JP3364388B2 - Flame retardant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a refractory resin composition containing an inorganic flame retardant. More specifically,
Homopolymer of ethylene having a narrow molecular weight distribution and a moderately wide composition distribution, or ethylene and α- having 3 to 20 carbon atoms
Copolymer with olefin (in the present specification, these homopolymers or copolymers are collectively referred to as ethylene (co))
It is called a polymer. ) And an inorganic phosphorus-free flame retardant or an inorganic phosphorus-free flame retardant and red phosphorus, or a composition containing an olefin polymer or an olefin polymer into which a functional group has been introduced, in addition to these, Have, heat resistance,
The present invention relates to a difficult resin composition which has excellent mechanical properties and does not generate harmful gas such as halogen gas during combustion.

[0002]

2. Description of the Related Art Polyolefin resins are excellent in physical properties and chemical properties, and films, sheets, pipes, containers, and coated electric wires (hereinafter simply referred to as electric wires) can be formed by various molding methods such as extrusion molding and injection molding. It is the most popular general-purpose resin that is molded into cables, etc. and is used for many purposes for household and industrial purposes. However, since polyolefin resins are easily flammable, various methods for making them flame-retardant have hitherto been proposed. The most common method is to add flame retardant to a polyolefin resin by adding an organic flame retardant such as halogen or phosphorus.

However, although these organic flame retardants are effective with a small blending amount, they have the drawback of generating harmful halogen gas during combustion. Therefore, recently, various methods of adding a hydrate of an inorganic metal compound such as aluminum hydroxide or magnesium hydroxide as a flame-retardant of pollution-free type, which emits no harmful gas during combustion, has a low smoke emission property, and has been studied. (Japanese Patent Laid-Open Nos. 2-53845 and 2-145632). However, in a flame-retardant resin composition using an inorganic flame retardant, it is necessary to fill a large amount of the inorganic flame retardant in order to enhance the flame retardancy. However, increasing the filling amount has practical difficulties such as deterioration in mechanical strength, flexibility, and processability.To improve this, a soft polyolefin resin is blended at a high concentration to receive an inorganic flame retardant. Techniques for increasing the capacity have also been disclosed (US Pat. No. 4722959, US Pat. No. 4845146).

However, the flame-retardant resin composition containing a large amount of such soft resin has been successful in general electric materials such as electric wires, cables, protective tubes, joint covers, and interior materials such as sheets and floor materials. However, when manufacturing molded products such as electric wires, cables or cabinets and boxes for automobiles, vehicles, aircraft, ships, industrial robots, etc., the harshness experienced during manufacturing work, transportation and use, etc. Due to high temperature, low temperature, vibration, etc., they are easily damaged by external damage, and improvements in mechanical strength, wear resistance, etc. have been demanded.

[0005]

Therefore, an object of the present invention is to provide a resin composition used for molding applications such as films, sheets, containers, electric wires, cables, backings, sealants, hoses, and injection molded products. Therefore, the flame-retardant resin composition retains mechanical strength, flexibility, processability, and high flame retardancy, and has well-balanced physical properties with improved heat resistance, mechanical properties, and wear resistance. To provide things.

[0006]

The first invention of the present application is (A) with respect to 100 parts by weight of a resin component composed of an ethylene (co) polymer satisfying the following conditions (a) to (f): (B) A flame-retardant resin composition comprising 30 to 200 parts by weight of an inorganic phosphorus-free flame retardant: (a) Density (d) 0.86 to 0.97 g / cm ³ , (b) Melt flow Rate (MFR) 0.01-200g /
10 minutes, (c) molecular weight distribution (Mw / Mn) 1.5 to 4.5, (d) composition distribution parameter (Cb) 1.08 to 2.0, (e) ortho-dichlorobenzene (ODC) at 25 ° C.
B) The relationship between the amount (X) (wt%) of the soluble component and the density (d) and the melt flow rate (MFR) is (1) d-0.00.
In the case of 8 × log MFR ≧ 0.93, X <2.0,
(2) When d−0.008 × logMFR <0.93, X
<9.8 x 10 ³ x (0.9300-d + 0.008 x logMFR) ² +
The relationship of 2.0 is satisfied. (F) There are a plurality of peaks on the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF).

The second invention of the present application is, as a resin component, 2% by weight or more of an ethylene (co) polymer satisfying the conditions (A) to (F) of (A) described in the first invention. When,
(A ') 100 parts by weight of a resin component containing less than 98% by weight of at least one olefin polymer selected from the following (A'1) to (A'3), and (B) an inorganic phosphorus-free system A flame-retardant resin composition comprising 30 to 200 parts by weight of a flame retardant: (A'1) Different from ethylene (co) polymers satisfying the above conditions (a) to (f). Ethylene / α-olefin copolymer, (A′2) ethylene copolymer by high pressure radical polymerization method, (A′3) rubber.

In a third invention of the present application, at least a part of the resin components (A), (A ') or (A) + (A') is at least selected from the following (a) to (f). One type of functional group is added from 10 ^{-7 to} 5 × 10 per 1 g of the resin component.
^-4 mol is contained in the flame-retardant resin composition according to the first or second invention: (a) carboxylic acid group or carboxylic acid anhydride group, (b)
Epoxy group, (c) hydroxyl group, (d) amino group,
(E) Alkenyl cyclic imino ether group, (f) silane group.

Further, the fourth invention of the present application is the above (A).
In the presence of a catalyst whose component ethylene (co) polymer has at least a conjugated double bond and a transition metal compound of Group IV of the periodic table, homopolymerize ethylene, or ethylene and carbon number The flame-retardant resin composition according to any one of the first to third inventions, which is an ethylene copolymer obtained by copolymerizing 3 to 20 α-olefins. Further, the fifth invention of the present application is the flame retardant resin composition according to any one of the first to fourth inventions, which further contains 0.1 to 20 parts by weight of red phosphorus as 100 parts by weight of the resin component as a flame retardant. Is.

The present invention will be described in detail below. The ethylene (co) polymer (A) in the present invention is an ethylene homopolymer and a copolymer of ethylene and one or more kinds selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably 3 to 1
2, specifically, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. In addition, the content of these α-olefins is usually 3 in total.
It is desirable to select 0 mol% or less, preferably 3 to 20 mol%.

The density of the ethylene (co) polymer (A) of the present invention is 0.86 to 0.97 g / cm ³ , preferably 0.88 to 0.945.
g / cm ^3, more preferably from 0.90~0.93g / cm ^3.

The ethylene (co) polymer (A) of the present invention has a melt flow rate (MFR) of 0.01 to 200 g / 10.
Min, preferably 0.1 to 100 g / 10 min, more preferably 0.2 to 50 g / 10 min. If the MFR is less than 0.01 g / 10 minutes, the moldability will be poor, and if it is 200 g / 10 minutes or more, the mechanical strength such as impact resistance will decrease.

