JP3198720B2 - Flame-retardant polyolefin resin composition suitable for extrusion molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyolefin resin composition suitable for extrusion molding. More specifically, it contains a polyolefin resin as a main component, does not generate corrosive gas or toxic gas, has little deterioration in moldability, exhibits high flame retardancy in the state of molded products, and has excellent mechanical properties And a flame-retardant polyolefin resin composition suitable for extrusion molding having a smooth surface appearance.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins have excellent suitability in processability, chemical resistance, weather resistance, electrical characteristics and mechanical characteristics, and have been used in home electric appliances, buildings and interior decorations. And in various fields such as automobile parts. Originally, polyolefin resin is a resin that easily burns. However, the performance as a flame-retardant material has been required for polyolefin resins with the expansion of the applications in which they are used, and the required flame-retardant performance is becoming severer year by year.

However, in the case of using a halogen-based flame retardant which has been conventionally used, in addition to the toxicity of the gas generated during combustion, the generated black smoke is regarded as a problem from the viewpoint of environmental problems. Various flame-retardant polyolefin resin compositions have been proposed in order to meet the demand for flame retardancy which is strengthened year by year.

Specific proposals include the following: JP-A-53-92855, JP-A-54-293.
No. 50, JP-A-54-77658, JP-A-5-77658
As disclosed in JP-A-6-26954, JP-A-57-87462, JP-A-60-110736, etc., water-containing inorganic compounds (for example, magnesium hydroxide,
A composition in which aluminum hydroxide, hydrotalcite, etc.) are added to a polypropylene resin; polyethylene and decabromodiphenyle having a melt index of 0.01 to 2.0 as disclosed in JP-B-55-30739. Ter (or dodecachlorododecahydromethanodibenzocyclooctene) and talc, kaolinite, sericite, silica in powder form,
A composition in which one or more inorganic fillers selected from diatomaceous earth are added to a polypropylene resin, JP-A-52-146452, JP-A-59-14
As disclosed in US Pat. No. 7,050,095, an aldehyde is reacted with an ammonium phosphate (or phosphoramide) and a nitrogen-containing compound containing a group> C ＝ O (or> C ＝ S or> NH) inserted into a cyclic structure. Reaction product or 1,
Compositions in which an oligomer (or polymer) of a 3,5-triazine derivative is added to a polypropylene resin have been proposed.

The effect of the proposed composition is to suppress the generation of toxic gases or to reduce the generation of black smoke.
However, in order for a composition in which a water-containing inorganic compound is added to a polypropylene resin, for example, a composition in which magnesium hydroxide is added, to exhibit high flame retardancy, it is necessary to contain a large amount of a water-containing inorganic compound. As a result, the composition has reduced moldability.

When molding a composition containing an inorganic filler together with a halogenated compound, a molded article having a relatively small decrease in molding processability and having a high degree of flame retardancy can be obtained. However, the control of corrosive or toxic gases generated during processing and combustion is still insufficient.

Further, Japanese Patent Application Laid-Open No. Sho 52-146452,
In the flame-retardant polypropylene resin composition disclosed in JP-A-59-147050, the decrease in moldability is relatively small, and the amount of corrosive gas or toxic gas generated during processing or combustion is also small. Has been suppressed.
Nevertheless, under high humidity conditions, a bleeding phenomenon of ammonium phosphate occurs on the surface of the molded article. The cause is required by the hygroscopicity of ammonium phosphate in the composition. In addition, there is a problem that the surface of an extruded product obtained from the composition is difficult to be smooth. Phenomenon of that is understood to be due to aggregate occurs.

[0008]

SUMMARY OF THE INVENTION The present inventors have developed a high degree of flame retardancy, that is, vertical combustion in the "flame test of plastic materials for equipment parts" specified in UL Subject 94 (Underwriter Laboratories, Inc.). Test based on the test (hereinafter "UL94 combustion test")
High flame retardancy and the addition of a flame retardant
Reduction in moldability caused less, yet proceeded to extensive studies to obtain a suitable flame-retardant polyolefin resin composition to create an extrusion molded article having excellent mechanical properties and smooth surface appearance.

