JP2002155174A - Flame-retardant resin composition and method for producing the same - Google Patents

Abstract

[57] [Abstract] [Problem] Maintains mechanical properties, flexibility, processability, and high flame retardancy, and possesses well-balanced physical properties with improved heat resistance, mechanical properties, and wear resistance. The present invention also provides a flame-retardant resin composition having significantly reduced costs and improved productivity. SOLUTION: Ethylene having a specific molecular structure (co)
Having a specific roughness on the polymer and other olefinic polymers,
And it is combined with magnesium hydroxide having a specific particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refractory resin composition containing a flame retardant containing magnesium hydroxide as a main component and a method for producing the same. More specifically, although it has a narrow molecular weight distribution, it has excellent mechanical strength, is rich in acceptability of a flame retardant, and has a moderately wide composition distribution. Copolymer with olefin (in the present specification, these homopolymers or copolymers are collectively referred to as "ethylene (co) polymer").
That. ) And a composition comprising a flame retardant containing magnesium hydroxide as a main component having a specific particle size, or a composition obtained by further blending a flame retardant aid such as red phosphorus with the composition, or A composition containing an olefin polymer or an olefin polymer into which a functional group is introduced, having flexibility, excellent heat resistance, excellent mechanical properties and productivity, and harmful gases such as halogen gas during combustion. TECHNICAL FIELD The present invention relates to an inevitable resin composition free from generation of a resin and a method for producing the same.

[0002]

2. Description of the Related Art Polyolefin resins are excellent in physical and chemical properties, and can be formed into films, sheets, pipes, containers, covered electric wires (hereinafter simply referred to as "electric wires") by various molding methods such as extrusion molding and injection molding. ), Molded into cables and the like, and is the most in demand general-purpose resin used in many applications such as home and industrial use. However, since polyolefin-based resins are flammable, various methods for making them flame-retardant have been proposed. The most common method is a method of flame retardation by adding an organic flame retardant such as halogen or phosphorus to a polyolefin resin.

However, although these organic flame retardants are effective with a small amount of compounding, they have the disadvantage that harmful halogen gas is generated during combustion. Therefore, recently, various methods of adding a hydrate of an inorganic metal compound such as aluminum hydroxide and magnesium hydroxide as a low-smoke-free, non-polluting flame retardant that does not generate harmful gas during combustion have been studied. (JP-A-2-53845)
JP, JP-A-2-145632). However,
In a flame-retardant resin composition using an inorganic flame retardant,
In order to enhance the flame retardancy, it is necessary to fill a large amount of an inorganic flame retardant. However, increasing the filling amount has practical difficulties such as a decrease in mechanical strength, flexibility, and workability. To improve this, a soft polyolefin resin is blended at a high concentration to receive an inorganic flame retardant. Techniques for increasing the capacity are also disclosed (US Pat. No. 4,722,959, US Pat. No. 484).
No. 5146).

However, such a flame-retardant resin composition containing a large amount of a soft resin has been used for general electric materials such as electric wires, cables, protective tubes and joint covers, and interior materials such as sheets and flooring materials. However, when manufacturing wires, cables or molded products such as cabinets, boxes, etc. for automobiles, vehicles, aircraft, ships, industrial robots, etc., when manufacturing, transporting and using, etc. Due to high temperatures, low temperatures, vibrations, etc., there is a demand for improvements in mechanical strength, abrasion resistance, etc., due to susceptibility to trauma. In response to such a demand, it has been proposed to use an inorganic flame retardant whose particle size is controlled finely for improving mechanical strength, but inorganic fillers are more expensive as the particle size becomes smaller. As a result, the production cost of the flame-retardant resin composition will increase significantly,
A compounding method for compounding such fine particles is difficult, and therefore, the productivity of the flame-retardant resin composition is reduced. That is, the method for producing a flame-retardant resin composition is generally described. After dry-blending resin pellets and a powdery inorganic flame retardant by an appropriate mixing means, for example, a Henschel mixer or the like, a screw-type single-screw or twin-screw extruder is generally used. The mixture is melt-mixed and pelletized by a machine (dry blending may be omitted as appropriate). Thereafter, it is molded into a predetermined shape by a molding machine using an appropriate molding method. At this time, the finer the filler, the more difficult it is to pelletize the melt-mixing, and in extreme cases, even sampling may not be possible due to surging. Here, magnesium hydroxide generally includes a synthetic product and a natural product (referred to as brute stone, talc, etc.). Although the synthetic product is likely to have a relatively fine particle size through operations such as precipitation and agglomeration, it is not easy to obtain a synthetic product having such a fine particle size that a reduction in mechanical strength can be prevented. On the other hand, since natural products are mined from natural deposits, it is necessary to pulverize them to a predetermined particle size. Since the pulverization is performed by mechanical pulverization, the pulverization operation for obtaining finer ones is not only costly and uneconomical, but also destroys the crystal structure of the bruceite itself, and may cause deterioration in performance as a filler.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a flame-retardant resin used for molding applications such as films, sheets, containers, electric wires, cables, packings, sealants, hoses, and injection molded articles. A composition comprising a combination of a specific ethylene (co) polymer, a specific roughness, and magnesium hydroxide having a specific particle size to provide mechanical strength, flexibility, workability, While maintaining a high level of flame retardancy and possessing well-balanced physical properties with improved heat resistance, mechanical properties, and abrasion resistance, a flame-retardant resin composition with significant cost reduction and improved productivity To provide.

[0006]

Means for Solving the Problems The first invention of the present application is:
(A) 100% by mass of a resin material containing 2% by mass or more of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 98% by mass or less of another olefin-based polymer. (C) a flame retardant comprising 30 to 200 parts by mass of a magnesium hydroxide-based flame retardant containing 30% by mass or more of particles having a particle median diameter of 3 μm or more and a particle diameter of 5 μm or more. (A) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) The temperature T ₂₅ (° C.) at which 25% of the whole is eluted and the temperature T at which 75% of the whole are eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF).
Difference from ₇₅ (° C.) T ₇₅ −T ₂₅ and density d (g / cm ³ )
T ₇₅ −T ₂₅ ≦ −670 × d + 644 (Equation 1) must be satisfied.

The second invention of the present application is characterized in that the other olefin polymer (B) is at least one olefin polymer selected from the following (B1) to (B3). The flame-retardant resin composition according to claim 1, wherein (B1) an ethylene (co) polymer obtained by ionic polymerization;
(B2) Ethylene (co) polymer by high pressure radical polymerization, (B3) rubber or elastomer.

According to a third aspect of the present invention, at least a part of the resin component (A), (B) or (A) + (B) is at least one kind selected from the following (A) to (F): The functional groups are added in an amount of 1 × 10 ^{−7 to} 5 × 10 per 1 g of the resin material.
3. The composition according to claim 1, wherein the content is ^-4 mol.
(A) a carboxylic acid group or a carboxylic anhydride group;
Epoxy group, (c) hydroxyl group, (d) amino group,
(E) alkenyl cyclic imino ether group, (f) silyl group.

Further, in the fourth invention of the present application, the resin component (A) is 3 to 50% by mass and (B1) + (B2) 97 to
(A), (B1) + (B2) or at least a part of (A) + (B1) + (B2)
1 g of carboxylic acid group or carboxylic anhydride group
The flame-retardant resin composition according to any one of claims 1 to 3, wherein the composition contains 1 x 10 ^{-7 to} 5 x 10 ^-4 mol per unit.

Further, in the fifth invention of the present application, the resin component (A) has a density of 0.86 to 0.94 g / cm ³ ,
An ethylene (co) polymer having an MFR of 0.5 to 10 g / 10 min.
1 to 20% by weight of an ethylene (co) polymer obtained by graft-modifying an ethylene / α-olefin copolymer of 6 to 0.97 g / cm ³ with maleic anhydride, and an ethylene / ethyl acrylate copolymer as a component (B2) Or 50 to 96% by mass of an ethylene-vinyl acetate copolymer (provided that the total of (A) + (B1) + (B2) is 100% by mass)
It is. The flame-retardant resin composition according to any one of claims 1 to 4, wherein

Further, the sixth invention of the present application is directed to the above-mentioned
(A) polymer (A) further satisfies the requirement of (e) below.
6. The method according to claim 1, further comprising:
(E) Elution temperature by continuous heating elution fractionation method (TREF)
25% of the total obtained from the integrated elution curve of the elution amount curve
Elution temperature T_{twenty five}(° C) and temperature T at which 75% of the whole elutes
₇₅(° C) T₇₅-T_{twenty five}And density d (g / cm^Three)But,
d <0.950 g / cm^Three When T₇₅-T_{twenty five}≧ −30
0 × d + 285, d ≧ 0.950 g / cm ^ThreeWhen T
₇₅-T_{twenty five}≧ 0 Satisfies the relationship of (Equation 2).

In a seventh aspect of the present invention, the ethylene (co) polymer (A) further comprises the following (f) and (g):
The flame-retardant resin composition according to any one of claims 1 to 6, which is an ethylene (co) polymer (A1) satisfying the following requirement: (f) orthodichlorobenzene (25 ° C) ODC
B) The soluble content X (mass%), density d (g / cm ³ ) and melt flow rate (MFR) (g / 10 min) are d-
When 0.008 log MFR ≧ 0.93, X <2.0
(Equation 3), and d-0.008 log MFR <0.
In the case of 93, X <9.8 × 10 ³ × (0.9300−d +
0.008 log MFR) ² +2.0 Satisfies the relationship of (Equation 4), and (g) continuous heating elution fractionation method (TREF)
A plurality of peaks of the elution temperature-elution amount curve due to

In an eighth aspect of the present invention, the ethylene (co) polymer (A) further comprises the following (h) and (i)
The flame-retardant resin composition according to any one of claims 1 to 6, which is an ethylene (co) polymer (A2) that satisfies the following condition: One peak of the elution temperature-elution amount curve by (TREF), (i) one or two melting point peaks, and the highest melting point T _{m1 of} them
(° C.) and density d (g / cm ³ ), T _m1 ≧ 150 × d−17
Satisfy the relationship of (Equation 5).

