of 0.86 g / cm ³ or more and less than 0.91 g / cm ^3, preferably 0.87~0.907g / cm ^3, more preferably 0.88~0.905g / cm ³ The ethylene-α olefin copolymer. When the density is less than 0.86 g / cm ³ , the heat resistance of the obtained flame retardant resin composition is poor, and when it is 0.91 g / cm ³ or more, the flexibility of the flame retardant resin composition is deteriorated. There is a risk that the physical property balance as the flame retardant composition cannot be maintained.

  The melt flow rate MFR (190 ° C., 21.18 N) of the ethylene-α-olefin copolymer (B3) is preferably 0.01 to 200 g / 10 minutes, more preferably 0.03 to 100 g / 10 minutes. More preferably, it is the range of 0.1-50 g / 10min. If the MFR is less than 0.01 g / 10 minutes, there is a risk of adversely affecting the moldability and flexibility, and if the MFR exceeds 200 g / 10 minutes, the mechanical strength and the like may be insufficient.

The molecular weight distribution parameter (Mw / Mn) of the ethylene-α olefin copolymer is preferably 1.5 to 5.0, more preferably 1.6 to 4.5, and still more preferably 1.8 to 4. A range of 0 is desirable. If Mw / Mn is less than 1.5, the extrudability deteriorates and it is difficult to obtain a good product appearance.
The ethylene-α olefin copolymer (B3) includes linear low density polyethylene and ultra low density polyethylene polymerized by a single site catalyst.

Hereinafter, linear low density polyethylene and ultra low density polyethylene polymerized by a single site catalyst will be described.
Linear low density polyethylene and ultra-low density polyethylene are obtained by copolymerization of ethylene and α-olefin, and are also referred to as ethylene-α-olefin copolymer.
The α-olefin preferably has 3 to 20 carbon atoms, specifically, propylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene, octene-1, dodecene-1. In particular, α-olefins having 4 to 12 carbon atoms such as butene-1, hexene-1, and octene-1 are preferable. Further, the total copolymerization amount of these α-olefins is usually selected to be 30 mol% or less, preferably 3 to 20 mol%.

  The ethylene-α-olefin copolymer (B3) is preferably produced by a general single-site catalyst (metallocene-containing catalyst), and an elution temperature-elution amount curve determined by a temperature rising elution fractionation method (TREF). 1 has one or more TREF peaks, and is excellent in transparency, flexibility, mechanical strength and the like.

  Examples of the method for producing the ethylene-α-olefin copolymer include JP-A-58-19309, JP-A-59-95292, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-60-35009, JP-A-63-130314, JP-A-3-16388, European patent applications The methods described in JP-A-420,436, U.S. Pat. No. 5,055,438, and International Publication No. WO09 / 04257, such as a single-site catalyst, a metallocene / alumoxane catalyst, Alternatively, for example, a metallocene compound as disclosed in, for example, the specification of International Publication No. W092 / 07123, and a single cycle described below. And a method of copolymerizing a main component ethylene and a secondary component C3-C20 α-olefin using a catalyst comprising a compound that reacts with a system catalyst to form stable ions. .

[Single-site catalyst]
The compound that reacts with the single-site catalyst and becomes a stable ion is an ionic compound or an electrophilic compound formed from an ion pair of a cation and an anion, and reacts with a metallocene compound to form a stable ion. Thus, a polymerization active species is formed. Among these, an ionic compound is represented by the following formula (I).
[Q] m + [Y] m- (I)
(M is an integer of 1 or more)

  Q in the formula is a cation component of an ionic compound, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation, and moreover, a metal that itself is easily reduced. And cations of organic metals and the like.

These cations are not only cations that can give protons as disclosed in JP-A-1-501950, but also cations that do not give protons.
Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylammonium, dipropylammonium, dicyclohexylammonium, tri Phenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, mercury Ion, ferrocenium ion, etc. are mentioned.

  Y in the above formula (I) is an anionic component of an ionic compound, which is a component that reacts with a metallocene compound to become a stable anion, and includes an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, Organic phosphorus compound anion, organic arsenic compound anion, organic antimony compound anion, and the like. Specifically, tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (tri) Fluoromethyl) phenyl) boron, tetrakis (3,5- (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis ( 3,5-di (trifluoromethyl) ) Phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3 , 5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, tetra Phenylarsenic, tetrakis (pentafluorophenyl) arsenic, tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc. It is.

  Among the electrophilic compounds, among those known as Lewis acid compounds, they react with metallocene compounds to form stable ions to form polymerization active species, and various metal halide compounds and solid acids. And metal oxides known as. Specific examples include magnesium halides and Lewis acidic inorganic compounds.

[Copolymerization]
The copolymer is preferably produced by a high pressure ionic polymerization method. This high-pressure ion polymerization method is a method described in JP-A-56-18607 and JP-A-58-225106. Specifically, 300~3,000kg / cm ² pressure, preferably 1,100~2,000kg / cm ^2, particularly preferably 1,300~1,800kg / cm ^2, temperature of 125 ° C. or higher, preferably Is carried out under reaction conditions of 130 to 250 ° C., particularly preferably 150 to 200 ° C.

(4) Polyethylene resin component (C)
The component (C) is a polyethylene resin having a density of 0.91 to 0.97 g / cm ³ . Specific examples include ion polymerization polyethylene resins such as Ziegler catalysts, Phillips catalysts, and single site catalysts, and high pressure radical polymerization polyethylene resins. Examples of the ion polymerization polyethylene resin include high density polyethylene, medium density polyethylene, and linear low density polyethylene. Examples of the high pressure radical polymerization polyethylene resin include polyethylene resins such as branched low density polyethylene. . From the viewpoint of balance between flexibility and heat resistance, linear low density polyethylene or high density polyethylene is preferable. These may be used alone or in combination of two or more.