The method for calculating the molecular weight distribution (Mw / Mn) of the ethylene (co) polymer (A) of the present invention is to measure the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). ), The ratio M
This is for determining w / Mn. Ethylene of the present invention (co)
The Mw / Mn of the polymer is 1.5 to 4.5, preferably 1.8 to 3.
5, more preferably 2-3. Mw / Mn is 1.5
If it is less than 4, the moldability is poor, and if it is 4.5 or more, the impact resistance is poor.

The composition distribution parameter (Cb) of the ethylene (co) polymer of the present invention is 1.08 to 2.00, preferably 1.12 to 1.70, and more preferably 1.15 to 1.50. When it is 2.00 or more, the strength of the molded product decreases.

The method for measuring the composition distribution parameter (Cb) of the ethylene (co) polymer of the present invention is as follows. A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved at 135 ° C. in ortho-dichlorobenzene (hereinafter abbreviated as ODCB) so that the sample concentration becomes 0.2% by weight. This heated solution
The sample is transferred to a column packed with diatomaceous earth (Celite 545), filled and cooled to 25 ° C. at 0.1 ° C./minute to deposit a sample on the surface of Celite. Next, while flowing ODCB at a constant flow rate through this column, the column temperature was increased by 12 in increments of 5 ° C.
While gradually raising the temperature to 0 ° C., a solution in which the sample is dissolved is collected at each temperature. After cooling this solution, the sample is reprecipitated with methanol, filtered and dried to obtain a sample at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of this separated sample are measured. The degree of branching is determined by ¹³ C-NMR.

With respect to each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the method of least squares,
Create a calibration curve. The correlation coefficient of this approximation is sufficiently large.
The value obtained from this calibration curve is the branching degree of each fraction. This correction is not performed for the fractions collected at an elution temperature of 95 ° C or higher, because the elution temperature and the degree of branching do not always have a linear relationship.

Next, the weight fraction w of each fraction
_i is the change amount (b _i of the branching degree b _i per elution temperature 5 ° C. ₎
-B _i-1 ) to obtain the relative concentration c _i and plot the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided with a constant width, and the composition distribution parameter (Cb) is calculated from the following equation. Cb = (Σc _j b _j ² / Σc _j b _j ) × (Σc _j / Σc
_j b _j ) Here, c _j and b _j are the relative density and the degree of branching of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and increases as the composition distribution spreads.

Many proposals have been made for the method of describing the composition distribution of the ethylene copolymer. For example, in JP-A-60-88016, numerical processing is performed assuming that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each separated sample obtained by separating the sample with a solvent. The ratio of the weight average branching degree (Cw) to the number average branching degree (Cn) is obtained. This approximation calculation becomes less accurate when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and the L
When measuring LDPE, the correlation coefficient is quite low,
The value is not accurate enough. This Cw / Cn and Cb of the present invention
Is different in definition and measurement method.

In the ethylene (co) polymer of the present invention, 2
The amount X of the ODCB-soluble component at 5 ° C. is ethylene (co).
It shows the proportion of the high branching component and the low molecular weight component contained in the polymer, and it is desirable that the proportion is small because it causes the deterioration of heat resistance and the stickiness of the surface of the molded article. ODCB
The amount of soluble components is influenced by the content and average molecular weight of α-olefin in the whole copolymer, that is, the density (d) and the melt flow rate (MFR). Therefore, the ODCB
The amount X (% by weight) of the soluble component has a relationship between d and MFR, d-
When 0.008 × logMFR ≧ 0.93 is satisfied, it is less than 2% by weight, preferably less than 1% by weight, and more preferably less than 0.5% by weight.

The relationship between d and MFR is d-0.008 ×
When logMFR <0.93 is satisfied, X <9.8 × 10 ³ ×
(0.9300-d + 0.008 × logMFR) ² + 2.0, preferably X <7.4 × 10 ³ × (0.9300-d
+ 0.008 x log MFR) ² + 1.0, more preferably X <5.6 x 10 ³ x (0.9300-d + 0.008 x log MF)
R) ² +0.5. The fact that the density, the MFR and the amount of the ODCB-soluble component satisfy the above-mentioned relations indicate that the α-olefin contained in the entire copolymer is not ubiquitous, and the characteristic that the mechanical strength is strong. Have.

The ODCB-soluble component X at 25 ° C. is measured by the following method. That is, the sample
0.5 g is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C.
After leaving this solution at 25 ° C. overnight, it is filtered with a Teflon filter to collect the filtrate. Infrared spectroscopic analysis was performed on the filtrate, which is a sample solution, and the wave number of the asymmetric stretching vibration of methylene was 2925 cm.
Measure the absorption peak intensity near ^-1 and calculate the sample concentration in the filtrate from the calibration curve prepared in advance. From this value, the ODCB-soluble component at 25 ° C. is determined.

The ethylene (co) polymer of the present invention preferably has a plurality of peaks in the elution temperature-elution amount curve determined by the continuous temperature rising elution fractionation method (TREF).
Further, it is particularly preferable that the peak on the high temperature side exists between 85 ° C and 100 ° C. The presence of this peak raises the melting point, raises the crystallinity, and improves the heat resistance and rigidity of the molded body. The elution temperature-elution amount curve of the copolymer of the present invention is as shown in FIG. 1, which is clearly different from the elution temperature-elution amount curve of the so-called metallocene-catalyzed copolymer.

The TREF measuring method according to the present invention is as follows. A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved in ODCB at 135 ° C. so that the sample concentration becomes 0.05% by weight.
After pouring 5 ml of this heated solution into a column filled with glass beads, it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit a sample on the surface of the glass beads. Next, while flowing ODCB at a constant flow rate through this column, the column temperature is raised at a constant rate of 50 ° C./hour to sequentially elute the sample soluble in the solution at each temperature. At this time, the sample concentration in the solvent was the wave number of the asymmetric stretching vibration of methylene, which was 2925 cm.
^The absorption for ^-1 is obtained by continuously detecting the absorption with an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained. Since the TREF analysis can analyze the change in the elution rate with respect to the temperature change continuously with a very small amount of sample, it is possible to detect relatively fine peaks that cannot be detected by the fractionation method.

The ethylene (co) polymer preferably used in the present invention is not particularly limited as long as it satisfies the above conditions (a) to (v), but its production method is an organic compound having at least a conjugated double bond. In the presence of a catalyst containing a cyclic compound and a transition metal compound of Group IV of the periodic table, ethylene is homopolymerized or ethylene and α having 3 to 20 carbon atoms are used.
-The method of copolymerizing olefins is preferred. The above catalyst comprises the following (1) transition metal compound of Group IV of the periodic table and (3)
It is desirable to polymerize with a catalyst obtained by bringing the following catalyst components (2) and (4) into contact with an organic cyclic compound having a conjugated double bond.