In a ninth aspect of the present invention, the ethylene (co) polymer (A2) further satisfies the following requirement (j): (J) The melt tension (MT) (g) and the melt flow rate (MFR) (g / 10 minutes) are logMT ≦ −
0.572 × logMFR + 0.3 Satisfies the relationship of (Equation 6).

In a tenth aspect of the present invention, there is provided a catalyst wherein the ethylene (co) polymer (A) comprises an organic cyclic compound having at least a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. The flame-retardant resin composition according to any one of claims 1 to 9, which is manufactured below.

[0016] Further, the eleventh invention of the present application is characterized in that (C)
The flame-retardant resin composition according to any one of claims 1 to 10, wherein the magnesium hydroxide as a flame retardant is a natural product.

The flame-retardant resin composition according to any one of claims 1 to 11, wherein the twelfth invention of the present application further comprises 0.1 to 50 parts by mass of a flame retardant aid per 100 parts by mass of the resin material. Things.

A thirteenth invention of the present application is the flame-retardant resin composition according to claim 12, wherein the flame-retardant auxiliary is at least one selected from red phosphorus, carbon black, and a boron compound. .

Further, the fourteenth invention of the present application relates to (A) 2% by mass or more of an ethylene (co) polymer satisfying the following requirements (a) to (d); (C) with respect to 100 parts by mass of the resin material containing not more than
Particle median diameter is 3μm or more and particle diameter is 5μm
A method for producing a flame-retardant resin composition obtained by blending 30 to 200 parts by mass of a flame retardant containing magnesium hydroxide as a main component containing 30% by mass or more of the above particles and extruding the mixture at a molding temperature of 150 to 270 ° C. Yes: (a) Density 0.86 ~
0.97 g / cm ³ , (b) the melt flow rate is 0.
01 to 100 g / 10 min, (c) molecular weight distribution (Mw / M
n) is 1.5 to 4.5, and (d) continuous heating elution fractionation method (T
REF) The difference T ₇₅ −T between the temperature T ₂₅ (° C.) at which ₂₅ % of the whole is eluted and the temperature T ₇₅ (° C.) at which 75% of the whole is eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by REF). ₂₅ and the density d (g / cm ³ ) are T ₇₅ −T ₂₅ ≦ −670 × d + 6
44 Satisfy the relationship of (Equation 1).

Hereinafter, the present invention will be described in detail. The ethylene (co) polymer (A) in the present invention is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin. Here, the α-olefin is a compound having 3 to 2 carbon atoms.
0, preferably 3 to 12, specifically propylene, 1-butene, 1-pentene, 4-methyl-1
-Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. In addition, these α
-It is desirable that the content of the olefin is generally selected in a range of usually 30 mol% or less, preferably 3 to 20 mol% or less.

The (a) density of the ethylene (co) polymer (A) in the present invention is 0.86 to 0.97 g / cm.
³ , preferably 0.89 to 0.94 g / cm ³ , more preferably 0.90 to 0.93 g / cm ³ . If the density is less than 0.86 g / cm ³ , rigidity (lumbar strength) and heat resistance are inferior. 0.97g
/ Cm ³ is difficult to produce industrially. The measurement of the density conforms to JIS K7112.

The (b) melt flow rate of the ethylene (co) polymer (A) in the present invention (hereinafter referred to as "MFR")
It is written. ) Is in the range of 0.01 to 100 g / 10 min, preferably 0.03 to 30 g / 10 min. If the MFR is less than 0.01 g / 10 minutes, the molding processability is inferior and 100
If it exceeds g / 10 minutes, mechanical strength such as impact resistance is inferior.
The measurement of MFR is based on JIS K7210.

The (c) molecular weight distribution (Mw / Mn) of the ethylene (co) polymer (A) in the present invention is from 1.5 to 1.5.
The range is 4.5, preferably 2.0 to 4.0, and more preferably 2.5 to 3.0. Mw / Mn is 1.
If it is less than 5, the moldability is poor, and if it exceeds 4.5, the impact resistance is poor. Here, the molecular weight distribution (Mw / Mn) of the ethylene (co) polymer is obtained by determining the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculating the ratio (Mw / Mw). / M
n).

The ethylene (co) polymer (A) in the present invention is obtained, for example, from the integrated elution curve of the elution temperature-elution amount curve (TREF) as shown in FIG. The temperature T _{25 at which} 25% of the total elutes
(° C.) and the temperature T ₇₅ (° C.) at which 75% of the total elutes, T ₇₅
-T ₂₅ and density d (g / cm ³ ) satisfy the relationship of the following (Equation 1). (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 That is, the elution temperature-elution amount curve of the ethylene (co) polymer (A) by TREF is represented by the elution temperature on the horizontal axis and the relative elution amount on the vertical axis. It is shown as 1. In this case, from the low temperature side, the temperature at which 25% of the total elution amount elutes is determined from the elution curve and defined as T ₂₅ (° C.).
_{When the} temperature is set to ₇₅ (° C.), the above relationship is satisfied.
When the T ₇₅ -T ₂₅ and density d do not satisfy the relation of the equation (1) would heat resistance is inferior.

Further, the ethylene (co) polymer (A) in the present invention preferably further satisfies the following requirement (e): (e) Elution temperature-elution by the continuous temperature-elution elution fractionation method (TREF) The temperature T ₂₅ (° C.) at which 25% of the whole is eluted and the temperature T at which 75% of the whole are eluted, obtained from the integrated elution curve of the amount curve
Difference from ₇₅ (° C.) T ₇₅ −T ₂₅ and density d (g / cm ³ )
Satisfy the relationship of the following (Equation 2). (Equation 2) When d <0.950 g / cm ³ , T ₇₅ −T ₂₅
≧ −300 × d + 285 d ≧ 0.950
In the case of g / cm ³ , T ₇₅ −T ₂₅ ≧ 0 If the relationship of the above (Equation 2) is not satisfied, the moldability will be poor.

The ethylene (co) polymer (A) in the present invention is an ethylene (co) polymer (A1) satisfying the requirements of (f) and (g) described below, or (h) further described below. And ethylene (co) polymer (A2) satisfying the requirements of (i).

In the present invention, the ethylene (co) polymer (A)
1) (f) Amount X (% by mass) of ODCB-soluble component at 25 ° C., density d (g / cm ³ ) and MFR (g / 10
Min) is X <2.0 (Formula 3) and d-0.008 log when d-0.008 log MFR ≧ 0.93.
When gMFR <0.93, X <9.8 × 10 ³ × (0.
9300-d + 0.008 log MFR) ² +2.0
(Equation 4) is satisfied, and preferably, d-0.
When 008 log MFR ≧ 0.93, X <1.0, d
If -0.008 log MFR <0.93, X <7.
4 × 10 ³ × (0.9300-d + 0.008 logMF
R) ² +1.0, and more preferably d−
When 0.008 log MFR ≧ 0.93, X <0.
5. If d−0.008 log MFR <0.93, X
<5.6 × 10 ³ × (0.9300−d + 0.008lo)
gMFR) ² +0.5.

Here, the amount X (% by mass) of the ODCB-soluble component at 25 ° C. is measured by the following method.
0.5 g of the sample is heated at 135 ° C. for 2 hours with 20 ml of ODCB to completely dissolve the sample and then cooled to 25 ° C. After leaving this solution at 25 ° C. overnight, the solution is filtered through a Teflon (registered trademark) filter to collect a filtrate. This filtrate, which is a sample solution, is measured for the absorption peak intensity near the wave number 2925 cm ^-1 of asymmetric stretching vibration of methylene by an infrared spectrometer, and the sample concentration is calculated from a calibration curve prepared in advance.
From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a component having a high degree of branching and a low molecular weight component contained in the ethylene (co) polymer, which causes a reduction in heat resistance and stickiness on the surface of a molded product, and a problem of hygiene. It is desirable that this content be small, because it causes blocking of the molded article. Also,
Low molecular weight components also cause smoke during molding. ODCB
The amount of solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR.
Therefore, these indices of density, MFR and ODCB
The fact that the amount of the soluble component satisfies the above relationship indicates that the α-olefin contained in the whole copolymer is less unevenly distributed.

As shown in FIG. 2, the ethylene (co) polymer (A1) of the present invention has a peak in the elution temperature-elution amount curve obtained by (g) continuous temperature elution fractionation (TREF), as shown in FIG. Are plural. Among these, it is particularly preferred that the high peak temperature is between 85 ° C and 100 ° C. The presence of this peak increases the melting point and crystallinity, and improves the heat resistance and rigidity of the molded body.

The method of measuring TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) has been added so that the sample concentration becomes 0.05% by mass, and the sample is heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature was raised to 50 ° C.
The sample is sequentially eluted while heating at a constant rate of ° C./hr. At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of the asymmetric stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate. T
According to the REF analysis, the change in the elution rate with respect to the temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

In the present invention, the ethylene (co) polymer (A)
2) is a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. The α-olefin has preferably 5 to 10 carbon atoms.
-Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. In addition, the content of these α-olefins,
Usually 30 mol% or less in total, preferably 3 to 20 mo
It is desirable to select within the range of 1% or less.

In the present invention, the ethylene (co) polymer (A)
2), as shown in FIG. 2, (h) one peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF) and (i) one or two melting point peaks. And the highest melting point T _m1 (° C.) and density d (g / cm ³ )
Satisfy the relationship of T _m1 ≧ 150 × d−17 (Equation 5). If the melting point T _m1 (° C.) and the density d (g / cm ³ ) do not satisfy the relationship of the above (Equation 5), the heat resistance will be poor. Here, the melting point is measured using a DSC as follows. First, a sheet having a thickness of 0.2 mm is formed by hot pressing, and a sample of about 5 mg is punched from the sheet. This sample was set in a DSC device (manufactured by PerkinElmer) and the
After holding at 0 ° C. for 10 minutes, the temperature is cooled to 0 ° C. at 2 ° C./min, and the temperature is again raised to 170 ° C. at 10 ° C./min. _m1 (° C).