As a result, the present inventors have found that the flame retardant (B) existing in a dispersed state in the polyolefin resin (A1) matrix via the olefin polymer (A2) layer adhered to the surface of the flame retardant component (B1). )), The extrudate obtained using the composition formed from the above was found to have both high flame retardancy, excellent mechanical properties and a smooth surface appearance. Further, the weight ratio (A2 / B1) of the olefin polymer (A2) and the flame retardant component (B1) adhered to the surface is from 1/99 to 25.
It has been found that by selecting a composition in the range of / 75, a further effect can be achieved to solve the above-mentioned problem. The present invention has been completed based on these findings.

Another object of the present invention is to provide a flame-retardant polyolefin resin composition suitable for preparing an extruded article having high flame retardancy, excellent mechanical properties and a smooth surface appearance.

[0011]

Suitable flame retardant polyolefin resin composition for extrusion molding of the problem-solving means for the present invention has the following configuration: 1) a polyolefin resin (A1) in the matrix below
Flame retardant component (B1) which is a combination of (B11) and (B2 )
There olefin polymer (A2) layer suitable for extrusion molding which is present in a dispersed state through a flame-retardant polyolefin resin composition which adheres to its surface: (B11) ammonium polyphosphate or melamine-modified ammonium polyphosphate, (B2) one or more selected from the following group: (B21) a one or more reaction products selected from the reaction product the following group, cyclic consisting of nitrogen atom from 5- or heterocyclic ring containing in the ring (B22) One or more reaction products selected from the following reaction products, wherein the five or more members contain two or more nitrogen atoms in the ring: (B23) 1,3,5-triazine derivatives containing a structure represented by the following general formula (Chemical Formula 2). 1 or more that.

Embedded image Wherein X is a morpholino or piperidino group, Y is a divalent group derived from piperazine, and n is a number from 2 to 50. 2) Constituting the flame retardant component (B1) with (B11) and (B11) Ratio with B2)
(B11 / B2) is in the range of 1/1 to 7/1 by weight
Suitable flame retardancy polio reflex to extrusion according to the claim 1 that
Resin composition. 3) heavy olefin for coating the flame retardant component (B1)
Melt flow index MI (190 ° C; 2.16 kgf) or MF of coalesced (A2)
R (230 ° C; 2.16 kgf) is the olefin weight of the matrix
The flow index of the combined (A1) +5 g / 10 min or more.
Item 1. Flame-retardant polyolefin resin suitable for extrusion molding according to item 1.
Fat composition. 4) Multi-stage multiple from upstream to downstream of extrusion barrel
Use an extruder with an inlet for
Ammonium polyphosphate or melamine modified
Ammonium phosphite (B11) and nitrogen-containing heterocyclic organic compound
Combination with at least one compound selected from compound (B2)
Olefin polymer (A2) to flame retardant component (B1)
Supply by weight ratio (A2 / B1) 1/99 to 25/75
And the surface of the flame retardant component (B1) is converted to an olefin polymer
At the stage when the coating is completed,
Do not supply polyolefin resin (A1) for
Flame-retardant polyolefin by melt kneading
A method for producing a resin composition.

The ratio (B11 / B2) of (B11) and (B2) belonging to the flame retardant component (B1) used in the present invention is preferably in the range of 1/1 to 7/1 by weight. 1 /
More preferably, it is in the range of 1 to 4/1.