That is, (1) General formula (I) Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹ _4-pqr (I) (wherein, Me ¹ is a transition metal of Group IV of the periodic table) Indicates R
¹ and R ^{3 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms, and R ² is a 2,4-pentanedionato ligand or a derivative thereof, a dibenzoylmethanato ligand, a benzoylacetonato ligand. X ¹ represents a halogen atom, p, q and r each represent 0 ≦ p ≦ 4,
A compound represented by 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4),

(2) General formula (II) Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn (II) (wherein Me ² represents an element of groups I to III of the periodic table, and R
⁴ and R ⁵ are each a hydrocarbon group having 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 the group III element of the periodic table), z represents the valence of Me ² , and m and n are It is an integer satisfying the ranges of 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z, respectively. ), An organic cyclic compound having a conjugated double bond (3), and (4) Al-
It is a catalyst obtained by bringing a modified organoaluminum oxy compound containing an O—Al bond and / or a boron compound into contact with each other.

Me ^{1 in} the formula of the compound represented by the general formula (I) of the catalyst component (1) represents zirconium, titanium or hafnium. The type of these transition metals is not limited, and a plurality thereof may be used, but it is particularly preferable that zirconium is contained because the copolymer obtained has excellent weather resistance.

R ¹ and R ³ each have 1 to 24 carbon atoms
A hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group; a vinyl group or an allyl group. Alkenyl groups such as groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryl groups, phenylbutyl groups, neofoyl groups, etc. And the aralkyl group of. These may have branches.

R ² is a 2,4-pentanedionato ligand or a derivative thereof, and a dibenzoylmethanato ligand,
Derivatives such as benzoylacetonato ligands are shown. X ¹
Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are 0 ≦ p ≦ 4 and 0 ≦ q, respectively.
The ranges are ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4.

Examples of the compound represented by the general formula (I) of the catalyst component (1) include tetramethylzirconium,
Examples thereof include tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium, dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium.

Specific examples of the 2,4-pentanedionato ligand or its derivative include tetra (2,4-
Pentandionato) zirconium, tri (2,4-pentanedionato) chloride zirconium, di (2,4-)
Pentandionato) diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di n
-Butoxide zirconium, di (2,4-pentanedionato) dibenzylzirconium, di (2,4-pentanedionato) dineofoilzirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) die Toxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium,
Di (benzoylacetonato) dietoxide zirconium, di (benzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n-
Butoxide zirconium etc. are mentioned. These are 2
It may be used as a mixture of two or more species.

Me ^{2 in} the formula of the compound represented by the general formula (II) of the catalyst component (2) represents a group I to III element of the periodic table, and specific examples thereof include lithium, sodium,
Potassium, magnesium, calcium, zinc, boron,
Such as aluminum. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, Alkyl group such as butyl group; Alkenyl group such as vinyl group and allyl group;
Aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group,
Examples thereof include aralkyl groups such as a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group and a neophyl group. These may have branches.

X ² represents a halogen atom such as fluorine, iodine, chlorine and bromine 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 exemplified by boron, aluminum and the like. Further, z represents the valence of Me ² , m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z.

Examples of the compound represented by the general formula (II) of the catalyst component (2) include organolithium compounds such as methyllithium and ethyllithium; dimethylmagnesium, diethylmagnesium, methylmagnesium chloride, ethylmagnesium chloride and the like. Organomagnesium compound; Organozinc compounds such as dimethylzinc and diethylzinc; Organoboron compounds such as trimethylboron and triethylboron; Trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum Chloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl al Derivatives of organoaluminum compounds such as benzalkonium hydride and the like.

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

The above-mentioned suitable compounds include cyclopentadiene, indene, azulene or their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Moreover, the compound which these compounds couple | bonded (bridge | crosslink) through the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula (III). A _L SiR ⁶ _4-L (III) Here, A represents the cyclohydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R ⁶ is a methyl group. , Alkyl groups such as ethyl group, propyl group, isopropyl group and butyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl groups such as phenyl group; aryloxy groups such as phenoxy group; benzyl group Represented by an aralkyl group such as, and represents a hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 and L is 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the above component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene and 4-methyl-1.
-C5-24 cyclopolyene or substituted cyclopolyene, such as indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadiene Examples thereof include enylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al--O--Al bond, which is obtained by reacting the organoaluminum compound of the catalyst component (4) with water, is usually obtained by reacting an alkylaluminum compound with water. It is a modified organoaluminum oxy compound called aluminoxane and usually contains 1 to 100, preferably 1 to 50, Al-O-Al bonds in the molecule.
The modified organoaluminum oxy compound may be linear or cyclic.

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

As the boron compound of the catalyst component (4),
For example, triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, butylammonium tetra (pentafluorophenyl) borate, N,
Examples thereof include N-dimethylanilinium tetra (pentafluorophenyl) borate and N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate.

In the present invention, the catalyst components (1) to
The catalyst obtained by bringing (4) into contact with each other,
It can also be used in the polymerization reaction by supporting it on an inorganic carrier and / or a particulate polymer carrier (5). Ingredient (5)
The inorganic carrier of, in the step of preparing the catalyst of the present invention, may be in any shape such as powder, granular, flakes, foil, and fibrous, as long as it retains the original shape, Regardless of the shape, the maximum length is usually 5 to 200 μm, preferably 10 to 100 μm. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² /
g, the pore volume is in the range of 0.05 to ³ cm ³ / g. As the inorganic carrier, a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof can be used, and these are usually in the air at 200 to 900 ° C. or an inert gas such as nitrogen or argon. Used by firing in.

Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Further, examples of the metal oxide include single oxides or complex oxides of Group I to VIII of the periodic table, and specifically, S
iO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , Ti
_{O 2, ZrO 2, Fe 2} O 3, SiO 2 -Al 2 O 3,
_{Al 2 O 3 -MgO, Al 2} O 3 -CaO, Al 2 O 3
_{-MgO-CaO, Al 2 O 3} -MgO-SiO 2, A
_{l 2 O 3 -CuO, Al 2} O 3 -Fe 2 O 3, Al 2 O
₃ -NiO, such as SiO ₂ -MgO and the like. The above formula represented by oxides is not a molecular formula, but only a composition. That is, the structure and the component ratio of the composite oxide used in the present invention are not particularly limited. The metal oxide used in the present invention is
It does not matter if it adsorbs a small amount of water, or if it contains a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably a carbonate of an alkali metal or an alkaline earth metal, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate. Examples of the carbonaceous substance include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but the use of metal oxides such as silica and alumina is particularly preferable.

On the other hand, as the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance during catalyst preparation and polymerization reaction,
From low molecular weight to ultra high molecular weight can be arbitrarily used.

Specifically, it is preferably an olefin having 2 to 12 carbon atoms, which is represented by a particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly-1-butene, and the like. Examples thereof include various types of polyolefins, polyesters, polyamides, polyvinyl chloride, poly (meth) acrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof obtained.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organoaluminum compound or a modified organoaluminum oxy compound containing an Al--O--Al bond. The fifth component (5) after contact treatment with
Can also be used as

The method for producing the (A) ethylene (co) polymer of the present invention is produced by a vapor phase method, a slurry method, a solution method or the like,
The one-step polymerization method and the multi-step polymerization method are not particularly limited.