Further, among the ethylene (co) polymers (A2), ethylene (co) polymers that further satisfy the following requirement (j) are preferred: (j) melt tension (MT) (g); MFR (g /
10 minutes), but logMT ≦ −0.572 × logMFR
+0.3 Satisfies the relationship of (Equation 6). MT and MF
When R satisfies the relationship of the above (formula 6), molding processability such as extrusion molding becomes good. Here, the MT is determined by measuring the stress when the molten polymer is stretched at a constant speed with a strain gauge. As a measurement sample, a granulated pellet is used, and a melt tension measuring device (manufactured by Toyo Seiki Seisaku-sho, Ltd.) is used. The orifice used has a hole diameter of 2.09 mmφ, a length of 8 mm, and a temperature of 19
0 ° C, cylinder lowering speed 20mm / min, winding speed 1
Measure under the condition of 5 m / min.

The ethylene (co) polymer (A) of the present invention comprises (A1) and (A2) in FIG.
The olefin copolymer is included, and the ethylene / α-olefin copolymers in FIGS. 2 and 3 are respectively positioned as follows. That is, as shown in FIG. 2, the peak of the ethylene (co) polymer (A) substantially has a peak in the elution temperature-elution amount curve obtained by the continuous heating elution fractionation method (TREF), as shown in FIG. Although it is plural, it satisfies all of the requirements of (a), (b), (c), and (d). Unlike the ethylene / α-olefin copolymer polymerized with a conventional Ziegler catalyst, It is something. On the other hand, FIG. 3 shows a continuous heating elution fractionation method (TRE).
In the elution temperature-elution amount curve obtained in F), an ethylene / α-olefin copolymer having substantially one peak is shown. Corresponds to. Further, the ethylene (co) polymer (A2) of the present invention has a T
Although there is only one REF peak, a copolymer using a conventional typical metallocene-based catalyst is clearly distinguished from not satisfying (Equation 2) as described above.

The ethylene (co) polymer (A) in the present invention is not particularly limited to a catalyst, a production method and the like as long as it satisfies the above parameters, but is preferably an organic cyclic compound having at least a conjugated double bond. A linear ethylene (co) polymer obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of a compound and a catalyst containing a transition metal compound of Group IV of the periodic table. It is desirable. Since such a linear ethylene (co) polymer has a narrow molecular weight distribution and a narrow composition distribution, it is a polymer having excellent mechanical properties, excellent heat resistance blocking properties, etc., and good heat resistance.

In the production of the ethylene (co) polymer (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4. a1: Compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr (wherein Me ¹ represents zirconium, titanium or hafnium, and R ¹ and R ³ each have a carbon number) 1-2
R ² is a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof, X ¹ is a halogen atom, , Q and r are each 0 ≦ p ≦
4, an integer satisfying the range of 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4. ). a2: a compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn (where Me ² is an element of Groups I to III of the periodic table, and R ⁴ and R ⁵ each have 1 to 24 carbon atoms) X ² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a Group III element of the periodic table), and z is the valence of Me ² And m and n are integers that satisfy the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.) a3: Organic cyclic compound having a conjugated double bond. a4: A modified organic aluminum oxy compound and / or boron compound containing an Al-O-Al bond.

The details will be described below. The above-mentioned catalyst component a1
In the formula of the compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium or hafnium. The types of these transition metals are not limited, and plural types can be used. Among them,
It is particularly preferable to include zirconium from which a copolymer having excellent weather resistance can be obtained. R ¹ and R ³ each represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. R ² represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine. p, q and r are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦
4, an integer satisfying the range of 0 ≦ r ≦ 4 and 0 ≦ p + q + r ≦ 4.

Examples of the compounds represented by the general formula of the above-mentioned catalyst component a1 include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodiconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrabutoxy titanium , Tetrabutoxy hafnium and the like, and particularly, Z such as tetrapropoxy zirconium and tetrabutoxy zirconium
r (OR) ₄ compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonato ligand or derivative thereof include tetra (2,4-pentanedionato) zirconium. , Tri (2,4-pentanedionato)
Zirconium chloride, di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4- Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionato) dineofylzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Zirconium toxide, zirconium di (dibenzoylmethanato) di-n-propoxide, zirconium di (dibenzoylmethanato), zirconium di-n-butoxide, zirconium diethoxide zirconium, di (benzoylacetonate) ) Di-n-propoxide zirconium, di (benzoylacetonate)
And di-n-butoxide zirconium.

The general formula Me of the catalyst component a2^TwoR^Four _m(O
R^Five)_nX^Two _zmn In the formula of the compound represented by^Two Is around
Elements of the Periodic Table Group I-III, lithium, sodium
, Potassium, magnesium, calcium, zinc, bor
Element, aluminum and the like. R ^Four And R^Five Is it
A hydrocarbon group having 1 to 24 carbon atoms, preferably 1 carbon atom
To 12, more preferably 1 to 8, and specifically,
Chill, ethyl, propyl, isopropyl, buty
Alkyl groups such as vinyl group; alkyl groups such as vinyl group and allyl group
Kenyl group; phenyl group, tolyl group, xylyl group, mesity
Aryl groups such as phenyl, indenyl, and naphthyl;
Benzyl, trityl, phenethyl, styryl, benzyl
Hydryl group, phenylbutyl group, neofuyl group, etc.
And an aralkyl group. These have branches
You may. X^Two Is fluorine, iodine, chlorine and bromine, etc.
Represents a halogen atom or a hydrogen atom. However
Then X ^Two Is Me when hydrogen is a hydrogen atom^Two Is boron, aluminum
Only in the case of Group III elements in the periodic table
Things. Z is Me^Two And m and m
And n satisfy the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
Is an integer, and 0 ≦ m + n ≦ z.

Examples of the compounds represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; Organic zinc compounds such as zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride , Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum Derivatives of organoaluminum compounds such as Idoraido the like.

The organic cyclic compound having a conjugated double bond of the catalyst component a3 has one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds. A cyclic hydrocarbon compound having two or more carbon atoms and having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically, A cyclic hydrocarbon compound substituted with an alkyl group or an aralkyl group of the formulas 1 to 12; two or more, preferably 2 to 4, more preferably 2 to 2, conjugated double bonds.
One or more rings having three rings and a total carbon number of 4
An organosilicon compound having a cyclic hydrocarbon group of from 24 to 24, preferably 4 to 12; said cyclic hydrocarbon group being partially substituted by 1 to 6 hydrocarbon residues or an alkali metal salt (sodium or lithium salt) Organosilicon compounds. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

Organosilicon compound having cyclic hydrocarbon group
Can be represented by the following general formula. A_LSiR_4-L  Here, A is a cyclopentadienyl group, a substituted cyclopentene
Exemplified by tadienyl group, indenyl group and substituted indenyl group
Represents a cyclic hydrocarbon group represented by the following formula:
Alkyl, propyl, isopropyl, butyl, etc.
Alkyl group; methoxy group, ethoxy group, propoxy group,
Alkoxy groups such as toxic groups; aryl groups such as phenyl groups
Aryl group such as phenoxy group; benzyl
Represented by an aralkyl group such as a group having 1 to 24 carbon atoms, preferably
Or 1 to 12 hydrocarbon residues or hydrogen, and L is
1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-
Indene, 4,7-dimethylindene, butylcycloheptadiene, 1-methyl-3-propylcyclopentadiene and indene, 1-methyl-3-butylcyclopentadiene and indene, propylcyclopentadiene, 1-
Methyl-3-ethylcyclopentadiene, 1,2,4-
Trimethylcyclopentadiene cycloheptatriene,
C5-C24 cyclopolyene or substituted cyclopolyene such as methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadiene Examples include enylsilane, monoindenylsilane, bisindenylsilane, trisindenylsilane, and methylcyclopentadientinemethylsilane.

In the present invention, a4: Al—O—Al
A modified organoaluminum compound containing a bond and / or a boron compound is used. Specific examples of the modified organoaluminum oxy compound containing an Al-O-Al bond include:
Modified organic aluminum oxy compounds, usually called aluminoxanes, obtained by reacting an alkyl aluminum compound with water are mentioned. The modified organoaluminum oxy compound usually has 1 to
Those containing 100, preferably 1 to 50 Al-O-Al bonds are mentioned. The modified organic aluminum oxy compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2.
/ 1, preferably 0.5 / 1 to 1/1.

Examples of the boron compound include triethylaluminum tetra (pentafluorophenyl) borate and triethylammonium tetra (pentafluorophenyl)
Borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N, N-
Dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5 difluorophenyl) borate and the like can be mentioned.

The above catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst by supporting it on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof, a thermoplastic resin, and a thermosetting resin. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ ,
CaO, ZnO, BaO, ThO ₂ and the like or mixtures _{thereof, SiO 2 -Al 2 O 3,} SiO 2 -V
₂ O ₅ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂
—MgO, SiO ₂ —Cr ₂ O _{3 and the} like. Among them, those mainly containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ are preferable. In addition, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are. However, as a pretreatment, these carriers are preferably converted to an organic aluminum compound or a modified organic aluminum compound containing an Al—O—Al bond. After the contact treatment, it can be used as the component a5.

The process for producing the ethylene (co) polymer (A) in the present invention is carried out by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like in the presence of the above-mentioned catalyst, which is substantially free of a solvent. In a state where oxygen, water, etc. are substantially turned off, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified as above. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C,
The polymerization pressure is usually from normal pressure to 7 MPa (70 k
g / cm ² ) Gauge, preferably normal pressure to 2 MPa (20 k
g / cm ² ) Gauge, usually 150M for high pressure method
Pa (1500 kg / cm ² ) Gauge or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of high pressure method, usually 1
Minutes to 30 minutes, preferably about 2 to 20 minutes.
In addition, the polymerization is not particularly limited to a single-stage polymerization method, or a two- or more-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other.