The melt flow rate (MFR) of the polyethylene resin (C) is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 80 g / 10 minutes, more preferably 0.1 to 70 g / 10 minutes. desirable. If it is less than 0.01 g / 10 min, there is a concern that the molding processability, the appearance and the like deteriorate. Moreover, when it exceeds 100 g / 10 minutes, there exists a possibility that mechanical strength may fall.
The density is 0.91 to 0.97 g / cm ³ , preferably 0.915 to 0.96 g / cm ³ , more preferably 0.92 to 0.95 g / cm ³ . If the density is less than 0.9 g / cm ³ , the resulting flame retardant resin composition has poor heat resistance, and the effect of adding the component (C) cannot be obtained, while if it exceeds 0.97 g / cm ³ , Whitening property, flexibility and the like are lowered, which is not preferable. In particular, the density of 0.915 to 0.96 g / cm ³ is preferable because a balance between flexibility, heat resistance, and mechanical resin performance is remarkably exhibited.
In addition, the polyethylene-based resin component (C) preferably has a molecular weight distribution (Mw / Mn) measured by GPC of 10 or more from the viewpoint of balance between flexibility and heat resistance and good product appearance. More preferably, it is 11 or more. If the molecular weight distribution is lower than this, the extrudability deteriorates, and in an extreme case, extrusion may not be possible and the product appearance may be poor.
As the component (C), linear low density polyethylene or high density polyethylene having a molecular weight distribution (Mw / Mn) of 10 or more is particularly preferable.

(5) Functional group-containing olefin polymer component (D)
The functional group-containing olefin polymer (D) of the present invention is an olefin polymer containing a functional group, and includes a propylene-ethylene copolymer (A), an ethylene copolymer (B), and a polyethylene resin ( C) has good compatibility with the flame retardant (E) and has a remarkable coupling effect, which promotes the mechanical strength of the flame retardant resin composition and the formation of a char layer during combustion. Used to improve flammability.
Specific examples include olefinic random copolymers containing carboxylic acid groups or acid anhydride groups, metal salts thereof (D1), and modified polyolefin resins (D2). However, the polymer belonging to component (B) is excluded.

[Carbonic acid group or acid anhydride group-containing olefin random copolymer or metal salt thereof (D1)]
Carboxylic acid group or acid anhydride group-containing olefin random copolymer or metal salt thereof is an olefin such as ethylene or propylene, a carboxylic acid group-containing monomer such as methacrylic acid or acrylic acid, or an acid anhydride such as maleic anhydride. It is a copolymer with a group-containing monomer or a metal salt thereof.

  Examples of the monomer containing a carboxylic acid group or an acid anhydride group include acrylic acid, methacrylic acid, furanic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid and other α, β-unsaturated dicarboxylic acids or anhydrides thereof. Thing etc. are mentioned. The preferred copolymers include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-maleic anhydride-vinyl acetate copolymer, ethylene-maleic anhydride. -A binary or ternary copolymer such as a methyl acrylate copolymer or an ethylene-maleic anhydride-ethyl acrylate copolymer may be mentioned. Examples of the metal of the metal salt include K, Na, Li, Ca, Zn, Mg, and Al.

[Modified polyolefin resin (D2)]
The modified polyolefin resin is a: unsaturated carboxylic acid or derivative thereof, b: epoxy group-containing compound, c: hydroxyl group-containing compound, d: amino group-containing compound, e: organosilane compound, f: organotitanate compound, etc. A polyolefin resin modified with a functional group-containing compound.

(Functional group-containing compound)
A: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinylacetic acid, pentenoic acid; maleic acid, fumaric acid, citraconic acid , Α, β-unsaturated dicarboxylic acids or anhydrides such as itaconic acid, or metal salts thereof.

  B: Epoxy group-containing compounds include glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester and α-chloroallyl, malee Examples thereof include glycidyl esters such as acid, crotonic acid and fumaric acid, or glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether and styrene-p-glycidyl ether, and p-glycidyl styrene. Examples thereof include glycidyl methacrylate and allyl glycidyl ether.

  Examples of the c: hydroxyl group-containing compound include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

Examples of the d: amino group-containing compound include tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate.
Examples of the e: organosilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.
Examples of the f: organic titanate compound include tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexoxy) titanate, and titanium lactate ammonium.

  The content of the functional group-containing compound in the modified polyolefin resin is preferably selected in the range of 0.05 to 10% by weight, more preferably 0.1 to 8.0% by weight. If the content is less than 0.05% by weight, the effect of the present invention may not be sufficient, and the coupling effect between the resin and the flame retardant may not be exhibited. On the other hand, if it exceeds 10% by weight, there is a possibility that decomposition, crosslinking reaction, etc. may occur at the time of modification.

The modified polyolefin resin modifies the polyolefin resin by heating the polyolefin resin and the functional group-containing compound in the presence of an organic peroxide, and the content of the functional group-containing compound is 0.05 to 10% by weight. Or those obtained by mixing the modified product with an unmodified polyolefin resin and adjusting the content of the functional group-containing compound to the above range.
Examples of polyolefin-based resins include polypropylene (polypropylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-α olefin copolymer (α-olefin examples include 1-butene, 1-hethenes). Xene, 4-methyl-pentene, etc.), polyethylene (low density polyethylene, high density polyethylene, linear polyethylene, ultra-low density polyethylene) and the like, or a mixture thereof. it can.

These polyethylene even density is 0.86~0.97g / cm ³ in, inter alia in the range of density 0.88~0.96g / cm ^3, very low density polyethylene, linear low density polyethylene, medium - high density A modified polyethylene resin is excellent in compatibility between the polyolefin resin and inorganic flame retardant, maintains heat resistance without impairing the flexibility of the soft resin, and promotes the formation of a carbonized layer during combustion. It is most preferable because it can improve the mechanical properties and improve the mechanical strength.

Among these, maleic anhydride-modified polypropylene and maleic anhydride-modified polyethylene are preferable.
A commercially available product can be used as the modified polyolefin resin (C). For example, trade name Modelek CMPP-2 (maleic anhydride modified polypropylene) manufactured by Mitsubishi Chemical Corporation, trade name Adtex (maleic anhydride modified polyethylene) manufactured by Nippon Polyethylene Co., Ltd., and the like can be given.

(6) Flame retardant component (E)
The flame retardant of the component (E) used in the present invention is a component necessary for making the material flame retardant, and is an organic flame retardant (E1) such as an organic halogen flame retardant and an organic phosphorus flame retardant. And an inorganic flame retardant (E2).