The melt flow index MI (190 ° C .; 2.16 kgf) of the olefin polymer (A2) for coating the flame retardant component (B1 )
Or the MFR (230 ° C .; 2.16 kgf) is the flow index of the matrix olefin polymer (A1) +5 g / 10 min or more,
Preferably, the flow index is set to at least 20 g / 10 min.
You.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION <Polyolefin Resin (A1)> Examples of the polyolefin resin (A1) constituting the matrix of the polyolefin resin composition of the present invention include the following:-Ethylene-based resin, for example, low density polyethylene One or more selected from medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; propylene-based resin, for example, a crystalline homopolymer of propylene, mainly composed of propylene, and
-A crystalline copolymer with one or more selected from olefins: the 1-olefin is ethylene, 1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
1-heptene, 1-octene, 1-decene, etc. Soft copolymer (A13) contained as a minor component, for example, ethylene-propylene elastomer and its partially crosslinked product, ethylene-vinyl acetate copolymer, styrene-butadiene Copolymers and hydrides thereof, and a mixture of at least one of the above resins and at least one of a soft copolymer.

In particular, the polyolefin resin (A1) suitable as a matrix is an ethylene polymer composition, which can be used in a molded article in addition to a high-density polyethylene (A11) and a linear low-density polyethylene (A12). It is preferable to include an ethylene-propylene-based elastomer or a partially crosslinked product thereof (A13) in an amount sufficient to impart properties.

The polyolefin resin (A1) constituting the matrix of the flame-retardant polyolefin resin composition suitable for extrusion molding of the present invention is an ethylene-based crystalline polymer.
In the case of coalescence, its melt flow index MI (190
° C; 2.16 kgf) 0.05 to 30 g / 10 mi
n, preferably 0.1 to 10 g / 10 min or
It is a non-ethylenic crystalline polymer such as propylene
When it is a crystalline polymer, its melt flow index MFR
(230 ° C; 2.16 kgf) 0.05-30 g / 10
min, preferably 0.1 to 10 g / 10 min, the desired effect can be realized in most cases.

<Olefin polymer layer (A)
Flame retardant (B) having 2)> * Olefin polymer (A2) As a practical means of bringing the olefin polymer (A2) into close contact with the surface of the flame retardant component (B1), a coating treatment can be used. Olefin polymer for coating (A2)
Is a polyolefin resin (A
Those having higher fluidity than 1) are preferred. In the description of the present invention, "Olefin polymer (A2) adhered to the surface"
"Having a layer" may be expressed as "surface-treated" for convenience.

[0018] Here, lever suppose olefin polymer (A2) is a Ru polymer der plain, its melt fluidity is usually
It can be displayed in one of the following two types. Olefi
Similar indications can be used for elastomers.
That: ◆ soluble if the polymer is of the ethylene units subject
Melt flow index MI; at (190 ℃ 2.16kgf), ◆ when the polymer is of the propylene units principal
In; (2.16kgf 230 ℃) melt flow index MFR.

When the olefin polymer (A2) is a composition comprising two or more olefin polymers,
MI (190 ° C .; 2.16 kgf) or MFR (230
° C; 2.16 kgf). In addition, the polyolefin resin (A1)
Crystalline polymer and non-ethylene crystalline polymer, for example,
A composition (mixture) with a propylene-based crystalline polymer
In such cases, in principle, regardless of the mixing ratio,
The measurement conditions applied to the polymer apply .

In order to coat the flame retardant component (B1),
Melt flow index MI of olefin polymer (A2) (190 ° C .; 2.16
kgf) or MFR (230 ° C .; 2.16 kgf) is set to be at least the flow index of the olefin polymer (A1) as a matrix + 5 g / 10 min , preferably at least the flow index + 20 g / 10 min .

In this case, the olefin weight for the coating treatment is
The flow index of the combined (A2) is
The operation of comparing with the numerical value of “flow index of the polymer (A1) + predetermined value” is simply an operation of evaluating the magnitude relation of the numerical value itself. That is, even when one is MI and the other is MFR, the difference between the two is mechanically calculated to evaluate the magnitude relationship.