The ethylene (co) polymer (A) in the present invention is produced by using a catalyst containing no halogen such as chlorine in the above-mentioned catalyst components, so that the halogen concentration is at most 10 ppm or less. Preferably 5 pp
m or less, more preferably substantially free of (ND: 2
ppm or less). By using such a halogen-free ethylene (co) polymer such as chlorine, it is not necessary to use an acid neutralizer (acid absorber) as in the prior art, and the chemical stability and hygiene are excellent. Products can be provided.

The (B) other olefin polymer in the present invention includes (B1) an ethylene (co) polymer obtained by ionic polymerization, (B2) an ethylene (co) polymer obtained by high-pressure radical polymerization, and (B3) It is at least one selected from rubber and elastomer.

The (B1) ethylene (co) polymer obtained by ionic polymerization refers to an ethylene homopolymer obtained by a medium-to-low pressure method using a Ziegler catalyst or a Phillips catalyst, or other known methods, or an α-polymer having 3 to 12 carbon atoms. A copolymer with an olefin, having a density of 0.86 to 0.97 g;
/ Cm ³ , preferably 0.86 to 0.94 g / cm ^{3, such as} an ethylene / α-olefin copolymer (that is, very low density polyethylene (VLDPE) and linear low density polyethylene (LLDPE)).

Specific α-olefins include α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-hexene.
Octene, 1-dodecene and the like can be mentioned. Of these, preferred are 1-butene and 4-methyl-1-
Penten, 1-hexene and 1-octene are preferred, with 1-butene being particularly preferred. The α-olefin content in the ethylene / α-olefin copolymer is 5 to 40 mol
%.

Examples of the ethylene-based (co) polymer obtained by subjecting the component (B2) to high pressure radical polymerization include branched low-density polyethylene (LDPE), ethylene and alkyl esters of α, β-unsaturated carboxylic acids and derivatives thereof, vinyl A copolymer with a carboxyl group-containing monomer such as an ester may be used.

Examples of the copolymer with the above-mentioned alkyl ethylene / α, β-unsaturated carboxylic acid ester and its derivatives include α, β-unsaturated carboxylic acid ester copolymers and metal salts, amides and imides thereof. No. Specific examples include an ethylene / acrylic acid (or methacrylic acid) methyl copolymer and an ethylene / acrylic acid (or methacrylic acid) ethyl copolymer. In particular, ethylene / ethyl acrylate copolymer (hereinafter referred to as “EE
A ". Is preferred. That is, a copolymer comprising 50 to 99.5% by mass of ethylene and 0.5 to 50% by mass of ethyl acrylate is preferred. The MFR of the copolymer is selected from the range of 0.1 to 50 g / 10 min, preferably 0.5 to 20 g / 10 min.
If the MFR is less than 0.1 g / 10 minutes, the fluidity of the resin composition will be poor, and if it exceeds 50 g / 10 minutes, the mechanical strength will be undesirably reduced.

The above-mentioned ethylene / vinyl ester copolymer is mainly composed of ethylene produced by a high-pressure radical polymerization method. It is a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate. Among them, particularly preferred is an ethylene / vinyl acetate copolymer (hereinafter, may be abbreviated as “EVA”). That is, 50 to 99.5% by mass of ethylene,
A copolymer comprising 0.5 to 50% by mass of vinyl acetate is preferred.

The above-mentioned copolymers of ethylene / α, β-unsaturated carboxylic acid alkyl esters and their derivatives and oxygen-containing copolymers such as ethylene / vinyl ester copolymers are mixed with inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide. When combined with a flame retardant, the flame retardant effect is further enhanced and the oxygen index (OI) is also increased. This is because the interaction between the oxygen-containing copolymer and the inorganic flame retardant during combustion promotes the formation of a char (carbonized layer), and the char formed on the surface of the combusted material impedes the supply of oxygen. Presumed. The effect of forming the char is particularly high in EEA and EVA, and the flame retardant effect is also large. Of these, EEA is particularly preferred.

The rubber or elastomer of the component (B3) in the present invention includes ethylene propylene rubber, butadiene rubber, isoprene rubber, natural rubber, nitrile rubber, isobutylene rubber and the like. These may be used alone or as a mixture.

The above-mentioned ethylene-propylene rubber includes:
A random copolymer (EPM) containing ethylene and propylene as main components, and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component
Random copolymer (EPD) containing as a main component
M).

The above-mentioned butadiene rubber refers to a copolymer containing butadiene as a constituent element. Styrene-butadiene block copolymer (SBS) and its hydrogenated or partially hydrogenated derivative, styrene-butadiene-ethylene copolymer. Coalescence (SBES), 1,2-polybutadiene (1,
2-PB), maleic anhydride / butadiene / styrene copolymer, modified butadiene rubber having a core-shell structure, and the like.

The above-mentioned isoprene-based rubber is a copolymer containing isoprene as a constituent element, and is a styrene / isoprene block copolymer (SIS) and its hydrogenated or partially hydrogenated derivative, styrene / isoprene / ethylene copolymer ( SIES), modified isoprene rubber having a core-shell structure, and the like.

The olefin polymer of the component (B) in the present invention can be used without a decrease in mechanical strength when a large amount of an inorganic flame retardant is blended to maintain a high degree of flame retardancy. It plays a role in enhancing the properties and impact resistance. Among these, the component (B2) is preferably used.

The amount of component (A) and component (B) in the resin material of the present invention is 100 to 2% by mass of component (A).
0 to 98% by mass of the component (B), preferably 50 to 3% by mass of the component (A) and 50 to 3% by mass of the component (B).
97% by mass.

Further, the resin component of the present invention comprises (A) a carboxylic acid group or a carboxylic acid anhydride group, at least one of the component (A), the component (B), and the component (A) + (B). A) epoxy group, (c) hydroxyl group, (d)
An amino group, an (e) alkenyl cyclic imino ether group,
(F) It is preferred that at least one functional group selected from silyl groups is in the range of 10 ^{-7 to} 5 × 10 ^-4 mol per 1 g of the total resin material.

The compound for introducing the functional group (a) (carboxylic acid group or carboxylic anhydride group) includes α, β such as maleic acid, fumaric acid, citraconic acid and itaconic acid.
-Unsaturated dicarboxylic acids or anhydrides thereof, acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid, unsaturated monocarboxylic acids such as pentenoic acid and the like.

Compounds for introducing the functional group (a) (epoxy group) include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, and butenetricarboxylic acid Triglycidyl ester and α-chloroacrylic acid,
Glycidyl esters such as maleic acid, crotonic acid, and fumaric acid or glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene and p-glycidyl ether, and p-glycidyl styrene are included. Preferred are glycidyl methacrylate and allyl glycidyl ether.

Examples of the compound for introducing a functional group (c) (hydroxyl group) include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

Compounds for introducing the functional group (d) (amino group) include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutyl Aminoethyl (meth)
Acrylate, aminopropyl (meth) acrylate,
Examples thereof include phenylaminoethyl (meth) acrylate and cyclohexylaminoethyl (meth) acrylate.

The compound for introducing the functional group (e) (alkenyl cyclic imino ether group) includes a compound represented by the following structural formula.

Embedded image

Here, n is 1, 2 and 3, preferably 2 and 3, and more preferably 2. Also R
⁷ , R ⁸ , R ⁹ and R each independently represent C 1 -C
A 12 (C 1 -C 12) inert alkyl group and / or
Alternatively, it represents hydrogen, and the alkyl group may have an inert substituent. The term “inert” as used herein means that the graft reaction or the function of the product is not adversely affected. Also, a plurality of Rs need not be the same. Preferably R ⁷ ＲR ⁸ ＨH, R ⁹ ＨH or Me, R ＝ H, ie 2-vinyl and / or 2-isopropenyl-
2-oxazoline, 2-vinyl and / or 2-isopropenyl-5,6-dihydro-4H-1,3-oxazine. These may be used alone or as a mixture. Among them, 2-vinyl and / or 2-isopropenyl-2-oxazoline are particularly preferred.

Examples of the compound for introducing the functional group (f) (silyl group) include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane and vinyltrichlorosilane. Among the functional groups (A) to (F), (A) a carboxylic acid group or a carboxylic anhydride group is most preferably used.

As a specific method for introducing a functional group into the resin material of the present invention, at least one kind of the functional group-containing monomer is added to the component (A), the component (B) or the component (A) +
(B) a method of introducing as a modified polymer grafted on a part or all of the component, and a method of introducing the functional group by blending and introducing a random copolymer of ethylene and a functional group-containing compound into a resin component. And the like.

The method for producing the grafted modified polymer of the present invention includes a melting method in which at least one compound having the functional group is melted in an extruder to modify the resin in the presence of a radical initiator, And a method of graft modification to a polymer by a solution method in which the polymer is mixed and reacted in a solution. Examples of the radical initiator include organic peroxides, dihydroaromatic compounds, and dicumyl compounds.

Examples of the organic peroxide include hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide,
Dipropionyl peroxide, dioctanoyl peroxide, benzoyl peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,5
Di (t-butylperoxy) hexane, t-butyloxyacetate, t-butylperoxyisobutyrate and the like are preferably used.

As the dihydroaromatic compound, dihydroquinoline or a derivative thereof, dihydrofuran, 1,2-
Dihydrobenzene, 1,2-dihydronaphthalene, 9,
10-dihydrophenanthrene and the like.

Examples of the dicumyl compound include 2,3-dimethyl-2,3-diphenylbutane and 2,3-diethyl-
2,3-diphenylbutane, 2,3-diethyl-2,3
-Di (p-methylphenyl) butane, 2,3-diethyl-2,3-di (p-bromophenyl) butane and the like are exemplified, and 2,3-diethyl-2,3-diphenylbutane is particularly preferably used. .

As a method for producing the functional group-containing random copolymer of the present invention, a tubular reactor or an autoclave reactor is used in the presence of a radical initiator and a chain transfer agent under a pressure of 250 to 300 MPa (25 MPa).
A method of copolymerizing ethylene and at least one of the compounds having a functional group under the conditions of about 00 to 3000 kg / cm ² ) and a temperature of about 250 ° C. Examples of the radical initiator include the above-mentioned organic peroxides.