[Organic flame retardant (E1)]
Organic halogen flame retardants include hexabromobenzene, decabromodiphenyl oxide, polydibromophenylene oxide, bis (tribromophenoxy) ethane, ethylene bis-pentabromobenzene, ethylene bis-dibromonorbornane dicarboximide, ethylene bis-tetra Bromophthalimide, dibromoethyldibromocyclohexane, dibromoneopentyl glycol, tribromophenol, tribromophenol allyl ether, tetrabromobisphenol A derivative, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, tris (2,3-dibromopropyl- 1) Isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyeth) Cis-3,5-dibromophenyl) propane, pentabromophenol, pentabromotoluene, pentabromodiphenyl oxide, hexabromocyclododecane, hexabromodiphenyl ether, octabromophenol ether, octabromodiphenyl ether, octabromodiphenyl oxide, dibromoneopentyl Glycol tetracarbonate, bis (tribromophenyl) fumaramide, N-methylhexabromophenylamine, brominated epoxy resin, chlorinated paraffin, chlorinated polyolefin, chlorinated polyethylene, perchlorocyclopentadecane, triallyl cyanurate bromide, etc. Illustrated.

  Examples of organophosphorous flame retardants include tris (chloroethyl) phosphate, tris (monochloropropyl) phosphate, tris (dichloropropyl) phosphate, triallyl phosphate, tris (3-hydroxypropyl) phosphine oxide, tris (tribromophenyl) phosphate, Tetrakis (2-chloroethyl) ethylene-diphosphate, glycidyl-α-methyl-β-di (butoxy) phosphinylpropionate, dibutylhydroxymethylphosphonate, di (butoxy) phosphinylpropylamide, dimethylmethyl Amine phosphates such as phosphonates, ethylene bis-tris (2-cyanoethyl) phosphonium bromides, ammonium polyphosphates, ethylene diamine phosphates and amine phosphones And melamine polyphosphate.

[Inorganic flame retardant (E2)]
Inorganic flame retardants include hydromagnesite, antimony trioxide, aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, huntite, dolomite, natural brucite ore , Potassium hydroxide, calcium hydroxide, zirconium hydroxide, barium hydroxide, calcium phosphate, zircon oxide, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium carbonate, basic magnesium carbonate, calcium carbonate, barium carbonate , Barium sulfate, barium borate, barium metaborate, zinc borate, zinc carbonate, zinc metaborate, tin oxide hydrate, borax, anhydrous alumina, molybdenum disulfide, clay, red phosphorus, diatomaceous earth, kaolinite, Mon Rironaito, hydrotalcite, talc, silica, white carbon, zeolite, asbestos or lithopone, and the like. Among the inorganic flame retardants, a preferable flame retardant component is a metal hydrate.

  The metal hydrate used in the present invention is not particularly limited. For example, a hydroxyl group such as aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite or the like. The compounds having crystal water can be used alone or in combination of two or more. Among these metal hydrates, at least one metal hydrate selected from aluminum hydroxide, magnesium hydroxide, or hydrotalcite is preferable. Magnesium hydroxide, aluminum hydroxide, combined use of magnesium hydroxide and hydrotalcite, and combined use of aluminum hydroxide and hydrotalcite are more preferable.

  From the viewpoint of dispersibility, the metal hydrate, particularly aluminum hydroxide and magnesium hydroxide, preferably has an average particle size of 0.1 to 6 μm, more preferably 0.2 to 5 μm. . In addition, natural and / or synthetic products can be used in the above magnesium hydroxide, but nowadays natural products obtained by pulverizing natural ore mainly composed of magnesium hydroxide are economically advantageous. Can be preferably used.

  Hydrotalcite may be a so-called hydrotalcite compound having the same crystal structure as hydrotalcite, such as stichtite, pyroaulite, leebesite, tacovitite, onesite, iowite, etc. It may be a product. The average particle size of the hydrotalcite is preferably 0.2 to 4 μm, more preferably 0.2 to 2 μm from the viewpoint of dispersibility.

  When aluminum hydroxide or magnesium hydroxide and hydrotalcite are used in combination, the quantity ratio (% by weight, the total is 100% by weight) is aluminum hydroxide or magnesium hydroxide: hydrotalcite = 90 to 0:10. -100, preferably 88-0: 12-100, more preferably 85-15: 15-85. This range is preferable because flame retardancy and wear resistance are remarkably improved.

Moreover, you may mix | blend a red phosphorus, a polyphosphate, a urea compound, silicone oil, silicone powder, etc. with a flame retardant component (E) as needed. Examples of the polyphosphate include ammonium polyphosphate and melamine polyphosphate. Examples of urea compounds include triazine and melamine cyanurate.
It goes without saying that flame retardants such as the above organic halogen flame retardants, organic phosphorus flame retardants and inorganic flame retardants may be used alone or in combination.

The inorganic flame retardant (E) is preferably surface-treated.
As the surface treatment agent, fatty acids such as stearic acid, oleic acid, palmitic acid or metal salts thereof, fatty acid esters, paraffin, wax, or modified products thereof, organic silane, organic borane or organic titanate, phosphate ester, castor oil or The hardened oil etc. are illustrated.
In addition to the above, it is also possible to use a metal hydrate subjected to surface treatment using a silane coupling agent having a functional group such as a vinyl group or an epoxy group at its terminal. Further, surface treatment may be performed with silicone, organopolysiloxane or the like.

As the silane coupling agent used for the surface treatment of metal hydrate, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane Silane coupling agents having a vinyl or epoxy group at the end, such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, etc. Silane coupling agent having a terminal mercapto group, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl A crosslinkable silane coupling agent such as a silane coupling agent having an amino group such as tripropyltrimethoxysilane or N- (β-aminoethyl) -γ-aminopropyltripropylmethyldimethoxysilane can be used.
Among such silane coupling agents, a silane coupling agent having an epoxy group and / or a vinyl group, a (meth) acryloyl group, and an amino group at the terminal is particularly preferable. These may be used singly or in combination of two or more, or a fatty acid, a fatty acid ester, a phosphate ester and the like may be used in combination with these silane coupling agents.