The weight ratio (A2) of the olefin polymer (A2) for surface treatment and the flame retardant component (B1) in the flame retardant component (B) which has been surface-treated with the olefin polymer (A2) in advance.
/ B1) is 1/99 to 25/75, preferably 3/97
~ 21/79, more preferably 11 / 89-20 / 80
(The sum of A2 and B1 is set to 100) .

In a molded article obtained from a composition having a composition in which the content of the olefin polymer (A2) in the surface-treated flame retardant (B) considerably exceeds this range, a decrease in mechanical properties is caused.
Occurs unacceptably , while the olefin polymer (A
In the case of a composition in which the content of 2) is considerably lower, the surface appearance of the obtained molded article is unacceptably lowered.

Furthermore, mixing ratio of the surface-treated flame retardant (B) and the matrix and such Luo olefin polymer (A1) in the final composition basis, through the content of the flame retardant (B) <br It is usually desirable that the content be 45% by weight or less. Rukoto The rationale is with increasing content of the flame retardants in the final composition, the final composition <br/> flame retardancy of a molded article obtained from the in contrary you above direction, mechanical properties make low Is required to balance. * Flame retardant component (B11) One essential component (B11) constituting the flame retardant component (B1) used in the present invention is ammonium polyphosphate or melamine-modified ammonium polyphosphate. Preferred ammonium polyphosphates have the general formula (NH ₄ PO ₃ ) _n (where
n is a number greater than or equal to 50), and as a commercial product, a product name “Bxolit 42
2 "(manufactured by Hoechst) and the trade name" Phos-Chek "
P-40 "(manufactured by Monsanto) and the like.

On the other hand, it is suitable for preparing the composition of the present invention.
Melamine modified ammonium polyphosphate used in (B1
1) is interpreted as powdery ammonium polyphosphate whose surface is coated with melamine. As a method for performing melamine coating, for example, a powdery ammonium II polyphosphate 200 is added to a kneader heated to 280 ° C. in advance.
0 parts, and 3 under nitrogen atmosphere or inert gas atmosphere.
The mixture was heated and mixed for an hour to remove ammonia.

At this time, the pH of a 1% by weight suspension of ammonium polyphosphate in which the amount of ammonia was less than the stoichiometric amount was 4.0. Melamine 2 is added to the powdery ammonium polyphosphate in a state where ammonia is insufficient.
Add 00 parts. At this point, close the upper lid of the kneader,
While maintaining this state, heat and mix (4 at 280 ° C).
time). Heat mixing was carried out without changing the form of the ammonium polyphosphate to obtain a powdery ammonium polyphosphate coated with melamine. * Flame retardant component (B2) The other flame retardant component (B2) (hereinafter, referred to as "nitrogen-containing heterocyclic organic compound") used to prepare the composition of the present invention.
) May mean the following (B2
1) One or more reaction products selected from the following reaction product group, which contains two or more nitrogen atoms in a ring:
(B22) One or more reaction products selected from the following reaction products, wherein at least two nitrogen atoms are contained in the ring: (B23) A group of 1,3,5-triazine derivatives containing a structure represented by the following general formula (Formula 3): [Wherein X represents a morpholino group or a piperidino group, Y represents a divalent group derived from piperazine, and n represents a number of 2 to 50].

[0027]

Embedded image

The above-mentioned flame retardant component (B) is contained in the composition of the present invention.
Non-flammable gases which can be generated as a result of pyrolysis caused by ignition or contact with a flame or the like in the presence of matrix polyolefin resin (A1) together with ammonium polyphosphate or melamine-modified ammonium polyphosphate (B11) Almost only carbonaceous residues along with (water, carbon dioxide and nitrogen, etc.).

These nitrogen-containing heterocyclic organic compounds (B
Examples of 2) include the following: • Reaction products of aldehydes with ethylene urea, ethylene thiourea, hydantoin, hexahydropyrimidin-2-one, piperazine-3,6-dione, barbituric acid, etc. Or an oligomer or polymer of 2-piperazinylene-4-piperidino-1,3,5-triazine.