As described above, the functional group in the resin material of the present invention is different from the component (A) or (A) + (B)
When using a graft-modified polymer, 10 ^{-7 to} 5 × 10
^-4 mol / g, and 5 when a random copolymer of ethylene and a functional group-containing compound is used.
It is adjusted so as to be in the range of × 10 ⁻⁶ mol to 5 × 10 ⁻⁴ mol / g. When a graft-modified polymer is used, the functional group is less than 10 ^-7 mol / g, and when a random copolymer of ethylene and a functional group-containing compound is used, the functional group is less than 5 × 10 ^-6 mol / g. In this case, the coupling effect between the resin component and the flame retardant containing magnesium hydroxide as the component (C) described below as a main component becomes insufficient, and the mechanical strength and the like may be poor. Further, the formation of char (carbonized layer) when the composition burns may be impaired, and the drip resistance may be reduced. In addition, the content of the functional group is 5 ×
If it exceeds 10 ^-4 mol / g, the coupling effect becomes too large, and the mechanical strength and especially the elongation of the resin composition decrease.

Among these modified polymers containing a functional group or random copolymers of ethylene and a functional group-containing compound, in particular, the components (A) and / or (B) have a density of 0.86 to 0.97 g. / Cm ^{3 of} an ethylene / α-olefin copolymer obtained by graft-modifying maleic anhydride is preferably used. As the composition of the present invention, 3 to 50% by mass of the resin component (A) and (B
1) + (B2) 97 to 50% by mass, (A), (B
1) + (B2) or (A) + (B1) + (B2) has at least a part of (a) a carboxylic acid group or a carboxylic anhydride group per 1 g of the resin material, from 1 × 10 ^{−7 to} 5 × 10 ^−. Those containing ⁴ mol are preferred. In particular, the component (A) has a density of 0.86 to 0.94 g / cm ³ and an MFR of 0.
3 to 50% by mass of an ethylene (co) polymer having a content of 5 to 10 g / 10 minutes and a density of 0.86 to 0.97 as the component (B1).
g / cm ³ ethylene / α-olefin copolymer, maleic anhydride graft-modified ethylene (co) polymer 1
20% by mass and ethylene-ethyl acrylate copolymer or ethylene-vinyl acetate copolymer 5 as component (B2)
A resin composition containing 0 to 96% by mass (provided that (A)
The sum of + (B1) + (B2) is 100% by mass. )
However, it has an excellent balance of mechanical strength, flexibility, high flame retardancy and the like, and is preferred.

The component (C) of the present invention comprises 30 particles having a median particle diameter of 3 μm or more and a particle diameter of 5 μm or more.
A flame retardant containing magnesium hydroxide as a main component and containing at least 3% by mass, preferably having a particle median diameter of 3 to 8 μm,
Further, it is a flame retardant containing magnesium hydroxide as a main component containing 30 to 60% by mass of particles having a particle size of 5 to 50 μm. Here, the main component means a purity of about 90% or more. One example of the magnesium hydroxide is obtained by using a naturally occurring brucite ore as a raw material and pulverizing it to the above specific particle size. Further, as another example, magnesium ions in seawater or bitterness, or magnesium and other components, for example, calcium carbonate, ore containing silica as a raw material, is obtained by synthesis, the above specific particle size It only has to be adjusted. If the particle median diameter is less than 3 μm and the particles having a particle diameter of 5 μm or more are less than 30% by mass, the supply amount from the supply port of the extruder becomes unstable, so that it becomes difficult to produce a flame-retardant composition, If the median diameter exceeds 8 μm and the particles having a particle diameter of 5 μm or more exceed 60% by mass, the surface of the obtained product becomes rough and the appearance is impaired. The particle diameter was measured by a laser method using SALD200V manufactured by Shimadzu Corporation, and the area corresponding to 50% by mass from the mass cumulative distribution diagram obtained therefrom was defined as the median diameter. Other flame retardant components that can be added to the magnesium hydroxide, magnesium hydroxide other than the above, aluminum hydroxide, zirconium hydroxide, dolomite, hydrotalcite,
Examples thereof include hydrates of calcium hydroxide, barium hydroxide, tin oxide, and hydrates of inorganic metal compounds such as borax.

The amount of the component (C) is 3 parts per 100 parts by mass of the resin material (A) or (A) + (B).
It is 0 to 200 parts by mass, preferably 40 to 150 parts by mass. If the compounding amount is less than 30 parts by mass, it is difficult to achieve sufficient flame retardancy, whereas if the compounding amount exceeds 200 parts by mass,
Mechanical strength such as tensile strength, elongation, and impact strength is reduced, flexibility is lost, and low-temperature properties are poor. Conventionally, magnesium hydroxide having a fine particle diameter such that the median diameter is 0.5 to 1 μm and contains almost no particles of 5 μm or more has been used to prevent the mechanical properties of the composition from decreasing. However, such a material is very expensive and has a low bulk density, so that when it is mixed with a resin to produce a composition, it is difficult to penetrate into an extruder and there is a problem in productivity. However, the magnesium hydroxide of the component (C) of the present invention can be obtained from a natural product, so that the cost is low, and the bulk density is high, so that the extruder has good penetration and good productivity. Further, by blending the magnesium hydroxide with the resin component (A) or (A) + (B), a resin composition excellent in mechanical properties and the like can be obtained even when large particles having a particle size of 5 μm or more are used. be able to.

In the present invention, the first invention to the first invention
According to the twelfth invention in which a flame retardant auxiliary is added to the composition of the first invention, a flame-retardant resin composition having higher flame retardancy can be provided. Examples of the flame retardant aid include boron compounds such as red phosphorus, carbon black, zinc borate, zinc metaborate, and barium metaborate, zinc carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, and antimony oxide. . Of these, red phosphorus, carbon black, and boron compounds are particularly preferred. These may be used alone or in combination of two or more. The compounding amount of the flame retardant aid is in the range of 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass of the resin material. If the compounding amount is less than 0.1 part by mass, the effect of addition may be small and a sufficient flame retardant effect may not be obtained. If the compounding amount exceeds 50 parts by mass, the flame retardancy is not further improved, and the physical properties are not improved. It is not favorable both economically and economically.

In the present invention, it is desirable to use red phosphorus which is preferably coated with an organic and / or inorganic compound. Red phosphorus coated with an organic and / or inorganic compound is obtained by coating the surface of red phosphorus particles with a thermosetting resin such as an epoxy resin, a phenol resin, a polyester resin, a silicone resin, a polyamide resin, and an acrylic resin. Coated with aluminum hydroxide, zinc, magnesium, etc., and further coated with a thermosetting resin, converted to a metal phosphide and then coated with a thermosetting resin, composite hydrated oxidation of metals such as titanium, cobalt, zirconium Red phosphorus such as one coated with a substance.

The red phosphorus preferably has an average particle size of 5 to 30 μm and a particle size of 1 μm or less and 100 μm or more and a content of 5% by mass or less. In the case of a composite hydrated oxide such as a titanium-cobalt type, the total metal component such as titanium and cobalt is 0.5 to 15% by mass with respect to the total mass of the red phosphorus particles. , 0.1
-20% by mass is preferred. These modified red phosphorus are excellent in heat stability and hydrolysis resistance, and the hydrolysis reaction in the presence of water or at a high temperature is almost completely suppressed, so that odorous and toxic phosphine gas is not generated. The compounding amount of the above-mentioned red phosphorus is 0.
It is in the range of 1 to 20 parts by mass, preferably 0.2 to 15 parts by mass. If the amount of red phosphorus is less than 0.1 part by mass, the effect of addition is small and a sufficient flame retardant effect may not be obtained.
If the amount exceeds 0 parts by mass, the flame retardant effect is not further improved, which is not preferable in terms of physical properties and economy.

In the present invention, the combined use of the above composition and an inorganic filler can reduce the blending amount of the flame retardant and can impart other properties.
As inorganic fillers, calcium carbonate, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite,
Silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, mica, glass plate, sericite, pyrophyllite, aluminum flake, graphite, shirasu balloon, metal balloon, glass balloon, pumice stone,
Glass fiber, carbon fiber, whisker, metal fiber, graphite fiber, silicon carbide fiber, wollastonite and the like can be mentioned. The inorganic filler is the composition 100 of the present invention.
It is blended up to about 100 parts by mass with respect to parts by mass. If the amount exceeds 100 parts by mass, the mechanical properties such as the impact strength of the molded product are undesirably deteriorated.

In the present invention, when the (C) flame retardant or inorganic filler containing magnesium hydroxide as a main component is used, the magnesium hydroxide,
The surface of the inorganic filler, stearic acid, oleic acid, fatty acids such as palmitic acid or metal salts thereof, paraffin,
It is preferable to perform a surface treatment such as coating with wax, polyethylene wax, or a modified product thereof, organic silane, organic titanate, or the like.

The main role of each component in the composition of the present invention is considered as follows. Component (A) (an ethylene (co) polymer satisfying specific parameters) plays a role in remarkably improving mechanical properties. The component (B) (other olefin-based polymer) has flexibility and resistance without lowering the mechanical strength when a large amount of an inorganic flame retardant is blended to maintain a high degree of flame retardancy. It plays a role in enhancing impact properties. Particularly, when an ethylene / ethyl acrylate copolymer or an ethylene / vinyl acetate copolymer is used, a strong carbonized layer is formed at the time of combustion, and a high degree of flame retardancy can be imparted.

Component (C) (Specific magnesium hydroxide)
Plays a role in achieving a high degree of halogen-free flame retardancy. The functional groups in the resin components (A) and (B) enhance the coupling effect between the resin components (A) and (B) and the magnesium hydroxide of the component (C) and the compatibility of the resins with each other. It plays a role in improving strength, abrasion resistance, heat resistance, and workability, and improving drip resistance due to formation of a char (carbonized layer) during combustion. In addition, the flame retardant aid plays a role in achieving a high degree of flame retardancy.