(7) Mixing ratio of each component in flame retardant resin composition The flame retardant resin composition of the present invention is composed of 5 to 90% by weight of component (A), 5 to 90% by weight of component (B), C) is 5 to 90% by weight (wherein the total amount of component (A), component (B) and component (C) is 100% by weight), the component ( D) is contained in an amount of 0 to 30 parts by weight, and component (E) is contained in an amount of 5 to 300 parts by weight. The resin component is preferably 10 to 80% by weight of the component (A), 10 to 80% by weight of the component (B), and 10 to 80% by weight of the component (C), more preferably the component (A). Is 20 to 70% by weight, component (B) is 20 to 70% by weight, and component (C) is 10 to 60% by weight.

When the component (A) is less than 5% by weight and the component (B) exceeds 90% by weight, the heat resistance is not sufficient, the component (A) exceeds 90% by weight, and the component (B) is less than 5% by weight. In this case, the flexibility is not sufficient. On the other hand, when the component (C) is less than 5% by weight, the surface appearance of the molded product is deteriorated, and when it exceeds 90% by weight, the flexibility is insufficient. That is, it is important for the balance between heat resistance, flexibility, elongation characteristics, and appearance of the molded product that the component (A), the component (B), and the component (C) are in a predetermined range.
In addition, component (D) generally does not have to be used in the case of using an organic flame retardant, but it does not impair flexibility due to mechanical strength and char formation of the composition. It is preferable to add at. As an addition amount, 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight of the component (D) with respect to 100 parts by weight of the resin components of the components (A), (B) and (C), More preferably, it is added in the range of 0.3 to 5 parts by weight.
On the other hand, when the flame retardant component (E) is an inorganic flame retardant, the component (D) is preferably essential, and relative to 100 parts by weight of the resin components of the components (A), (B) and (C). The content is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, particularly 3 to 20 parts by weight.
If the component (D) is less than 1 part by weight, there is a possibility that the coupling effect and char formation between the resin component and the inorganic flame retardant will not occur, and the mechanical strength and flame retardancy may not be improved. Moreover, when exceeding 30 weight part, there exists a possibility that the softness | flexibility and flexibility of a flame-retardant resin composition may be impaired.

In general, the oxygen index (JIS K7201 3 mm thick sheet) of the flame-retardant molded article is preferably 21 or more, more preferably 23 or more, and further preferably 25 or more, and has excellent flame retardancy and self-extinguishing properties. Is required.
Therefore, content of a flame retardant (E) needs to exist in the range of 3-300 weight part with respect to 100 weight part of resin components of component (A), (B) and (C).
In the case where the flame retardant is an organic flame retardant, it is desirably selected in the range of 3 to 30 parts by weight, preferably 4 to 25 parts by weight, more preferably 5 to 20 parts by weight. If the organic flame retardant is less than 3 parts by weight, the flame retardancy may not be exhibited. Moreover, even if 30 parts by weight or more is added, the effect of improving flame retardancy reaches its peak, resulting in an economic disadvantage.
On the other hand, when only an inorganic flame retardant is used, it is generally 20 to 300 parts by weight, preferably 20 to 250 parts by weight, more preferably 30 to 200 parts by weight. If the flame retardant (E) is less than 20 parts by weight, there is a possibility that an appropriate flame retardancy may not be obtained with an inorganic flame retardant alone, and a partial use with an organic flame retardant becomes necessary. On the other hand, if the amount exceeds 300 parts by weight, the mechanical strength such as the intended tensile elongation at break is lowered, and the bending whitening resistance is lowered.

3. Production method of composition of the present invention The flame retardant resin composition of the present invention is difficult to produce with a propylene-ethylene copolymer component (A), an ethylene copolymer component (B), and a polyethylene resin component (C). The flame retardant (E) is an essential component, or in addition to these components, the functional group-containing olefin polymer component (D) is an optional component, and if desired, additional components are blended within a range that does not impair the efficacy (effect) of the present invention. These can be mixed and produced using a known melt-kneading method such as a twin screw extruder, roll, or Banbury mixer.
For example, the components may be mixed at room temperature and then melt kneaded using a twin-screw kneading extruder, or a feed hole may be provided in the middle of the kneading extruder to feed the flame retardant. Alternatively, it may be produced by performing melt kneading simultaneously.
The flame-retardant molded article of the present invention is generally a pellet made from the flame-retardant resin composition obtained above, but in the masterbatch method or the dry blend method, the state of pellet blending is used. It is also possible to perform molding using a weight-type feeder or the like, and to perform molding while continuously weighing and weighing.

4). Additional component An additional component can be mix | blended with the flame-retardant resin composition of this invention in order to provide another characteristic in the range which does not impair the effect of this invention.
Examples of main additional components include other polyolefins described below, thermoplastic elastomer components, cross-linking agents (or cross-linking aids), other additive components, and the like.
Other polyolefins include polypropylene homopolymers such as isotactic polypropylene polymers and syndiotactic polypropylene polymers, block copolymers of propylene and other α-olefins, and interpolymers such as random polymers, Polypropylene resins such as binary or multi-component copolymers such as propylene-ethylene-butene-1 copolymer, polybutene-1 resin, poly-4-methyl-pentene-1 resin, and their copolymerization with other α-olefins And a copolymer with ethylene-cyclic olefin.

Thermoplastic elastomers are generally modifiers for thermoplastic resin materials and are added and added to increase the flexibility and impact resistance of the resin composition.
In the present invention, the addition of the thermoplastic elastomer component contributes to the improvement of wear resistance, which is contrary to flexibility. As the thermoplastic elastomer component, styrene-vinylisoprene block copolymer and hydrogenated product thereof, styrene-butadiene-styrene copolymer and hydrogenated product thereof, isoprene copolymer, ethylene-propylene copolymer elastomer, ethylene- Examples thereof include a propylene-diene copolymer elastomer and a butadiene elastomer. Among these, use of a styrene-vinylisoprene block copolymer or a hydride thereof is preferable from the viewpoint of wear resistance. The MFR of the thermoplastic elastomer component may be 0.05 to 15 g / 10 minutes, preferably 1 to 10 g / 10 minutes.

  The blending ratio of the thermoplastic elastomer component is 0 to 100 parts by weight, preferably 0 to 80 parts by weight, more preferably 0 to 60 parts by weight when the resin components (A), (B) and (C) are 100 parts by weight. Parts by weight. An amount exceeding 100 parts by weight is disadvantageous for economic efficiency.