The (A ') olefin polymer component in the present invention means an ethylene (A) different from the ethylene (co) polymer (A) satisfying the conditions (A'1) to (F) above. It is at least one olefin polymer or rubber selected from α-olefin copolymer, (A′2) ethylene copolymer by high pressure radical method, and (A′3) rubber.

An ethylene / α different from the ethylene (co) polymer satisfying the above conditions (A) to (F) of (A′1)
-Olefin copolymer is ethylene and an α-olefin copolymer having 3 to 12 carbon atoms and having a density of 0.86 to 0.94 g / cm 3 by a medium and low pressure method using a Ziegler catalyst, a Phillips catalyst or the like and other known methods. ³ ethylene
It is an α-olefin copolymer (that is, very low density polyethylene (VLDPE) and linear low density polyethylene (LLDPE)).

As specific α-olefins, α-olefins having 3 to 12 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-
Examples include octene and 1-dodecene. Of these, preferred are 1-butene and 4-methyl-1-
Pentene, 1-hexene and 1-octene, and particularly preferred is 1-butene. The content of α-olefin in the ethylene / α-olefin copolymer is 5 to 40 mol%.
Is preferred.

Examples of the ethylene-based copolymer of the component (A'2) obtained by the high-pressure radical polymerization method include branched low-density polyethylene (LDPE), ethylene and α, β-unsaturated carboxylic acid alkyl esters and their derivatives, and vinyl. Examples thereof include copolymers with a carboxyl group-containing monomer such as ester.

Examples of the copolymer with the above-mentioned ethylene / α, β-unsaturated carboxylic acid alkyl ester and its derivative include α, β-unsaturated carboxylic acid ester copolymers, their metal salts, amides and imides. Can be mentioned. Specific examples include ethylene / acrylic acid (or methacrylic acid) methyl copolymer, ethylene / acrylic acid (or methacrylic acid) ethyl copolymer, and the like. In particular, an ethylene / ethyl acrylate copolymer (hereinafter sometimes abbreviated as EEA) is preferable. That is, ethylene 5
0-99.5% by weight, acrylic acid ethyl ester 0.5-50
Copolymers consisting of wt% are preferred. Copolymer MFR
Is 0.1 to 50 g / 10 minutes, preferably 0.5 to 20 g / 1
It is better to select from the range of 0 minutes. MFR is 0.1g / 1
If it is less than 0 minutes, the fluidity of the resin composition is deteriorated, and 50 g /
If it exceeds 10 minutes, the mechanical strength is lowered, which is not desirable.

The above-mentioned ethylene-vinyl ester copolymer is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate containing ethylene as a main component, which is produced by a high pressure radical polymerization method. It is a copolymer with a vinyl ester monomer such as trifluorovinyl acetate. Among these, an ethylene-vinyl acetate copolymer (hereinafter, sometimes abbreviated as EVA) is particularly preferable. That is, a copolymer composed of 50 to 99.5% by weight of ethylene and 0.5 to 50% by weight of vinyl acetate is preferable.

Oxygen-containing copolymers such as copolymers with the above-mentioned ethylene / α, β-unsaturated carboxylic acid alkyl ester and its derivatives and ethylene-vinyl ester copolymers are treated with inorganic materials 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 at the time of combustion promotes the formation of char (carbonized layer), and the char formed on the surface of the combustion product hinders the supply of oxygen. Presumed. The char-producing effect is particularly high in EEA and EVA, and the flame-retarding effect is also large. Of these two, EEA is particularly preferable.

As the rubber of the component (A'3) in the present invention, ethylene propylene rubber, butadiene rubber,
Examples thereof include isoprene-based rubber, natural rubber, nitrile rubber, and isobutylene rubber. These may be used alone or as a mixture.

As the above ethylene propylene rubber,
Random copolymer (EPM) containing ethylene and propylene as main components, and diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as third component
Random copolymer (EPD)
M).

The butadiene-based rubber is a copolymer having butadiene as a constituent element, and is a styrene-butadiene block copolymer (SBS) and its hydrogenated or partially hydrogenated styrene-butadiene-ethylene copolymer. Combined (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 isoprene rubber is a copolymer having isoprene as a constituent element, and is a styrene-isoprene block copolymer (SIS) and its hydrogenated or partially hydrogenated styrene-isoprene-ethylene copolymer (SIES). ) And modified isoprene rubber having a core-shell structure.

The olefin polymer as the component (A ') in the present invention can be blended with a large amount of an inorganic flame retardant in order to maintain a high degree of flame retardancy without lowering the mechanical strength. It plays a role of improving flexibility and impact resistance.

The amount of the component (A) and the component (A ') in the polymer component of the present invention is 0 to 98% by weight, preferably 100 to 2% by weight of the component (A), and more preferably 0 to 98% by weight. Is 20 to 80% by weight of the component (A ') relative to 80 to 20% by weight of the component (A).

Further, in the resin component of the present invention, at least one of the component (A), the component (A '), or the component (A) + (A') contains (a) a carboxylic acid group or a carboxylic acid anhydride group. , (B) epoxy group, (c) hydroxyl group,
At least one functional group selected from (d) amino group, (e) alkenyl cyclic iminoether group, and (f) silane group is in the range of 10 ^{−7 to} 5 × 10 ⁻⁴ mol per 1 g of the total polymer. Preferably there is.

Examples of the compound for introducing the functional group (a) (carboxylic acid group or carboxylic acid anhydride group) include α, β such as maleic acid, fumaric acid, citraconic acid and itaconic acid.
-Unsaturated dicarboxylic acids or their anhydrides, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinylacetic acid, pentenoic acid, and the like.

Examples of compounds for introducing the functional group (b) (epoxy group) include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconic acid, monoglycidyl butenetricarboxylic acid, diglycidyl butenetricarboxylic acid, butenetricarboxylic acid. Triglycidyl ester and α-chloroacrylic acid,
Glycidyl esters such as maleic acid, crotonic acid, fumaric acid or vinyl glycidyl ether, allyl glycidyl ether, glycidyl oxyethyl vinyl ether, glycidyl ethers such as styrene / p-glycidyl ether, p-glycidyl styrene, etc. Preferred examples include glycidyl methacrylate and allyl glycidyl ether.

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

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

Examples of the compound for introducing the functional group (e) (alkenyl cyclic iminoether group) include the compounds represented by the following structural formulas.

[Chemical 1]

Here, n is 1, 2 and 3, preferably 2 and 3, and more preferably 2. R ⁷ , R ⁸ , R ⁹ and R are each independently C1 to
C12 represents an inactive alkyl group and / or hydrogen, and the alkyl group may have an inactive substituent. The term "inert" as used herein means that the graft reaction and the function of the product are not adversely affected. Moreover, a plurality of R need not be the same. Preferably R ⁷ = R ⁸ =
H, R ⁹ = H or Me, R = H, that is, 2-vinyl and / or 2-isopropenyl-2-oxazoline, 2-vinyl and / or 2-isopropenyl-
It is 5,6-dihydro-4H-1,3-oxazine.
These may be used alone or as a mixture. Among these, especially 2-
Vinyl and / or 2-isopropenyl-2-oxazoline are preferred.