In the present invention, mineral oils, waxes, paraffins, higher fatty acids and their esters, amides or metal salts, silicones, and partial fatty acids of polyhydric alcohols, as long as the physical properties of the flame retardant composition of the present invention are not impaired. At least one whitening inhibitor of esters or fatty acid alcohols, fatty acids, fatty acid amides, alkyl phenols or alkyl naphthol alkylene oxide adducts can be incorporated. Further, organic fillers, antioxidants, lubricants, organic or inorganic pigments, ultraviolet inhibitors, dispersants, copper damage inhibitors, neutralizers, plasticizers, nucleating agents, and the like may be added.

The flame-retardant resin composition of the present invention comprises a flame retardant 30 to 200 containing magnesium hydroxide as the main component (C) per 100 parts by mass of the resin materials (A) and (B).
By blending parts by mass and extruding at a temperature of 150 to 270 ° C., it can be manufactured with high productivity. As mentioned above, since magnesium hydroxide with a specific particle size is used, the bulk density is higher than the conventional one and the bite into the extruder is good, so the resin component and magnesium hydroxide etc. are dry blended and specially supplied It can be produced simply by feeding to the hopper of the extruder without using equipment.

Specific examples of the flame-retardant resin composition of the present invention include, for example, an ethylene / α-olefin copolymer (SP) polymerized using a single-site catalyst as the component (A).
E), linear low-density polyethylene (abbreviated as LLDPE) as component (B1), ethylene / ethyl acrylate copolymer (abbreviated as EEA) as (B2),
Ethylene-vinyl acetate copolymer (abbreviated as EVA), (B
3) As ethylene-propylene-diene copolymer (E
PDM) or ethylene-propylene copolymer rubber (abbreviated as EPM), or a polymer composition obtained by modifying these with maleic anhydride or the like to introduce a functional group, and magnesium hydroxide as the component (C). (I) (A) SPE + (C) flame retardant,
(A) SPE + (B1) LLDPE + (C) flame retardant,
(A) SPE + (B2) EEA + (C) flame retardant, (A)
SPE + (B2) EVA + (C) flame retardant, (A) SPE
+ (B1) LLDPE + (B2) EVA + (C) flame retardant, (A) SPE + (B1) LLDPE + (B2) EE
A + (C) flame retardant, (A) SPE + (B3) EPDM +
(C) Flame retardant, (A) SPE + (B1) LLDPE +
(B3) EPDM + (C) flame retardant, (A) SPE + (B
2) EEA + (B3) EPM + (C) flame retardant, (A) S
PE + (B1) LLDPE + (B2) EEA + (B3)
An unmodified composition such as EPM + (C) flame retardant or (I
I) (A ') modified SPE + (C) flame retardant, (A) SPE
+ (A ′) modified SPE + (C) flame retardant, (A ′) modified S
PE + (B2) EEA + (C) flame retardant, (A) SPE +
(A ′) modified SPE + (B2) EEA + (C) flame retardant,
(A) SPE + (B1 ′) modified LLDPE + (B2) E
EA + (C) flame retardant, (A) SPE + (B1 ') modified L
LDPE + (B2) EVA + (C) flame retardant, (A) SP
E + (B1 ′) modified LLDPE + (B1) LLDPE +
(B2) EVA + (C) flame retardant, (A) SPE + (B
1 ′) Modified LLDPE + (B3) EPDM + (C) Flame retardant, (A) SPE + (B1 ′) Modified LLDPE + (B
2) EEA + (B3) EPM + (C) flame retardant, (A) S
PE + (B1) LLDPE + (B2 ′) modified EEA +
(B3) EPDM + (C) flame retardant, (A) SPE + (B
1 ′) Modified LLDPE + (B2 ′) Modified EEA + (B
3) EPM + (C) a functional group-containing resin composition such as a flame retardant. The mixing ratio of these components is (A) component, (B)
(C) Flame retardant 30 with respect to 100 parts by mass of the resin material of the component
To 200 parts by mass, and the mixing ratio of the component (A) and the component (B) is appropriately selected depending on the purpose of use, application, and the like.

[0094]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, “parts” is “parts by mass” unless otherwise specified.

Various components used in Examples and Comparative Examples are as follows. 1) Ethylene (co) polymer (A1) (resin names A11 and A12) was polymerized by the following method. (A11) Ethylene copolymer [Preparation of solid catalyst] In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ), 75 g of indene and 75 g of methylbutylcyclohexane were added. 88 g of pentadiene was added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C.
The reaction was performed at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration 2.5 mmol /
3200 ml) and stirred for 2 hours. Next, 2000 g of silica (Grace, # 952, surface area: 300 m ² / g) previously calcined at 450 ° C. for 5 hours was added, and after stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. A solid catalyst having good properties was obtained.

[Gas Phase Polymerization] Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 65 ° C. and a total pressure of 2 MPa (20 kgf /
cm ² ) Copolymerization of ethylene and 1-hexene was performed using Gauge. The solid catalyst (i) is continuously supplied, and ethylene,
The polymerization was carried out by supplying 1-hexene and hydrogen so as to keep them at a predetermined molar ratio, to obtain an ethylene copolymer (A11). The physical properties are shown in Table 1.

(A12) Ethylene copolymer [Preparation of solid catalyst] In a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) ₄ ) and 74 g of indene were added. In addition, 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C.
Thereafter, the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., a toluene solution of methylalumoxane (concentration: 2.5 m
(mol / ml) and stirred for 2 hours.
Next, silica (manufactured by Grace, # 952, surface area 300 m ² / g) 2 previously calcined at 450 ° C. for 5 hours 2
After stirring at room temperature for 1 hour, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (filter) having good fluidity.

[Gas Phase Polymerization] Using a continuous type fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70 ° C. and a total pressure of 2 MPa (20 kgf /
cm ² ) Copolymerization of ethylene and 1-hexene was performed using Gauge. The solid catalyst (filter) is continuously supplied, and ethylene,
The polymerization was carried out by supplying 1-hexene and hydrogen so as to keep them at a predetermined molar ratio, to obtain an ethylene copolymer (A12). The physical properties are shown in Table 1.

2) The ethylene copolymer (A2) (resin name (A2)) was polymerized by the following method. [Preparation of solid catalyst] To a catalyst preparation device equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetrabutoxyzirconium (Zr (OBu) ₄ ), 40 g of indene and 21 g of methylpropylcyclopentadiene were added. While maintaining the temperature at 100 ° C., 100 g of tripropyl aluminum was added dropwise over 100 minutes, and then reacted at the same temperature for 2 hours. After cooling to 40 ° C,
Toluene solution of methylalumoxane (concentration 2.5mm
1 / ml) and stirred for 2 hours. Next, silica (manufactured by Grace, # 952, surface area: 300 m ² / g) 2000 previously calcined at 450 ° C. for 5 hours
After stirring for 1 hour at room temperature, nitrogen blowing and drying under reduced pressure were performed at 40 ° C. to obtain a solid catalyst (ha) having good fluidity.

[Gas Phase Polymerization] Using a continuous type fluidized bed gas phase polymerization apparatus, a polymerization temperature of 80 ° C. and a total pressure of 2 MPa (20 kgf /
cm ² ) Copolymerization of ethylene and 1-hexene was performed using Gauge. The solid catalyst is continuously supplied, and ethylene,
Polymerization was carried out by supplying 1-hexene and hydrogen so as to maintain a predetermined molar ratio to obtain an ethylene copolymer (A2).
The physical properties are shown in Table 1.

3) Ethylene catalyzed by a general metallocene catalyst
The hexene-1 copolymer (resin name (A3)) was polymerized by the following method. Purified toluene was placed in a pressurized reactor equipped with a stirrer replaced with nitrogen, 1-hexene was added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) was further added. After adding (Al / Zr molar ratio = 500), the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Then, ethylene was added and the total pressure was increased to 0.6 while ethylene was continuously polymerized.
Polymerization was carried out while maintaining the pressure at MPa (6 kg / cm ³ ) to produce an ethylene / hexene-1 copolymer (A3). The physical properties are shown in Table 1.

[0102]

[Table 1]

4) (A) Ethylene (co) polymer containing functional group (A1M1): Modified maleic anhydride grafted product of component (A11) [density = 0.91 g / cm ³ , MF
R = 0.8 g / 10 min, maleic anhydride reaction amount = 1.5
× 10 ^-5 mol / g, manufactured by Nippon Polyolefin Co., Ltd.]. (A1M2): Modified maleic anhydride grafted product of component (A12) [density = 0.91 g / cm ³ , MF
R = 0.9 g / 10 min, maleic anhydride reaction amount = 5.1
× 10 ^-6 mol / g, manufactured by Nippon Polyolefin Co., Ltd.]. (A1A): Modified alkenyl cyclic imino ether graft modified by component (A11) [density = 0.91 g /
cm ³ , MFR = 0.7 g / 10 min, reaction amount = 1.6 ×
^10-5 mol / g, manufactured by Nippon Polyolefin Co., Ltd.]. (A1S): Melt-processed vinyltrimethoxylane graft modified product of the component (A11) [density = 0.91 g / cm
³ , MFR = 0.8 g / 10 min, reaction amount = 1.1 × 10 ⁻⁵
mol / g, manufactured by Nippon Polyolefin Co., Ltd.].

5) (B1) Ethylene (co) polymer by ionic polymerization (B11): Linear low-density polyethylene (LLDPE) with commercially available Ziegler catalyst [density = 0.91 g / cm
³ , MFR = 1.1 g / 10 min, manufactured by Nippon Polyolefin Co., Ltd.]. Table 1 shows the physical properties of (B11). (B12): ethylene-butene-1 copolymer (VLDP
E) [Density = 0.900 g / cm ³ , MFR = 1.0 g
/ 10 minutes, manufactured by Nippon Polyolefin Co., Ltd.]. 6) (B1) Ethylene (co) polymer by ion polymerization containing functional group (B11M): Melt-modified maleic anhydride graft modified product of component (B11) [density = 0.91 g / cm ³ , MF
R = 0.8 g / 10 min, maleic anhydride reaction amount = 1.6
× 10 ^-5 mol / g, manufactured by Nippon Polyolefin Co., Ltd.]. (B11A): Modified alkenyl cyclic imino ether graft modified by melt method of component (B11) [density = 0.91 g]
/ Cm ³ , MFR = 0.7 g / 10 min, reaction amount = 1.6
× 10 ^-5 mol / g, manufactured by Nippon Polyolefin Co., Ltd.]. (B11S): Modified vinyltrimethoxysilane grafted product of the component (B11) [density = 0.91 g / c
m ³ , MFR = 0.8 g / 10 min, reaction amount = 1.3 × 1
0 ^-5 mol / g, manufactured by Japan Polyolefin Co., Ltd.].