Further, it is desirable to add a crosslinking agent and / or a crosslinking aid in order to enhance heat resistance within the range where the efficacy of the present invention is not impaired.
Examples of the crosslinking agent include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert -Butylperoxy) hexane-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 -Bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropylcarbonate, diacetylperoxide Kishido, lauroyl peroxide, etc. tert- butyl cumyl peroxide and the like.

  As the polyfunctional monomer mixed as a crosslinking aid, triallyl isocyanurate, triallyl trimethacrylate, trimethylolpropane trimethacrylate, benzoerythritol tetramethacrylate, divinylbenzene or the like is used.

Other additive components include, for example, heat stabilizers, antioxidants, weathering stabilizers, ultraviolet absorbers, crystal nucleating agents, copper damage inhibitors, antistatic agents, slip agents, antiblocking agents, and antifogging agents. , Colorants, fillers, metal deactivators, process oils, castor oil or hardened oils thereof, petroleum resins, antibacterial agents, antproofing agents, plasticizers, carbon black, anti-scratch agents, and the like.
Examples of the anti-scratch agent include 12-hydroxystearic acid metal salt, basic 12-hydroxystearic acid metal salt, carboxylic acid amide wax, and fluorine-based elastomer.

5. Application and molding method of the present invention As the application of the flame-retardant molded article of the present invention, a self-extinguishing molded article is particularly suitable, but is not limited thereto, and examples thereof include films, sheets, containers, packing, and sealing agents. , Hoses, protective equipment, injection products, and wire extrusion, optical fiber coating, steel pipe coating, steel wire coating, cable coating, corrugated tube, etc. And automobile parts.
The flame-retardant molded product of the present invention can be preferably produced, for example, by coating extrusion and / or profile extrusion molding of a flame-retardant resin composition. Preferred examples of the coated extrusion-molded body include wire coating, steel pipe coating, steel wire coating, and cable coating.
In addition, various molding methods such as injection molding and compression molding are used for various flame-retardant molded products.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. The measurement methods and materials used in this example are as follows.

I. Measurement method and evaluation method 1) Melt flow rate (MFR)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C. (component (A)), 190 ° C. (other than component (A))
Nominal load: 2.16kg Die shape: Diameter 2.095mm Length 8.00mm

2) Temperature rising elution fractionation method (TREF)
(Create elution curve)
According to the method described above.
〔apparatus〕
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column
Column packing material: 100 μm-surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino-Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C Temperature distribution: ± 1 ° C Valve: 6-way valve-4-way valve

(Sample injection part)
Injection method: Loop injection method Injection amount: Loop size -0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO-MIRAN 1A
Detection wavelength: 3.42 μm High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5 mm Window shape 2φ × 4 mm long circle-synthetic sapphire window Measurement temperature: 140 ° C.
(Pump part)
Liquid feed pump: manufactured by Senshu Kagaku Co., Ltd.-SSC-3461 pump [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL, Sample injection amount: 0.1 mL, Solvent flow rate: 1 mL / min

3) Differential scanning calorimetry (DSC)
Using a Seiko DSC, take 5.0 mg of sample, hold it at 200 ° C. for 5 minutes, crystallize it to 40 ° C. at a rate of 10 ° C./min. The melting peak temperature was Tm (unit: ° C.). DHm was determined from the area of the endothermic curve at the time of temperature increase.

4) Calculation of ethylene content According to the method described above.

5) Evaluation of flexibility A tensile test piece was punched out from a sheet having a thickness of 1 mm press-molded at 180 ° C., a tensile test was performed at a test speed of 200 mm / min in accordance with JIS K6251, and an elastic modulus was measured. A tensile elastic modulus of less than 1000 MPa was considered good, and 1000 MPa or more was considered bad.

6) Evaluation of tensile breaking elongation A tensile test piece was punched out from a 1 mm thick sheet press-molded at 180 ° C., and a tensile test was performed at a test speed of 200 mm / min in accordance with JIS K6251. The elongation at break between marked lines was determined to be good if it was 350% or more, and poor if it was less than 350%.

7) Evaluation of oxygen index (conforming to JIS K7201) A specimen having a shape IV of a test piece was prepared from a 3 mm thick sheet press-molded at 180 ° C., and the oxygen index was measured according to JIS K7201. It was evaluated with.
Flame retardance pass: Oxygen index 21 or more Flame retardance: Oxygen index less than 21

8) Evaluation of heat resistance A test piece was cut out from a sheet having a thickness of 2 mm press-molded at 180 ° C., and heat deformation measurement was performed in accordance with JIS C3005. After preheating (no load) at 90 ° C. for 30 minutes, a load for 30 minutes (load 3 kg) was applied at the same temperature, the displacement in the thickness direction after the load was measured, and the reduction rate relative to the original thickness was calculated. A reduction rate of less than 10% was judged as good and 10% or more was judged as defective.

9) Appearance evaluation and evaluation of center line average roughness of extruded product Extrusion temperature 170 ° C. using capillary rheometer (capillary: thickness 1 mm × width 5 mm × length 14.5 mm, cylinder diameter 9.5 mmφ) manufactured by Intesco The resin composition was extruded at an extrusion speed of 500 mm / min (piston descending) to obtain an extruded product.
The surface state of the extruded product was visually observed, and the presence or absence of melt fracture and crust was observed.
Furthermore, the center line average roughness surface roughness (μmRa) of the surface of the extrusion-molded product was measured using a surface roughness meter AS-3C manufactured by Kosaka Laboratory Ltd., and 1.5 μmRa or less was good. More than 5 μmRa was regarded as defective.

II. Material 1) Propylene-ethylene copolymer component (A)
The following PP-1 and PP-2 were used as the component (A).
[Polymer Production Example A-1]
(Preparation of prepolymerization catalyst)
Silicate chemical treatment: To a glass separable flask with a 10 liter stirrer blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical-Inner diameter 50 mm-Heating zone 550 mm (Electric furnace) Revolving speed with lifting blade: 2 rpm Tilt angle: 20/520 Silicate feed rate: 2.5 g / min Gas flow rate: Nitrogen-96 liters / hour Countercurrent drying temperature: 200 ° C (powder temperature)

(Preparation of catalyst)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was sufficiently replaced with nitrogen. 200 g of the above-mentioned dry silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry to 2,000 ml. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 270 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane The mixture obtained by adding 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) and reacting at room temperature for 1 hour was added to the silicate slurry after the above reaction, and the mixture was stirred for 1 hour, and then mixed heptane was added. To 5,000 ml.