Examples of the compound introducing the functional group (f) silane group include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane and vinyltrichlorosilane.

As a specific method for introducing a functional group into the polymer component of the present invention, at least one kind of the functional group-containing monomer is used as the component (A), the component (A ') or the component (A).
+ A method of introducing as a modified polymer grafted onto a part or all of the component (A '), a method of incorporating the functional group by incorporating a random copolymer of ethylene and a functional group-containing compound into a resin component, and And a method of mixing both of them.

The method for producing the grafted modified polymer of the present invention includes a melting method in which at least one compound having the above-mentioned functional group is melted and modified in the extruder in the presence of a radical initiator, or a resin is used. And a method of graft-modifying the polymer by a solution method of mixing and reacting in a solution. Examples of the radical initiator include organic peroxides, dihydroaromatic compounds, dicumyl compounds and the like.

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 its derivative, dihydrofuran, 1,2-
Dihydrobenzene, 1,2-dihydronaphthalene, 9,
10-dihydrophenanthrene and the like can be mentioned.

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 particularly 2,3-diethyl-2,3-diphenylbutane is 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, a pressure of 2500 to 3000 kg / cm ² , and a temperature of A method of copolymerizing ethylene and at least one kind of the compound having the functional group under the condition of about 250 ° C. may be mentioned. Examples of the radical initiator include the above organic peroxides.

The above-mentioned functional group in the polymer component of the present invention is (A), (A ') or (A) + (A') as described above.
1 when the graft-modified polymer is used for the component
In the range of 0 ^{-7 to} 5 × 10 ^-4 mol / g, and when using a random copolymer of ethylene and a functional group-containing compound, 5 × 10 ^-6 mol to 5 × 10 ^-4 mol It is adjusted to be in the range of / 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. Then, the coupling effect between the resin component and the inorganic flame retardant of the component (B) described below becomes insufficient, and mechanical strength and the like may be poor. Also, char (carbonized layer) when the composition burns
Formation may be impaired and drip resistance may be reduced. Further, when the content of the functional group is 5 × 10 ⁻⁴ mol / g or more, the coupling effect becomes too large and the mechanical strength and particularly the elongation of the resin composition deteriorate.

Among the modified polymers containing these functional groups or the random copolymers of ethylene and the functional group-containing compound, in particular (A), (A ') or (A) + (A').
Of the components, ethylene / α with a density of 0.86 to 0.94 g / cm ³
An ethylene (co) polymer obtained by modifying the olefin copolymer with maleic anhydride is preferably used.

Examples of the inorganic phosphorus-free flame retardant which is the component (B) of the present invention include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide and tin oxide. Hydrate, hydrate of inorganic metal compound such as borax, zinc borate,
Examples thereof include zinc metaborate, barium metaborate, zinc carbonate, calcium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide and tin oxide.

These may be used alone or in combination of two or more. Among these, hydrates of at least one metal compound selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, and hydrotalcite, especially aluminum hydroxide and water. Magnesium oxide has a good flame retardant effect and is economically advantageous. The particle size of these inorganic phosphorus-free flame retardants varies depending on the type, but in the above aluminum hydroxide and magnesium hydroxide, the average particle size is preferably 20 μm or less, more preferably 10 μm or less.

The blending amount of the inorganic phosphorus-free flame retardant of the component (B) of the present invention is the polymer component (A) or (A) +
The amount is 30 to 200 parts by weight, preferably 40 to 150 parts by weight, relative to 100 parts by weight of (A ′). If the blending amount is less than 30 parts by weight, it is difficult to achieve sufficient flame retardancy by using the inorganic phosphorus-free flame retardant alone, so it is necessary to use an organic flame retardant together. While 2
If the amount is more than 00 parts by weight, mechanical strength such as tensile strength, elongation, impact strength is lowered,
Inflexibility and poor low temperature properties.

In the present invention, the first to fourth inventions
The fifth invention in which red phosphorus is added to the composition of the invention can provide a flame-retardant resin composition having higher flame retardancy. In the present invention, it is desirable to use red phosphorus coated with an organic and / or inorganic compound as the red phosphorus. Red phosphorus coated with an organic and / or inorganic compound means that the surface of red phosphorus particles is coated with a thermosetting resin such as epoxy resin, phenol resin, polyester resin, silicone resin, polyamide resin, or acrylic resin. Those coated with aluminum hydroxide, zinc, magnesium, etc. and further coated with a thermosetting resin, those made into metal phosphide and then coated with a thermosetting resin, metal complex hydrated oxides of titanium, cobalt, zirconium, etc. Modified red phosphorus such as those coated with.

The red phosphorus preferably has an average particle size of 5 to 30 μm, and the content of the particles having a particle size of 1 μm or less and 100 μm or more is 5% by weight or less. In the case of complex hydrated oxides of titanium, cobalt, etc., Ti based on the total weight of red phosphorus particles
0.5 to 15% by weight as a metal component such as + Co, and similarly, 0.1 to 20% by weight based on the total weight of the organic resin is preferable. These modified red phosphorus have excellent heat resistance stability and hydrolysis resistance, and the hydrolysis reaction in the presence of water or at high temperature is almost completely suppressed, so that no odorous and toxic phosphine gas is generated. The amount of the red phosphorus compounded is in the range of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of the resin component. If the compounding amount of red phosphorus is less than 0.1 part by weight, the effect of addition may be small and a sufficient flame retarding effect may not be obtained, and even if the amount of compounding exceeds 20 parts by weight, the flame retardant effect will not be further improved. It is not preferable in terms of physical properties and economy.

In the present invention, by using the above composition and the inorganic filler in combination, the blending amount of the flame retardant can be reduced and other characteristics can be imparted.
As the inorganic filler, 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, whiskers, metal fiber, graphite fiber, silicon carbide fiber, asbestos, woo Last night etc. are mentioned. The inorganic filler is added in an amount of about 100 parts by weight based on 100 parts by weight of the composition of the present invention. Compounding amount is 1
If the amount exceeds 100 parts by weight, mechanical properties such as impact strength of the molded product deteriorate, which is not preferable.

In the present invention, when the inorganic flame retardant or the inorganic filler is used, the surface of the flame retardant or the filler is a fatty acid such as stearic acid, oleic acid or palmitic acid or a metal salt thereof. Surface treatment such as coating with paraffin, wax, polyethylene wax, or modified products thereof, organic borane, organic titanate, or the like is preferable.

The main role of each component played in the composition of the present invention is considered as follows. The component (A) (ethylene (co) polymer satisfying specific parameters) plays a role of remarkably improving mechanical properties. The component (A ′) (olefin polymer) has flexibility and impact resistance without lowering mechanical strength when a large amount of inorganic flame retardant is blended in order to maintain high flame retardancy. Plays a role of enhancing sex. Further, 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.