Among these, the following compounds are preferred in terms of imparting flame retardancy: (B21): a reaction product of ethylene urea with formaldehyde; and (B22): a reaction product of ethylene thiourea with formaldehyde. Or (B23): 2-piperazinylene which is a derivative of 1,3,5-triazine having a structure represented by the following general formula (Formula 4)
-4-morpholino-1,3,5-triazine oligomer or polymer wherein X is a morpholino group or a piperidino group, Y is a divalent group derived from piperazine and n
Is a number from 2 to 50].

[0031]

Embedded image

In the composition of the present invention, various additives usually added to the polyolefin resin, such as an antioxidant, an antistatic agent, a lubricant, a neutralizer (metal stearate,
Hydrotalcite, etc.), a pigment, a nucleating agent, and the like can be added as necessary.

<Method for Preparing Composition> The flame-retardant polyolefin resin composition suitable for extrusion molding of the present invention can be prepared, for example, by the following procedure. Using an extruder equipped with multiple inlets in a multistage manner from upstream to downstream of the extrusion barrel, use the first feed port (located at the most upstream side).
A flame retardant comprising a mixture of at least one member selected from nitrogen-containing heterocyclic organic compounds identified by the and ammonium polyphosphate or melamine-modified ammonium polyphosphate (B11) a flame retardant component from the location) (B2) (B1 ) To the olefin polymer (A2) in a weight ratio ( A2 / B1) 1 /
By supplying at 99 to 25/75 , the flame retardant surface is coated with the olefin polymer. Obtaining the desired flame-retardant composition by performing melt-kneading while supplying the matrix polyolefin resin (A1) from the second supply port ( positioned downstream of the first input port) to this state. Can be.

An olefin polymer for surface treatment (A
2) and a mixture of the flame retardant component (B1) [weight ratio (A2 / B
1) = 1/99 to 25/75] was separately mixed with a kneader, and the resulting flame retardant composition (B1) was melt-kneaded in an extruder together with the polyolefin resin for matrix (A1). It is also possible to perform the surface treatment of the fuel component (B1) and its mixing with the matrix resin (A1) in a series.

[0035]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods used in the examples and comparative examples are as follows. <UL94 Vertical Burning Test> Compliant with the burning test of the "flaming test of plastic materials for equipment parts" specified in UL Subject 94 (Underwriter Laboratories, Inc.). 1.2 mm and 1.6 mm thickness of test piece. <Tensile elongation> Based on JIS K 6758. <DuPont impact strength> Test piece: flat plate ( length 50) prepared by injection molding
mm × width 50 mm × thickness 2 mm) 20 pieces ・ Test equipment: Test equipment indicated by the method B of JIS K 5400-6.13 ・ Test conditions: temperature 10 ° C., radius of curvature of the tip of the shooting type 1 /
4 in. , Measured and evaluated under various loads at a drop height of 1 m. <Surface Appearance> - Test piece: Extruder [trade name: Labo Plastomill (manufactured by Toyo Seiki Co.) molded sheet and Test Methods were prepared using: visual judgment and assess the presence or absence of aggregates on the test piece surface: A smooth surface state in which no aggregates are found is rated as “good (表面)” in surface appearance, and a surface state in which aggregates are clearly observed is rated as “poor (x)” in surface appearance.

[0036]