(Preliminary polymerization)
Subsequently, the temperature in the tank was raised to 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours. After completion of the prepolymerization, the residual monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5,600 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 5,600 ml of the supernatant was removed. It was. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / L, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the presence in the supernatant with respect to the charged amount The amount was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
Using this prepolymerized catalyst, a propylene-ethylene copolymer was produced according to the following procedure.

(First step)
Propylene-ethylene random copolymerization was carried out using a liquid phase polymerization tank equipped with a stirrer having an internal volume of 0.4 m ³ . Liquefied propylene, liquefied ethylene, and triisobutylaluminum were continuously fed at 90 kg / hour, 4.2 kg / hour, and 21.2 g / hour, respectively. The hydrogen supply amount was adjusted so that the MFR in the first step became a target value. Further, the above prepolymerized catalyst was supplied as a catalyst (excluding the weight of the prepolymerized polymer) so as to be 6.9 g / hour. The polymerization tank was cooled so that the polymerization temperature was 45 ° C.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, BD (bulk density) was 0.46 g / cc, MFR was 7.0 g / 10 min, and ethylene content was 3.7% by weight. It was.

(Second step)
Propylene-ethylene random copolymerization was carried out using a stirred gas phase polymerization tank having an internal volume of 0.5 m ³ . The slurry containing polymer particles was continuously extracted from the liquid phase polymerization tank in the first step, and after liquefied propylene was flushed, the pressure was increased with nitrogen and continuously supplied to the gas phase polymerization tank. The polymerization tank was controlled so that the temperature was 80 ° C. and the total partial pressure of propylene, ethylene and hydrogen was 1.5 MPa. At that time, the concentrations of propylene, ethylene, and hydrogen in the total partial pressure of propylene, ethylene, and hydrogen were controlled to be 66.97 vol%, 32.99 vol%, and 420 vol ppm, respectively. Furthermore, ethanol was supplied to the gas phase polymerization tank as an activity inhibitor. The supply amount of ethanol was set to 0.3 mol / mol with respect to aluminum in triisobutylaluminum supplied accompanying the polymer particles supplied to the gas phase polymerization tank.
When the obtained propylene-ethylene copolymer was analyzed, the activity was 8.7 kg / g-catalyst, BD was 0.41 g / cc, MFR was 7.0 g / 10 min, and the ethylene content was 8.7 wt. %Met.

The obtained propylene-ethylene copolymer (PP-1) was measured for MFR, TREF, NMR (ethylene content), DMA, DSC, and GPC (molecular weight). Table 3 shows the data obtained by the measurement.
From the measurement results obtained, PP-1 has one peak due to the glass transition observed in the temperature range of −60 to + 20 ° C., the peak temperature is −16.4 ° C., and in the TREF elution curve, Two peaks were observed at T (A1) 76.2 ° C and T (A2) 23.6 ° C. In addition, the component (A2) eluting up to the midpoint temperature T (A3) between T (A1) and T (A2) has an amount W (A2) of 50% by weight and an ethylene content of 13.7% by weight. Furthermore, the elution component (A1) of T (A3) or higher has an amount W (A1) of 50% by weight and an ethylene content of 3.7% by weight. From the above, PP-1 is used in the present invention. It can be said that the propylene-ethylene copolymer component (A) to be satisfied satisfies all the conditions of the second invention that defines more preferable characteristics of the component (A).
Furthermore, the 99% by weight elution temperature T (A4) is 79.3 ° C., the temperature difference between T (A4) and T (A1) is 3.1, and PP-1 is a more preferred component (A). It can be said that all the conditions of the fourth invention defining the characteristics are satisfied.

[Polymer Production Example A-2]
(Preparation of supported solid catalyst component)
75 ml of purified heptane, 75 ml of titanium tetrabutoxide, and 10 g of anhydrous magnesium chloride are added to a glass three-necked flask with a 500 ml thermometer and a stir bar purged with nitrogen, and then the flask is heated to 90 ° C. The anhydrous magnesium chloride was completely dissolved over 2 hours. Next, the temperature of the flask was lowered to 40 ° C., and 15 ml of methyl hydrogen polysiloxane was added to precipitate a magnesium chloride-titanium tetrabutoxide complex. This was washed with purified heptane to obtain an off-white precipitated solid. 65 ml of the resulting heptane slurry containing 20 g of the precipitated solid was put into a glass three-necked flask with a 300 ml thermometer and a stirring rod with a nitrogen purge, and then 25 ml of a heptane solution containing 8.7 ml of silicon tetrachloride was added. It added over 30 minutes at room temperature, and was then made to react at 30 degreeC for 30 minutes. Furthermore, it was made to react at 90 degreeC for 1 hour, and it wash | cleaned by the refinement | purification heptane after completion | finish of reaction. Next, 50 ml of a heptane solution containing 1.6 ml of phthaloyl chloride was added and reacted at 50 ° C. for 2 hours. This was washed again with purified heptane, and further 25 ml of titanium tetrachloride was added and reacted at 90 ° C. for 2 hours. Was washed with purified heptane to obtain a supported solid catalyst component. The titanium content of the supported solid catalyst component was 3.22% by weight.

(Production of propylene-ethylene block copolymer (component (A)))
After sufficiently replacing the stirred autoclave having an internal volume of 200 liters with propylene, 60 liters of dehydrated and deoxygenated n-heptane was introduced, and further 15.0 g of triethylaluminum, 3.0 g of the supported solid catalyst component and 4.3 g of tert-butylmethyldimethoxysilane was introduced at 70 ° C. in a propylene atmosphere. The first stage polymerization was started by heating the autoclave to 75 ° C. and then feeding propylene at a rate of 9 kg / hour while maintaining the hydrogen concentration at 13%. After 228 minutes, the propylene feed was stopped and the polymerization was continued at 75 ° C. for 90 minutes. Vapor phase propylene was purged to 0.2 kg / cm ² G. Next, after adding 4.9 g of n-butanol and lowering the temperature of the autoclave to 60 ° C., feeding the second stage polymerization at a rate of 2.58 kg / hour of propylene and 1.72 kg / hour of ethylene for 53 minutes. It carried out by.