The component (B) (inorganic flame retardant) plays a role of achieving a high degree of halogen-free flame retardancy. The functional groups in the polymer components (A) and (A ') have a coupling effect between the polymer components (A) and (A') and the inorganic flame retardant of the component (B), and compatibility with the resin. To improve the mechanical strength, wear resistance, heat resistance and workability, and to improve the drip resistance due to the formation of char (carbonized layer) during combustion. In addition, red phosphorus 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 acid esters of polyhydric alcohols are used as long as the physical properties of the flame-retardant composition of the present invention are not impaired. Or at least one scratch whitening agent, fatty acid alcohol, fatty acid amide, alkylphenol or alkylnaphthol alkylene oxide adduct, organic filler, antioxidant, lubricant, organic or inorganic pigment, UV inhibitor, dispersant, You may add a copper damage inhibitor, a neutralizer, a plasticizer, a nucleating agent, etc.

[0088]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. In the following description, “part” is “part by weight” unless otherwise specified.

[Resin and Materials Used] Polymerization of (A) Component Sample A (1) Preparation of Catalyst 150 ml of purified toluene was added to a 500 ml eggplant type flask equipped with an electromagnetic induction stirrer under nitrogen, and then tetrapropoxyzirconium (Zr (On -Pr) ₄ ) 0.60 g and 1.0 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and the system was kept at 0 ° C to give triisobutylaluminum (Al (i-B
u) 3.2 g of ₃ ) was added dropwise over 30 minutes, and after the addition was completed, the system was brought to room temperature and stirred for 24 hours. Next, a toluene solution of methylalumoxane (concentration 1 mmol / ml) was added to this solution.
200 ml was added and reacted at room temperature for 1 hour. Separately, in a 1.5-liter three-necked flask equipped with a stirrer under nitrogen at 600 ° C.
Time-fired silica (Fuji Davison, grade # 9
52, surface area 300 m ² / g) 50 g, the whole amount of the solution was added, and the mixture was stirred at room temperature for 2 hours. Then, the solvent was removed by nitrogen blowing to obtain a powder having good fluidity.

(2) Polymerization Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70
Ethylene and butene at ℃ and total pressure of 20kgf / cm ² · G
1 was copolymerized. Polymerization was carried out while continuously supplying each gas in order to continuously supply the catalyst and keep the gas composition in the system constant. The MFR was adjusted by adjusting the hydrogen concentration in the system. The physical properties of the produced polymer are shown in Table 1.
As described in. For comparison, the value for polymerization using a Ziegler-based catalyst (A'1-1 component) is also shown. In Table 1, X (calculated value) is the upper limit value of X under the condition (e) required for the ethylene (co) polymer of the present invention. For the resins in Table 1, d-0.008 x logMF
Since R <0.93, 9.8 × 10 ³ × (0.9300−d + 0.00
It is a value calculated according to 8 × logMFR) ² +2.0.

[0091]

[Table 1] Table 1: Physical property values of component (A) Item (unit) (A) component (A'1-1 component) MFR (g / 10 min) 1.0 1.0 Density (g / cm ³ ) 0.920 0.922 Molecular weight distribution (Mw / Mn) 2.7 4.7 ODCB soluble content (wt%) ) 1.0 4.8 X (calculated value) (wt%) 2.98 2.63 Cb (-) 1.25 1.75 TREF peak (-) multiples multiples

(AM-1): A modified maleic anhydride graft-modified product of the component (A) [density = 0.92 g / c]
m ³ , MFR = 0.8 g / 10 min, maleic anhydride reaction amount = 1.5 × 10 ⁻⁵ mol / g, Nippon Polyolefin Co., Ltd.
Manufactured], (AM-2): Modified maleic anhydride graft modified product of the component (A) [Density = 0.92 g / cm ³ , MFR =
0.9 g / 10 minutes, maleic anhydride reaction amount = 5.1 × 10 ^-6
mol / g, manufactured by Nippon Polyolefin Co., Ltd.], (A-A): Melt-processed alkenyl cyclic iminoether graft modified product of the component (A) [density = 0.92 g / cm ³ ,
MFR = 1.2 g / 10 min, reaction amount = 1.6 × 10 ⁻⁵ mol
/ G, manufactured by Nippon Polyolefin Co., Ltd., (A-S): Melt method vinyltrimethoxylane graft modified product of the component (A) [density = 0.92 g / cm ³ , MFR
= 1.2 g / 10 min, reaction amount = 1.1 × 10 ⁻⁵ mol / g,
Made by Nippon Polyolefin Co., Ltd.,

Component (A'1) (A'1-1): Linear low-density polyethylene (LLDPE) shown in Table 1 [density = 0.922 g / cm ³ , MFR
= 1.0 g / 10 min, manufactured by Nippon Polyolefin Co., Ltd.], (A'1-1-M): Melt-processed maleic anhydride graft modified product of the component (A'1-1) [Density = 0.92 g / c]
m ³ , MFR = 0.8 g / 10 min, maleic anhydride reaction amount = 1.6 × 10 ⁻⁵ mol / g, Nippon Polyolefin Co., Ltd.
[Production], (A'1-1-A): Melting method alkenyl cyclic iminoether graft modified product of the component (A'1-1) [density =
0.92 g / cm ³ , MFR = 0.7 g / 10 min, reaction amount =
1.6 × 10 ^-5 mol / g, Nippon Polyolefin Co., Ltd.
Manufactured], (A'1-1-S): a modified vinyl trimethoxysilane graft product of the component (A'1-1) [density = 0.92 g
/ Cm ³ , MFR = 0.8 g / 10 min, reaction amount = 1.3 × 1
0 ^-5 mol / g, manufactured by Nippon Polyolefin (Ltd.)], (A'1-2): ethylene-butene-1 copolymer (VL
DPE) [density = 0.900 g / cm ³ , MFR = 1.0 g /
10 minutes, manufactured by Nippon Polyolefin Co., Ltd.],

(A'2-1): Ethylene / ethyl acrylate copolymer (EEA) [EA content = 10 wt%, MF
R = 0.4 g / 10 minutes, manufactured by Nippon Polyolefin Co., Ltd.], (A'2-2): ethylene / vinyl acetate copolymer (EV
A) [VA content = 10 wt%, MFR = 1.0 g / 10
Min., Manufactured by Japan Polyolefin Co., Ltd.], (A′2-G): ethylene / glycidyl methacrylate copolymer (EGMA) [GMA content = 1.2 × 10 ⁻³ mol
/ G, MFR = 4.0 g / 10 minutes, manufactured by Nippon Polyolefin Co., Ltd.],

(A'3): Ethylene / propylene copolymer rubber (EPM) [propylene = 27 wt%, MFR =
0.7g / 10min EP07P, manufactured by Japan Synthetic Rubber Co., Ltd.],

Component (B) (B-1): Magnesium hydroxide [Product name: Kisuma 5A
Kyowa Chemical Industry Co., Ltd.], (B-2): Aluminum hydroxide [Product name: Heidilite H-42M Showa Denko KK],

Test Method (1) Tensile Test (kg / cm ² ) and Elongation (%) A test piece punched with a No. 3 dumbbell from a sheet having a thickness of 1 mm was measured with a tensilon at a pulling speed of 200 mm / min. did. (2) Oxygen index (OI) The oxygen index was measured according to JIS K7201. The oxygen index is defined as the minimum oxygen concentration required to sustain combustion, and the higher this number, the higher the flame retardancy.