Embodiment 1 A twin screw extruder equipped with a multistage inlet [L / D = 4
4, screw rotation in the same direction; trade name: PCM45 (manufactured by Ikegai Iron Works)], and the following components are mixed in advance in a Henschel mixer (trade name) from the first supply port (upstream side). (3min) was supplied prepared <br/> was composition by (supply rate 35.5 parts by weight / h): · ammonium polyphosphate (B11) [trade name: Bxol
it 422 (manufactured by Hoechst)] 22.5% by weight, as a nitrogen-containing heterocyclic organic compound (B23), a polymer of 2-piperazinylene-4-morpholino-1,3,5-triazine (n = 11, molecular weight: about 2770) ) 7. Low-density polyethylene (A2) [ abbreviation: LDPE; MI]
(190 ° C .; 2.16 kgf) 100 g / 10 min;
Trade name: Petrocene 356 (manufactured by Tosoh Corporation)] 5% by weight and the following names and amounts of various additives: • 2,6-di-t-butyl-p-cresol 0.15
Parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t)
-Butyl-4'-hydroxyphenyl) propionate] methane 0.05 part by weight, dimyristyl-β, β'-thiodipropionate 0.2 part by weight, calcium stearyl phosphite 0.1 part by weight.

On the other hand, from the second supply port ( located downstream of the first supply port), the high-density polyethylene (A1) [HDP
E; MI (190 ° C .; 2.16 kgf) 0.3 g / 10
min; trade name: B743 (manufactured by Tosoh Corporation)] (65 parts by weight / h).

Melt kneading (temperature 200) in the above extruder
C.) and extruded to form strands. The strands were cooled with water, cut with a cutter, and pelletized. [Preparation of various test pieces] <For evaluation of flame retardancy and evaluation of mechanical characteristics> Injection molding machine (set the maximum cylinder temperature to 200 ° C)
To form predetermined test pieces. <Surface Appearance Observation> A sheet-shaped test piece was prepared using an extruder [trade name: Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.)]. Table 1 shows the evaluation results.

[0039]

Comparative Example 1 Ammonium polyphosphate (B11) 22.5
Wt%, nitrogen-containing heterocyclic organic compound (B23) 7.5
High-density polyethylene (A for weight percent and the surface treatment
2) 70% by weight and various additives blended in Example 1 were supplied to a Henschel mixer and then stirred and mixed (3 min). The obtained mixture was supplied only from the second supply port of the extruder barrel, and pellets were obtained according to Example 1.

Using the obtained pellets, a test piece for measurement was prepared and measured according to Example 1. Table 1 shows the evaluation results.

[0041]

Example 2 Table 1 ammonium polyphosphate from the first supply port As described in (B11) 22.5 wt%, nitrogen-containing heterocyclic organic compound (B23) 7.5 wt% and its
Low density polyethylene for the surface treatment of [LDPE; (A
2)] 5% by weight and various additives blended in Example 1 were supplied to a Henschel mixer and then stirred and mixed (3 min). The obtained mixture was supplied to the first supply port of the extruder (35.5 parts by weight / h). At the same time, a composition obtained by stirring and mixing (3 min) the following components in the following amounts in a Henschel mixer from the second supply port was supplied (65 parts by weight / h). Pellets were obtained: High density polyethylene [HDPE; (A11)] 27.
5% by weight,-Linear low density polyethylene (A12) [LLDPE;
MI (190 ° C; 2.16 kgf) 0.8 g / 10 mi
n; trade name: Nisseki Linirex AM1720 (manufactured by Nippon Petrochemical Co., Ltd.)] 27.5% by weight, ethylene-propylene elastomer (A13) [EP
R; MFR (230 ° C; 2.16 kgf) 0.7 g / 1
0 min; trade name: EP07P (manufactured by Nippon Synthetic Rubber Co., Ltd.)]
10% by weight.

Using the obtained pellets, a test piece for measurement was prepared in accordance with Example 1, and the measurement was performed using the test piece. Table 1 shows the results.

[0043]

COMPARATIVE EXAMPLE 2 As shown in Table 1, ammonium polyphosphate (B11), nitrogen-containing heterocyclic organic compound (B23), and matrix were supplied only from the second feed port of the extruder.
High-density polyethylene to form a (A11), linear low density polyethylene (A12) and ethylene - propylene elastomer (A13) in addition to those used in the respective predetermined amounts to obtain a pellet in conformity with Comparative Example 1. A test piece for measurement was prepared using the obtained pellets in accordance with Comparative Example 1, and measurement was performed using the test piece. Table 1 shows the results.