The slurry thus obtained was filtered and dried to obtain a powdery propylene-ethylene block copolymer (PP-2). The physical properties of the copolymer are as shown in Table 3.
PP-2 has two peaks due to glass transition observed in the temperature range of −60 to + 20 ° C., the peak temperatures are −36 ° C. and + 4 ° C., and two peaks are observed in the TREF elution curve. However, T (A1) is 116 ° C., W (A1) is 93 wt%, W (A2) is 7 wt%, E (A2) is 43 wt%, and PP-2 is used in the present invention. It can be said that the propylene-ethylene copolymer component (A) does not satisfy the requirements of the second invention that defines the characteristics of the preferred component (A).

2) Ethylene copolymer component (B)
The following B-1 to B-3 were used as the components (B1) to (B3) of the component (B), respectively.
B-1: Ethylene-ethyl acrylate copolymer (Nippon Polyethylene, A1200)
MFR [190 ° C.] = 0.8 g / 10 min, ethyl acrylate content = 20% by weight
B-2: Ethylene-vinyl acetate copolymer (Nippon Polyethylene Co., Ltd., LV430)
MFR [190 ° C.] = 1.0 g / 10 min, vinyl acetate content = 15% by weight
B-3: Ethylene-α-olefin copolymer produced with a single site catalyst (Kernel (registered trademark) KS340T manufactured by Nippon Polyethylene Co., Ltd.)
MFR [190 ° C.] = 3.5 g / 10 min, density = 0.880 g / cm ³
Molecular weight distribution Mw / Mn = 2.5

3) Polyethylene resin component (C)
The following C-1 to C-3 were used as the component (C): C-1: linear low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec (registered trademark) LL UE320)
MFR [190 ° C.] = 0.6 g / 10 min, density 0.922 g / cm ³
Molecular weight distribution Mw / Mn = 11
C-2: High density polyethylene (Nippon Polyethylene, Novatec HD HE120)
MFR [190 ° C.] = 0.2 g / 10 min, density 0.938 g / cm ³
Molecular weight distribution Mw / Mn = 15
C-3: High density polyethylene (Nippon Polyethylene, Novatec HD HY320)
MFR [190 ° C.] = 0.15 g / 10 min, density 0.951 g / cm ³
Molecular weight distribution Mw / Mn = 4.5

4) Functional group-containing olefin polymer component (D)
The following modified polyethylene D-1 was used as the component (D).
D-1: Maleic anhydride graft-modified linear low density polyethylene Density = 0.923 g / cm ³ , MFR [190 ° C.] = 2 g / 10 min. 25 parts by weight, 0.02 part by weight of perhexine 25B as an organic peroxide, melt kneaded in an extruder, and graft-modified linear low density polyethylene with maleic anhydride (containing maleic anhydride) (0.2% by weight)

5) Flame retardant component (E)
The following D-1 was used as the component (E).
D-1: Synthetic magnesium hydroxide (Kisuma-5A manufactured by Kyowa Chemical Industry Co., Ltd.)
Average particle diameter of about 1μm, stearic acid surface-treated product

[Example 1]
60% by weight of the propylene-ethylene copolymer (PP-1) obtained in Polymer Production Example A-1 as the component (A) and B-1 (ethylene-ethyl acrylate copolymer as the component (B) ) 5 parts of D-1 (modified polyethylene) as component (D) with respect to 100 parts by weight of the total amount of 30% by weight and 10% by weight of C-1 (linear low density polyethylene) as component (C). As a part by weight, 100 parts by weight of E-1 (magnesium hydroxide) was added as a component (E), and the following components were added as additives.
Dispersant: 0.3 parts by weight of magnesium stearate (reagent grade 1) Antioxidant 1: Tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgaphos 168, manufactured by Ciba Specialty Chemicals) 2 parts by weight Antioxidant 2: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-
Hydroxyphenyl) propionate] Methane (Ciba Specialty Chemicals, trade name Irganox 1010) 0.1 parts by weight Antioxidant 3: Dimyristylthiodipropionate (Sumitomo Chemical, trade name Sumilyzer TPD) 0.2 weight Part

These were blended using a super mixer, and melt-kneaded under the following conditions using a twin screw extruder to obtain resin composition pellets. Table 4 shows the formulation and various evaluation results.
(Melting and kneading) Equipment: NCM50 manufactured by Nakatani Seisakusho
Kneader temperature: 180 ° C. Rotor rotation speed: 500 rpm
Resin temperature: 170 ° C. Screw speed of extruder: 65 rpm

[Examples 2 to 12]
Except for changing the types and blending ratios of the component (A), the component (B), the component (C), the component (D), and the component (E) as shown in Table 4, the same blending as in Example 1, Granulation, molding and evaluation were performed under the same conditions. Table 4 shows the formulation and various evaluation results.

[Comparative Examples 1-6]
Except for changing the blending ratio of component (A), component (B), component (C), component (D), and component (E) as shown in Table 5, the same blending as in Example 1 Granulation, molding and evaluation were performed under the conditions. Table 5 shows the formulation and various evaluation results.

[Consideration of results of Examples and Comparative Examples]
In Examples 1 to 12, the oxygen index is all good, the heat resistance is good, the flame retardancy is very good, and the tensile elongation at break is 350% or more, which is exceptionally excellent. In the extruded product, no melt fracture or scab is observed, and the flexibility is excellent.
On the other hand, in Comparative Examples 1 and 2, because of the conventional propylene-ethylene block copolymer (component A-2), the flexibility and tensile elongation are poor, and the occurrence of wrinkles and poor surface smoothness are observed. In Comparative Example 3, since the component (C) is not used, the skin becomes dark and the average roughness is as large as 2.5 μm. In Comparative Example 4, since the component (A) and the component (C) are not included, the heat resistance is poor.
Moreover, in Comparative Examples 5-6, the softness | flexibility and tensile elongation were inferior only for the component (C).
Furthermore, in Comparative Example 7, the heat resistance and flame retardancy are very high due to the blending of a large amount of inorganic flame retardant, but the mechanical properties are not maintained at all, and there is a problem that melt fracture occurs. .
From the above data of each example and the comparison results of each example and each comparative example, the flame retardant resin composition of the present invention is much more effective in each performance while maintaining flame retardancy than conventional materials. The rationality and significance of the requirements of the configuration of the present invention are demonstrated, and the superiority to the prior art is also revealed.