Examples 1 to 41: The compositions having the formulations shown in Tables 2 to 7 were dry blended, and then melt-kneaded at a resin temperature of 200 ° C. using a 50 mmφ extruder and pelletized.
Further, a sample was prepared by press molding at 180 ° C., a pressure of 100 kg / cm ² , and a time of 5 minutes, and the sample was provided for the test. The test results are shown in Tables 2 to 7.

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[0104]

[Table 7]

Examples 1 and 2 140 parts of magnesium hydroxide or aluminum hydroxide was mixed with 100 parts of the component (A) to prepare a sample, which was subjected to the test. The tensile strength at break and the tensile elongation at break showed sufficient values, and the oxygen index also showed high values.

Examples 3 to 6 Magnesium hydroxide was added to 140 parts of the resin component prepared by blending the component (A) with the component (A'1-1) LLDPE.
A partly mixed sample was prepared and subjected to the test. The tensile strength at break and the tensile elongation at break showed sufficient values, and the oxygen index also showed high values.

Examples 7 to 9 Samples were prepared by mixing 140 parts of magnesium hydroxide with 100 parts of the resin component prepared by mixing the component (A) with EEA of the component (A'2-1), and used for the test. The tensile breaking strength and tensile breaking elongation showed sufficient values. Further, the oxygen index also showed a sufficiently high value due to the effect of char formation by the oxygen-containing copolymer.

Examples 10 to 11 Resin component 100 prepared by blending component (A) with component (A'1-1) LLDPE and component (A'2-1) EEA.
A sample was prepared by mixing 140 parts of magnesium hydroxide with respect to 1 part, and the sample was subjected to the test. The tensile breaking strength and tensile breaking elongation showed sufficient values. Further, the oxygen index also showed a sufficiently high value due to the effect of char formation by the oxygen-containing copolymer.

Examples 12 to 15 The component (A) was graft-modified with maleic anhydride (AM).
-1) component, EEA of (A'2-1) component or (A '
2-2) 1 part of magnesium hydroxide or aluminum hydroxide to 100 parts of the resin component containing EVA as the component
A sample containing 40 parts was prepared and used for the test. The oxygen index was remarkably improved because the char formation effect of the oxygen-containing copolymers EEA and EVA and the coupling force of the introduced functional group with the inorganic flame retardant resulted in stronger char formation.

Example 16 The component (A) was graft-modified with maleic anhydride (AM
A sample was prepared by mixing 140 parts by weight of magnesium hydroxide with 100 parts by weight of a resin component consisting of the EPR of the component (A'3) in the component -1) and used for the test. Sufficient tensile rupture strength was exhibited by the coupling force of the introduced functional group with the inorganic flame retardant.

Examples 17 to 19 EEA of the (A-M-1) component and the (A'2-1) component obtained by graft-modifying the (A) component with the maleic anhydride.
100 parts of a resin component blended with, or (A) a component (A'1-1) LLDPE, and a component (A) maleic anhydride graft-modified (A-M-1) component and (A'2-). 1) Resin component 100 containing EEA as component
A sample was prepared by mixing 140 parts of magnesium hydroxide with respect to 1 part, and the sample was subjected to the test. A significant improvement in tensile rupture strength was observed by blending the component (A). Further, the oxygen index was found to have a remarkable improvement in the oxygen index due to the char forming effect of EEA, which is an oxygen-containing copolymer, as well as the stronger char formation due to the coupling force of the introduced functional group with the inorganic flame retardant.

Examples 20 to 22 Component (A'1-1) LLDPE component (A'1-1-M) component (A'1-1) and component (A'2-1) component (A'1-1) LLDPE were modified. Resin component 100 containing EEA
Part or LLD of (A'1-1) component to (A) component
Resin component 100 in which PE and LLDPE of (A'1-1) component are graft-modified with maleic anhydride and (A'1-1-M) component and (A'2-1) component EEA are mixed.
A sample was prepared by mixing 140 parts of magnesium hydroxide with respect to 1 part, and the sample was subjected to the test. A significant improvement in tensile rupture strength was observed by blending the component (A). Further, the oxygen index was found to have a remarkable improvement in the oxygen index due to the char forming effect of EEA, which is an oxygen-containing copolymer, as well as the stronger char formation due to the coupling force of the introduced functional group with the inorganic flame retardant.

Examples 23 to 26 Component (A) was added to component (A) by maleic anhydride graft modification (AM-1) or alkenyl cyclic imino ether graft modification (AA) component or vinyltriene. A sample was prepared by mixing 140 parts of magnesium hydroxide with 100 parts of a resin component containing the (AS) component modified with methoxysilane, and the sample was subjected to the test. A significant improvement in tensile rupture strength was observed due to the compounding of the component (A) and the coupling effect of the introduced functional groups with the inorganic flame retardant. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Example 27 Sample in which 140 parts of magnesium hydroxide was mixed with 100 parts of resin component in which EGMA of component (A′2-G) obtained by random copolymerization of ethylene and glycidyl acrylate in component (A) was blended Was prepared and subjected to the test. A significant improvement in tensile rupture strength was observed due to the compounding of the component (A) and the coupling effect of the introduced functional groups with the inorganic flame retardant. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Examples 28 to 31 Component (A'1-1) LLDPE or (A'1-2)
Resin component 1 in which component (A) is graft-modified with maleic anhydride (AM-1) is added to component VLDPE
A sample in which 140 parts of magnesium hydroxide was mixed with 00 parts of the sample was prepared and subjected to the test. A significant improvement in tensile rupture strength was observed due to the blending of the component (A-M-1) in which the component (A) was graft-modified with maleic anhydride and the coupling effect with the inorganic flame retardant by the introduced functional group. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Examples 32 to 35 Component (A), component (A'1-1) LLDPE and component (A) were graft-modified with maleic anhydride (AM).
-1) 100 parts of a resin component containing the component, or (A)
Sample in which 140 parts of magnesium hydroxide was mixed with 100 parts of resin component in which VLDPE of component (A′1-2) and component (A-M-1) in which the component (A) was graft-modified with maleic anhydride were mixed into component Was prepared and subjected to the test.
The component (A) was graft-modified with maleic anhydride (AM
-1) A significant improvement in tensile rupture strength was observed due to the compounding of the component and the coupling effect with the inorganic flame retardant by the introduced functional group. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Examples 36 to 38 The component (A) was modified by grafting the LLDPE component (A'1-1) with maleic anhydride (A'1-1-M) or the alkenyl cyclic imino ether graft ( A'1-1-A) component or vinyltrimethoxysilane-modified (A'1-1-S) component was mixed with 140 parts of magnesium hydroxide to 100 parts of a resin component, and a sample was prepared for use in the test. did. A significant improvement in tensile rupture strength was observed due to the compounding of the component (A) and the coupling effect of the introduced functional groups with the inorganic flame retardant. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Examples 39 to 40 The component (A), the component (A'1-1) LLDPE and the component (A'1-1) LLDPE component were graft-modified with maleic anhydride (A'1-1-). A sample was prepared by mixing 140 parts of magnesium hydroxide with 100 parts of the resin component containing M), and the sample was subjected to the test. A significant improvement in tensile rupture strength was observed due to the compounding of the component (A) and the coupling effect of the introduced functional groups with the inorganic flame retardant. Moreover, char formation was achieved by the coupling force of the introduced functional group with the inorganic flame retardant, and the oxygen index was improved.