7) (B2) Ethylene (co) polymer by high pressure radical polymerization (B21): Ethylene / ethyl acrylate copolymer (E
EA) [EA content = 10% by mass, MFR = 0.4 g / 1
0 minutes, manufactured by Nippon Polyolefin Co., Ltd.]. (B22): Ethylene / vinyl acetate copolymer (EVA)
[VA content = 10% by mass, MFR = 1.0 g / 10 min,
Nippon Polyolefin Co., Ltd.]. (B2G): ethylene-glycidyl methacrylate copolymer (EGMA) [GMA content = 1.2 × 10 ⁻³ mol /
g, MFR = 4.0 g / 10 min, manufactured by Nippon Polyolefin Co., Ltd.].

8) (B3) Rubber or elastomer (B3) Ethylene / propylene copolymer rubber (EPM)
[Propylene = 27 mass%, MFR = 0.7 g / 10 min EP07P, manufactured by Nippon Synthetic Rubber Co., Ltd.].

9) Component (C) (C-1): Magnesium hydroxide [particles having a median diameter of 3.9 μm, 41% by mass of particles having a particle diameter of 5 μm or more, natural product]. (C-2): Magnesium hydroxide [particles having a median diameter of 5.0 μm and a particle diameter of 5 μm or more 53% by mass]. (C-3): magnesium hydroxide [particles having a median diameter of 1.8 μm and a particle diameter of 5 μm or more 17% by mass].

10) Flame retardant aid Red phosphorus [Average particle size 7 μm]

The test method used in the present invention is as follows. (1) Tensile breaking strength (MPa) and elongation (%) A test piece punched out from a sheet having a thickness of 1 mm with a No. 3 dumbbell was measured at a tensile speed of 200 mm / min using Tensilon. (2) Oxygen index (OI) This was performed in accordance with JIS K7201. The oxygen index is defined as the lowest oxygen concentration required to sustain combustion, and the higher the value, the higher the flame retardancy. (3) Extrudability After the resin and magnesium hydroxide and other components are dry-blended using a Henschel mixer at a predetermined mixing ratio,
The mixture was melt-kneaded at a resin temperature of 210 ° C. using a twin screw extruder having a diameter of 30 mm to form pellets. The extruding stability at that time was evaluated, and the sample that could be extruded and sampled stably without surging (extrusion amount was not stable and severely unable to take up strands) was evaluated as good, and surging was extremely normal The sample that could not be sampled was marked as x.

In Examples 1 to 23, the compositions having the compositions shown in Tables 2 to 5 were dry-blended and then melt-kneaded at a resin temperature of 210 ° C. using a 30 mmφ twin screw extruder to form pellets. 180 ° C, pressure 10MPa (100kg / c
m ² ), a sample was prepared by press molding for 5 minutes, and subjected to a test. The test results are also shown in Tables 2 to 5.

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

[Table 4]

[0114]

[Table 5]

(Examples 1 to 5) (C-1) or (C-
2) A sample was prepared by blending 100 parts of magnesium hydroxide as a component and subjected to a test. Table 2 shows the results. The tensile strength at break and the tensile elongation at break showed sufficient values, and the oxygen index also showed high values. Extrudability was also good.

(Examples 6 and 7) (B11) was added to the component (A11).
A sample was prepared by mixing 100 parts of the magnesium hydroxide as the component (C-1) with 100 parts of the resin material containing the LLDPE as the component 1) and subjected to a test. Table 2 shows the results.
The tensile strength at break and the tensile elongation at break showed sufficient values, and the oxygen index also showed high values. Extrudability was also good.

(Example 8) (B11) was added to the component (A11).
A sample was prepared by mixing 100 parts of the magnesium hydroxide of the component (C-1) with 100 parts of the resin material containing the LLDPE of the component and the VLDPE of the component (B12), and subjected to a test. Table 2 shows the results. Tensile breaking strength and tensile breaking elongation showed sufficient values. Further, the oxygen index also showed a high value, and the extrudability was good.

(Example 9) (B21) was added to the component (A12).
With respect to 100 parts of the resin material containing EEA as the component, (C-
1) A sample containing 100 parts of magnesium hydroxide as a component was prepared and subjected to a test. Table 2 shows the results. Tensile breaking strength and tensile breaking elongation showed sufficient values. The oxygen index also showed a sufficiently high value due to the effect of char formation by the oxygen-containing copolymer. Extrudability was also good.

(Examples 10 to 11) A component (A1M1) obtained by graft-modifying the component (A11) with maleic anhydride,
EEA of component (B21) or EVA of component (B22)
A sample in which 100 parts of the magnesium hydroxide of the component (C-1) was blended with 100 parts of the resin material blended with was prepared and subjected to a test. Table 3 shows the results. The oxygen index showed a remarkable improvement as well as the char forming effect of EEA and EVA, which are oxygen-containing copolymers, and further stronger char formation due to the coupling force of the introduced functional group with the inorganic flame retardant. Extrudability was also good.

(Examples 12 to 14) The component (A11) was modified with the maleic anhydride graft to the component (A12).
The component (A1M2) obtained by graft-modifying the component (A1) or the component (A12) with maleic anhydride, or the component (B1)
1) Component was graft-modified with maleic anhydride (B11)
A sample was prepared by mixing 100 parts of the magnesium hydroxide of the component (C-1) with 100 parts of the resin material containing the EEA of the component (M) and the component (B21) and subjected to a test. Table 3 shows the results. A remarkable improvement in tensile breaking strength was observed by blending the component (A). Further, the oxygen index was found to have a char-forming effect of EEA, which is an oxygen-containing copolymer, and a stronger char was formed by the coupling force of the introduced functional group with the inorganic flame retardant, so that the oxygen index was significantly improved. Extrudability was also good.

(Examples 15 and 16) The (C12) component was blended with maleic anhydride-grafted component (B11M) and LEEPE (B11M) and EEA as the component (B21). -2) A sample containing 70 parts of magnesium hydroxide as a component or 5 parts of red phosphorus was further prepared and subjected to a test. Table 4 shows the results. A remarkable improvement in tensile breaking strength was observed by blending the component (A). In addition, the oxygen index is E
In addition to the char forming effect of EA, a stronger char was formed due to the coupling force of the introduced functional group with the inorganic flame retardant, and a remarkable improvement in the oxygen index was observed. Extrudability was also good.

(Example 17) (B12) was added to the component (A12).
A sample in which 120 parts of (C-1) magnesium hydroxide was blended with 100 parts of a resin material in which (B11M) component and (B21) component EEA were blended with maleic anhydride graft-modified LLDPE of 1) component. It was prepared and subjected to a test. Table 4 shows the results. A remarkable improvement in tensile breaking strength was observed by blending the component (A). Further, the oxygen index was found to have a char-forming effect of EEA, which is an oxygen-containing copolymer, and a stronger char was formed by the coupling force of the introduced functional group with the inorganic flame retardant, so that the oxygen index was significantly improved. Extrudability was also good.

(Example 18) (B12) was added to the component (A12).
Component (B11M) is obtained by subjecting LLDPE of component 1) to maleic anhydride graft modification, EEA of component (B21),
3) A sample was prepared by mixing 100 parts of the magnesium hydroxide of the component (C-1) with 100 parts of the resin material mixed with the EPM of the component, and subjected to a test. Table 4 shows the results.
A remarkable improvement in tensile breaking strength was observed by blending the component (A). Further, the oxygen index is EEA which is an oxygen-containing copolymer.
In addition to the char forming effect of the above, a stronger char was formed due to the coupling force of the introduced functional group with the inorganic flame retardant, and a remarkable improvement in the oxygen index was observed. Extrudability was also good.

(Examples 19 and 20) The component (A11)
Resin material 100 containing component (A1A) obtained by graft-modifying component (A11) with alkenyl cyclic imino ether or component (A1S) obtained by modifying vinyltrimethoxysilane.
Parts of magnesium hydroxide (C-1) per 100 parts
A sample in which the components were mixed was prepared and subjected to a test. Table 5 shows the results. A remarkable improvement in tensile breaking strength was observed due to the effect of coupling the component (A) and the inorganic flame retardant by the introduced functional group. In addition, a char was formed by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved. Extrudability was also good.

(Examples 21 to 22) The component (A11)
100 parts of a resin material containing the (B11A) component obtained by modifying the LLDPE component of the (B11) with the alkenyl cyclic imino ether graft-modified (B11A) component or the (B11S) component modified by vinyltrimethoxysilane, was added with 100 parts of magnesium hydroxide as the (C-1) component. A sample in which the components were mixed was prepared and subjected to a test. Table 5 shows the results. A remarkable improvement in tensile breaking strength was observed due to the effect of coupling the component (A) and the inorganic flame retardant by the introduced functional group. In addition, a char was formed by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved. Extrudability was also good.

(Example 23) Ethylene and glycidyl methacrylate were randomly copolymerized with the component (A11) (B2
A sample was prepared by mixing 100 parts of the magnesium hydroxide of the component (C-1) with 100 parts of the resin material mixed with the EGMA of the component G) and subjected to a test. Table 5 shows the results.
A remarkable improvement in tensile breaking strength was observed due to the effect of coupling the component (A) and the inorganic flame retardant by the introduced functional group. In addition, a char was formed by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved. Extrudability was also good.