[0044]

Comparative Example 3 Pellets were obtained in accordance with Comparative Example 2 except that melt kneading was performed by supplying various compounding components only from the first supply port of the extruder. Using the obtained pellets, test specimens for measurement were prepared in accordance with Comparative Example 2, and measurements were performed using them. Table 1 shows the results.

[0045]

Example 3 of the flame retardant supplied from the first supply port of the extruder
Propylene homopolymer resin (A2) instead of low-density polyethylene (A2) for surface treatment [ abbreviation: PP-1; MF
R (230 ° C; 2.16 kgf) 80 g / 10 min]
A pellet was obtained in accordance with Example 1 except for using. Using the obtained pellets, a test piece for measurement was prepared in accordance with Example 1, and the measurement was performed. Table 1 shows the results.

[0046]

Example 4 The flame retardant supplied from the first supply port of the extruder
Low-density polyethylene (A2) for surface treatment, high-density polyethylene (A11) forming a matrix supplied from the second supply port, linear low-density polyethylene (A1)
2) and ethylene-propylene elastomer (A13)
Was the amount described in Table 1, respectively, the ratio thereof of the supply
Pellets were obtained according to Example 1 except that the (supply speed) was supplied at a rate of 37 parts by weight / h from the first supply port and 63.5 parts by weight / h from the second supply port. Using the obtained pellets, test pieces for measurement were prepared in accordance with Example 1, and measurements were performed using them. Table 1 shows the results.

[0047]

Example 5: Flame retardant supplied from the first supply port of the extruder
Low-density polyethylene (A2) for surface treatment, high-density polyethylene (A11) forming a matrix supplied from the second supply port, linear low-density polyethylene (A1)
2) and ethylene-propylene elastomer (A13)
Was the amount described in Table 1, respectively, are their feed rate from the first supply port 38.5 parts by weight / h, in addition to from the second supply port was supplied with 62 parts by weight / h Example 1 A pellet was obtained in accordance with Using the obtained pellets, test pieces for measurement were prepared in accordance with Example 1, and measurements were performed using them. Table 1 shows the results.

[0048]

Comparative Example 4 The flame retardant supplied from the first supply port of the extruder
Low-density polyethylene (A2) for surface treatment, high-density polyethylene (A11) forming a matrix supplied from the second supply port, linear low-density polyethylene (A1)
2) and ethylene-propylene elastomer (A13)
Each and amounts described in Table 1, carried out in addition to the supply thereof feed rate at the first from the supply port is 30.7 parts by weight / h, from the second supply port 69.8 parts / h Pellets were obtained according to Example 1. Using the obtained pellets, a test piece for measurement was prepared in accordance with Example 1, and the measurement was performed. Table 1 shows the results.

[0049]

Comparative Example 5 Matrix supplied from the first supply port of the extruder
Low density polyethylene (A2) and high-density polyethylene to form a Matorikkusuru supplied from the second supply port (A11), linear low density polyethylene (A12) and ethylene to form a Kusuru - propylene elastomer (A
13) were the blending amounts shown in Table 1, respectively , and the supply ratio was 42.5 parts by weight / h from the first supply port and 58 parts by weight / h from the second supply port. Example 1
A pellet was obtained in accordance with Using the obtained pellets, test pieces for measurement were prepared in accordance with Example 1, and measurements were performed using them. Table 1 shows the results.

[0050]

Example 6 Ammonium polyphosphate (B11) 16.1
% By weight, nitrogen-containing heterocyclic organic compound (B23) 5.3
5% by weight of a low-density polyethylene (A2) for surface treatment of a flame retardant and various additives according to Example 1 were charged into a Henschel mixer and then stirred and mixed (3 min). The obtained mixture was supplied from the first supply port of the extruder at a rate of 26.9 parts by weight / h.