Example 41 To 100 parts of the same resin composition as in Example 18, 80 parts of magnesium hydroxide and 3 parts of red phosphorus were blended. Both strength and oxygen index were good.

Comparative Example 1 Without using the component (A), with respect to the component (A′2),
Table 8 shows a mixture of the inorganic flame retardant as the component (B). As a result, the strength and elongation were significantly lower than those of the examples.

Comparative Example 2 As in Example 15, as a method of introducing a functional group, the component (A) was modified with maleic anhydride at different concentrations (AM-2).
One part of the component was added so that the amount of the component (A) in the resin component was out of the range. The results are shown in Table 8. As a result, the tensile strength at break and the tensile elongation at break were significantly lower than those of the examples.

Comparative Examples 3 to 4 Without using the component (A), with respect to the component (A′1),
Table 8 shows a mixture of the inorganic flame retardant as the component (B). As a result, the tensile strength at break and the tensile elongation at break were significantly lower than those of the examples.

Comparative Examples 5 to 6 The same resin component as in Example 23 was used, and an inorganic flame retardant was added to 250 parts.
Parts (Comparative Example 5) and 25 parts (Comparative Example 6). The results are shown in Table 8. At 250 parts, the tensile rupture strength and tensile rupture elongation were remarkably low, and at 25 parts, the flame retardancy was not satisfactory.

[0124]

[Table 8]

[0125]

INDUSTRIAL APPLICABILITY The present invention is a flame-retardant resin composition comprising an ethylene (co) polymer satisfying a specific parameter range, an olefin polymer, a polymer component containing a specific amount of a specific functional group, and an inorganic flame retardant. The mechanical properties are significantly improved while maintaining low pollution, such as flexibility, high flame retardancy, and generation of no harmful gas such as halogen gas during combustion. In particular, the component (A) is an ethylene (co) polymer having a narrow molecular weight distribution, a moderately wide composition distribution, and a small amount of highly branched low molecular weight components, and therefore contributes to a remarkable improvement in mechanical strength. ing. Further, in particular, the specific functional group plays a role of coupling the polymer component and the inorganic flame retardant or the inorganic filler, enhances the compatibility of the resins with each other, and improves mechanical strength, processability, wear resistance, etc. Improve. Further, during combustion, it also contributes to the formation of char (carbonized layer) to prevent resin dripping and self-extinguishing.

As described above, the resin composition of the present invention has a high degree of flame retardancy, does not generate a toxic gas such as a halogen gas at the time of combustion, is excellent in abrasion resistance and heat resistance, and is safe and easy to use. It has excellent flexibility, mechanical properties, chemical resistance, and electrical properties, so it can be used as a film, sheet,
It is used for molding applications such as extrusion molded products such as pipes or injection molded products, and for electric wires and cables.
It can be used in various fields such as electricity, electronics, automobiles, ships, aircraft, construction, and civil engineering.

[Brief description of drawings]

FIG. 1 is a TREF curve of the copolymer of the present invention.

FIG. 2 is a TREF curve of a copolymer with a metallocene catalyst.

Continuation of the front page (72) Satoshi Kaneko 2-3-2 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Polyolefin Co., Ltd. Kawasaki Research Center (56) Reference JP-A-5-331324 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) C08F 10/02 C08F 110/02 C08F 210/02 C08L 23/04-23/08 C08L 23/16 EUROPAT (QUESTEL)

Claims (5)

(57) [Claims] 1. An inorganic phosphorus-free flame retardant 30-200 (B) with respect to 100 parts by weight of a resin component (A) consisting of an ethylene (co) polymer satisfying the following conditions (A) to (F): Flame-retardant resin composition characterized by containing parts by weight: (a) density (d) 0.86 to 0.97 g / cm ³ , (b) melt flow rate (MFR) 0.01 to 200 g /
10 minutes, (c) molecular weight distribution (Mw / Mn) 1.5 to 4.5, (d) composition distribution parameter (Cb) 1.08 to 2.0, (e) ortho-dichlorobenzene (ODC) at 25 ° C.
B) The relationship between the amount (X) (wt%) of the soluble component and the density (d) and the melt flow rate (MFR) is (1) d-0.00.
In the case of 8 × log MFR ≧ 0.93, X <2.0,
(2) When d−0.008 × logMFR <0.93, X
<9.8 x 10 ³ x (0.9300-d + 0.008 x logMFR) ² +
The relationship of 2.0 is satisfied. (F) There are a plurality of peaks on the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF). 2. As a resin component, 2% by weight or more of an ethylene (co) polymer satisfying the conditions (A) to (F) of (A) according to claim 1, and (A ') A '
1) to 100 parts by weight of a resin component containing less than 98% by weight of at least one kind of olefin polymer selected from (A′3), (B) inorganic phosphorus-free flame retardant 30 to 200
Flame-retardant resin composition characterized by containing parts by weight: (A'1) Ethylene / α-olefin copolymerization different from ethylene (co) polymer satisfying the above conditions (a) to (f) Combined, (A'2) ethylene copolymer by high pressure radical polymerization method, (A'3) rubber. 3. At least a part of the resin component (A), (A ′) or (A) + (A ′) is the following (a) to (a).
The flame-retardant resin composition according to claim 1 or 2, wherein at least one functional group selected from (f) is contained in an amount of 10 ^{−7 to} 5 × 10 ⁻⁴ mol per 1 g of the resin component. Products: (a) carboxylic acid group or carboxylic acid anhydride group, (b)
Epoxy group, (c) hydroxyl group, (d) amino group,
(E) Alkenyl cyclic imino ether group, (f) silane group. 4. Ethylene is used alone in the presence of a catalyst in which the ethylene (co) polymer of the component (A) contains at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. The flame retardant according to any one of claims 1 to 3, which is an ethylene copolymer obtained by polymerizing or copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms. Resin composition. 5. The resin component 10 as a flame retardant.
The flame-retardant resin composition according to claim 1, which contains 0.1 to 20 parts by weight of red phosphorus with respect to 0 parts by weight.