  According to the present invention, even if the flame retardancy of the thermoplastic resin is sufficiently increased, it has excellent heat resistance, flexibility, elongation characteristics, etc. while retaining excellent mechanical resin performance (wear resistance, whitening resistance, etc.) In addition, a thermoplastic resin material that is excellent in surface smoothness and appearance of a molded product and has high flame retardancy, and a flame retardant molded product using the thermoplastic resin material are obtained. Therefore, its industrial utility is very high.

Claims (11)

5 to 90% by weight of propylene-ethylene copolymer component (A) produced with a single site catalyst,
5 to 90% by weight of at least one ethylene copolymer component (B) selected from the following (B1) to (B3):
(B1) Ethylene-α, β-unsaturated carboxylic acid ester copolymer (B2) Ethylene-vinyl ester copolymer (B3) Ethylene-α olefin copolymer having a density of 0.86 or more and less than 0.91 g / cm ³ as well as,
5 to 90% by weight of polyethylene resin component (C) having a density of 0.91 to 0.97 g / cm ³
(Here, the total of components (A) to (C) is 100% by weight.)
A flame retardant resin composition comprising 0 to 30 parts by weight of a functional group-containing olefin polymer component (D) and 3 to 300 parts by weight of a flame retardant component (E).   The difficulty of claim 1, wherein the polyethylene resin component (C) is a linear low density polyethylene or high density polyethylene having a molecular weight distribution (Mw / Mn) measured by GPC of 10 or more. A flammable resin composition. The flame retardant resin composition according to claim 1 or 2, wherein the propylene-ethylene copolymer component (A) has the following characteristics (i) to (ii).
(I) In the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA), the peak due to the glass transition observed in the temperature range of −60 to + 20 ° C. is a single peak. Temperature is 0 ° C. or less (ii) Plot of elution amount (dwt% / dT) against temperature by temperature rising elution fractionation method (TREF) in the temperature range of −15 ° C. to 140 ° C. using o-dichlorobenzene solvent In the TREF elution curve obtained as follows, two peaks are observed in the (ii-A) elution curve having the following characteristics (ii-A) to (ii-C), and the peak T (A1 observed on the high temperature side) ) Is in the range of 65 to 95 ° C., and the peak T (A2) observed on the low temperature side is 45 ° C. or less. (Ii-B) The temperature T at the midpoint between both T (A1) and T (A2) peaks (A3) The amount W (A2) of the component (A2) eluted in is 5 to 70% by weight, and the component is a propylene-ethylene random copolymer containing 6 to 15% by weight of ethylene (ii-C) T ( A propylene homopolymer or propylene-ethylene in which the amount W (A1) of the component (A1) eluted after elution of the component eluted until A3) is 95 to 30% by weight, and the component contains 0 to 6% by weight of ethylene Random copolymer The flame retardant resin composition according to any one of claims 1 to 3, wherein the propylene-ethylene copolymer component (A) further has the following property (iii).
(Iii) 95-30 wt% of a crystalline propylene homopolymer or crystalline propylene-ethylene random copolymer component (A1) having an ethylene content of 0-6 wt% in the first step using a single-site catalyst, It is obtained by sequentially polymerizing 5 to 70% by weight of a low crystalline propylene-ethylene random copolymer component (A2) having an ethylene content of 6 to 15% by weight in the second step. The flame retardant resin composition according to any one of claims 1 to 4, wherein the propylene-ethylene copolymer component (A) further has the following characteristics (iv).
(Iv) In a TREF elution curve obtained as a plot of elution amount (dwt% / dT) against temperature by a temperature rising elution fractionation method (TREF) in a temperature range of −15 ° C. to 140 ° C. using an o-dichlorobenzene solvent, Two peaks are observed in the (iv-A) elution curve having the following characteristics (iv-A) to (iv-D), and the peak T (A1) observed on the high temperature side is in the range of 65 to 88 ° C. Yes, the peak T (A2) observed on the low temperature side is 45 ° C. or less. (Iv-B) A component that elutes up to the temperature T (A3) at the midpoint between the T (A1) and T (A2) peaks ( The amount W (A2) of A2) is 30 to 70% by weight, and the component is a propylene-ethylene random copolymer containing 8 to 14% by weight of ethylene. (Iv-C) Elution by T (A3) Elute after elution of components The amount W (A1) of the component (A1) is 70 to 30% by weight, and the component is a propylene-ethylene random copolymer containing 1 to 5% by weight of ethylene (iv-D) 99% by weight is eluted. The temperature T (A4) is 90 ° C. or less, and the temperature difference ΔT (T (A4) −T (A1)) from the peak T (A1) to T (A4) is 5 ° C. or less.   6. The difficulty according to claim 1, wherein the ethylene copolymer component (B) is an ethylene- (meth) acrylic acid alkyl ester copolymer or an ethylene-vinyl acetate copolymer. A flammable resin composition.   1 to 30 parts by weight of component (D) and 20 to 300 parts by weight of inorganic flame retardant component (E) are added to 100 parts by weight of the total amount of component (A), component (B) and component (C). The flame-retardant resin composition according to any one of claims 1 to 6, wherein   The functional group-containing olefin polymer component (D) is a component selected from an acid anhydride group-containing olefin copolymer or a metal salt thereof, or a modified polyolefin resin. Flame retardant resin composition.   The flame retardant resin composition according to claim 7 or 8, wherein the inorganic flame retardant is aluminum hydroxide and / or magnesium hydroxide.   The molded object formed by shape | molding the flame-retardant resin composition in any one of Claims 1-9.   It is an electric wire-cable, The molded object of Claim 10 characterized by the above-mentioned.