In Comparative Examples 1 to 6, the compositions having the compositions shown in Table 6 were used in the same manner as in Examples. Table 6 shows the mixing ratio and the results.

[0128]

[Table 6]

(Comparative Examples 1 to 3) Without using the component (A),
Table 6 shows a mixture of the component (B) and the magnesium hydroxide of the component (C-1). As a result, the tensile strength at break or elongation was (remarkably) lower than in the examples.

(Comparative Example 4) (A1)
2) Component was modified with maleic anhydride graft (A1M
2) One part of the component was added, and the amount of the component (A) in the resin component was outside the scope of the claims. Table 6 shows the results. Tensile strength at break and elongation were (remarkably) lower than those of the examples.

(Comparative Examples 5 to 6) The procedure was carried out in the same manner as in Example 1 or Example 12, except that the component (C-3) magnesium hydroxide having a small particle median diameter was used. Table 6 shows the results. Surging was severe, extrusion was not stable, and a normal sample could not be collected.

[0132]

According to the present invention, an ethylene (co) polymer, an olefin polymer and a resin component containing a specific amount of a specific functional group satisfying a specific parameter range, and a magnesium hydroxide having a specific particle size are contained as main components. It is a flame-retardant resin composition consisting of a flame retardant that is flexible, has high flame retardancy, mechanical properties, and maintains low pollution such as no generation of harmful gas such as halogen gas during combustion, Cost reduction and productivity have been improved. In particular, the component (A) is an ethylene (co) polymer having a narrow molecular weight distribution, a moderately wide composition distribution, and a high degree of branching and low molecular weight components.
It contributes to remarkable improvement in mechanical strength. In particular, specific functional groups play a role in coupling the resin component with the inorganic flame retardant or inorganic filler, increasing the compatibility between the resins, and improving the mechanical strength, workability, wear resistance, etc. I do. During combustion, it also contributes to the formation of char (carbonized layer), prevents dripping of the resin, and has a role of self-digestion. In particular, magnesium hydroxide as the component (C) can be obtained at low cost using brucite ore, which is naturally produced, as a raw material, and has a higher bulk density than conventional ones, so that it can easily penetrate into an extruder. Excellent.
As described above, the resin composition of the present invention has high flame retardancy, does not generate toxic gases such as halogen gas during combustion, has excellent abrasion resistance and heat resistance, and has safety, flexibility, Excellent in mechanical properties, chemical resistance, electrical properties, etc., it is used for molding applications such as extruded products such as films, sheets, pipes and injection molded products, and for electric wires and cables, etc. It can be used in various fields such as electricity, electronics, automobiles, ships, aircraft, architecture, civil engineering, and the like.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of (Equation 1) using a graph showing a relationship between an elution temperature and an elution amount by TREF of an ethylene (co) polymer (A) in the present invention.

FIG. 2 is an ethylene (co) polymer (A1) of the present invention.
6 is a graph showing the relationship between the elution temperature and the amount of elution by TREF in (A2).

FIG. 3 is a graph showing the relationship between the elution temperature and the elution amount of an ethylene copolymer by TREF using a general metallocene catalyst.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 21/00 C08L 21/00 23/02 23/02 23/26 23/26 H01B 3/28 H01B 3 / 28 3/44 3/44 FP (72) Inventor Hideo Kawabata 2-3-2 Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture F-term in the Research and Development Center, Technology Headquarters, Japan Polyolefin Co., Ltd. 4J002 AC01X AC03X AC06X AC06X AC07X BB03X BB04W BB04X BB06X BB07X BB15W BB15X BB18X BG07W BH00W BP01X BQ00X CD19W DA037 DA057 DE076 DK007 FA086 FD136 FD137 5G305 AA14 AB15 AB17 AB25 AB35 BA15 BA26 CA01 CC47 CA51 CC

Claims (14)

[Claims] 1. A resin material containing (A) 2% by mass or more of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 98% by mass or less of another olefin polymer. 10
(C) Flame retardant containing magnesium hydroxide as a main component and containing 30% by mass or more of particles (C) having a particle median diameter of 3 μm or more and a particle diameter of 5 μm or more with respect to 0 parts by mass.
A flame retardant resin composition containing 0 parts by mass: (a) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 min,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) The temperature T ₂₅ (° C.) at which 25% of the whole is eluted and the temperature T at which 75% of the whole are eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF).
Difference from ₇₅ (° C.) T ₇₅ -T ₂₅ and density d (g / cm ³ )
Satisfy the following relationship (Equation 1). (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 2. The flame retardant according to claim 1, wherein the other olefin polymer (B) is at least one olefin polymer selected from the following (B1) to (B3). Resin composition: (B1) an ethylene (co) polymer obtained by ionic polymerization;
2) Ethylene (co) polymer by high pressure radical polymerization, (B3) rubber or elastomer. 3. At least a part of the resin component (A), (B) or (A) + (B) is as follows:
The flame retardant according to claim 1, wherein the resin contains at least one functional group selected from the group consisting of 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per 1 g of the resin material. Resin composition: (A) carboxylic acid group or carboxylic anhydride group, (A)
Epoxy group, (c) hydroxyl group, (d) amino group,
(E) alkenyl cyclic imino ether group, (f) silyl group. 4. The resin component (A) in an amount of 3 to 50% by mass,
(B1) + (B2) 97 to 50% by mass, (A)
(B1) + (B2) or (A) + (B1) + (B2)
At least a part of (a) a carboxylic acid group or a carboxylic anhydride group per 1 g of the resin material, from 1 × 10 ^{−7 to} 5 × 10
The flame-retardant resin composition according to any one of claims 1 to 3, which contains ^-4 mol. 5. The resin component (A) having a density of 0.8
6 to 0.94 g / cm ³ , MFR 0.5 to 10 g / 1
0 to 3 to 50% by mass of an ethylene (co) polymer, and (B
1) 1 to 20% by mass of an ethylene (α) -olefin copolymer having a density of 0.86 to 0.97 g / cm ^{3 and} a maleic anhydride graft-modified ethylene (co) polymer as a component
And 50 to 96% by mass of an ethylene / ethyl acrylate copolymer or an ethylene / vinyl acetate copolymer as the component (B2) (provided that (A) + (B1) + (B
The sum of 2) is 100% by mass. The flame-retardant resin composition according to any one of claims 1 to 4, wherein 6. The flame-retardant resin composition according to claim 1, wherein the ethylene (co) polymer (A) further satisfies the following requirement (e): (E) The temperature T ₂₅ (° C.) at which 25% of the whole is eluted and the temperature T at which 75% of the whole are eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF)
Difference from ₇₅ (° C.) T ₇₅ −T ₂₅ and density d (g / cm ³ )
Satisfy the relationship of the following (Equation 2). (Equation 2) When d <0.950 g / cm ³ , T ₇₅ −T ₂₅ ≧ −300 × d + 285 When d ≧ 0.950 g / cm ³ , T ₇₅ −T ₂₅ ≧ 0 7. The ethylene (co) polymer (A1), wherein the ethylene (co) polymer (A) further satisfies the following requirements (f) and (g):
(F) orthodichlorobenzene (ODC) at 25 ° C.
B) The soluble content X (% by mass), the density d (g / cm ³ ) and the melt flow rate (MFR) (g / 10 minutes) satisfy the following relationship: (Formula 3) d-0.008 log MFR If ≧ 0.93, X <2.0 (Equation 4) d−0.008 log If MFR <0.93, X <9.8 × 10 ³ × (0.9300−d + 0.008l)
(ogMFR) ² +2.0 (g) A plurality of peaks in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). 8. The ethylene (co) polymer (A2), wherein the ethylene (co) polymer (A) further satisfies the following requirements (h) and (i).
The flame-retardant resin composition according to any one of (1) to (6): (h) a single peak of an elution temperature-elution amount curve by continuous temperature-elution fractionation (TREF), and (i) a melting point peak of 1 Having two or more and having the highest melting point T _m1
(° C.) and the density d (g / cm ³ ) should satisfy the relationship of the following (Equation 5). (Equation 5) T _m1 ≧ 150 × d−17 9. The ethylene (co) polymer (A2)
The flame-retardant resin composition according to claim 8, further satisfying the following requirement (j): (j) melt tension (MT) (g) and melt flow rate (MFR) (g / 10 minutes). ) Satisfy the following relationship (Equation 6). (Formula 6) logMT ≦ −0.572 × logMFR +
0.3 10. The ethylene (co) polymer (A),
The method according to any one of claims 1 to 9, wherein the compound is produced in the presence of a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. Flame retardant resin composition. 11. The method according to claim 1, wherein the magnesium hydroxide (C) is a natural product.
The flame-retardant resin composition according to any one of the above. 12. The flame-retardant resin composition according to claim 1, further comprising 0.1 to 50 parts by mass of a flame retardant aid per 100 parts by mass of the resin material. 13. The flame-retardant resin composition according to claim 12, wherein the flame-retardant auxiliary is at least one selected from red phosphorus, carbon black, and a boron compound. 14. A resin material containing (A) 2% by mass or more of an ethylene (co) polymer satisfying the following requirements (a) to (d) and (B) 98% by mass or less of another olefin polymer. 1
(C) The particle median diameter is 3 μm with respect to 00 parts by mass.
The flame retardant containing magnesium hydroxide as a main component containing 30% by mass or more of particles having a particle size of 5 μm or more
200 parts by mass are blended and molding temperature is 150-270 ° C
A method for producing a flame-retardant resin composition formed by extrusion molding at (a) a density of 0.86 to 0.97 g / cm ³ , (b) a melt flow rate of 0.01 to 100 g / 10 minutes,
(C) a molecular weight distribution (Mw / Mn) of 1.5 to 4.5;
(D) The temperature T ₂₅ (° C.) at which 25% of the whole is eluted and the temperature T at which 75% of the whole are eluted, obtained from the integrated elution curve of the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF).
Difference from ₇₅ (° C.) T ₇₅ −T ₂₅ and density d (g / cm ³ )
Satisfies the following relationship (Equation 1). (Equation 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644