[0051] On the other hand, pre in a Henschel mixer Each formulation the following ingredients from the second feed port of the same extruder at the following amounts
Then, the composition mixed and stirred (3 min) was supplied (73.6).
Parts by weight / h) and molded into pellets according to Example 1: ethylene-propylene block copolymer (A11)
[PP-2; MFR (230 ° C; 2.16 kgf) 2.
6 g / 10min] 52.9% by weight, - linear low density polyethylene (A12) 10 wt% and ethylene - propylene elastomers (A13) 10 wt% and ... hydrotalcite [abbreviation: HDTCT; trade name:
DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.)] 0.7% by weight.

Using the obtained pellets, a test piece for measurement was prepared according to Example 1, and the measurement was performed using the test piece. Table 2 shows the results.

[0053]

Comparative Example 6 Ammonium polyphosphate (B11) and nitrogen-containing heterocyclic organic compound (B23) were used in a matrix.
The ethylene-propylene block copolymer to be formed (A1
Pellets were obtained according to Comparative Example 1, except that 1), linear low-density polyethylene (A12), ethylene-propylene elastomer (A13) and hydrotalcite were blended in the amounts shown in Table 2, respectively . Using the obtained pellets, a test piece for measurement was prepared in accordance with Comparative Example 1.
The measurement was performed using it. Table 2 shows the results.

[0054] Experimental Results Findings] (1) It can be seen from the results compared between Example 1 and Comparative Example 1 is that prior to melt-kneaded with the polyolefin resin (A1) that form a matrix flame retardant component (B1) By treating the surface with the olefin polymer (A2), the surface appearance of a molded article obtained from the final composition is significantly improved. (2) The results of Example 2 and Comparative Examples 2 and 3 show that when the matrix polyolefin resin (A1) contains a linear low-density polyethylene (A12) and an ethylene-propylene elastomer (A13), The flame retardant component (B1) to be compounded is mixed with an olefin polymer (A
By performing the surface treatment in 2), not only the surface appearance of the molded article obtained from the final composition, but also its tensile elongation and Dupont impact strength are remarkably improved. (3) It can be seen from the results of Example 3 that the flame retardant component (B
The effect is obtained even when the polypropylene resin (A1) is used as the olefin polymer (A2) for surface-treating 1). (4) It can be seen from the results of Examples 4 and 5 and Comparative Examples 4 and 5 that the flame retardant component (B1) is an olefin polymer (A
The weight ratio (A2 / B1) between the surface-treated olefin polymer (A2) and the flame-retardant component (B1) in the flame-retardant (B) previously surface-treated in 2) is in the range of 1/99 to 25/75. In this case, the effect of improving the tensile elongation and the Dupont impact strength of a molded article obtained from the final composition into which the composition is blended is recognized. (5) It can be seen from the results of Example 6 and Comparative Example 6 that, even when the polyolefin resin (A1) serving as the matrix is a polypropylene resin, the flame retardant component (B1) is surface-treated with the olefin polymer (A2). Thereby, the tensile elongation, the DuPont impact strength and the surface appearance of the molded article obtained from the final composition are all improved.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

The composition of the present invention has the following various effects: (1) a polyolefin resin composition exhibiting excellent flame retardancy; (2) corrosive gas during processing or combustion. (3) Suitable for extrusion molding, (4) The composition is suitable as a material for producing buildings, interior decorations, parts for home electric appliances, parts for automobiles, etc. Certain (5) molded articles obtained from the composition have a smooth surface appearance and excellent mechanical properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 5/405 C08K 5/405 9/04 9/04 C08L 61/26 C08L 61/26 // C08L 23:02 (58) Survey Field (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08J 3/20-3/22 C08K 3/32 C08K 5/34-5/357 C08K 5/405 C08K 9/04 C08L 61 / 26

Claims (4)

(57) [Claims] 1. A flame retardant component (B1), which is a combination of the following (B11) and (B2), dispersed in a polyolefin resin (A1) matrix via an olefin polymer (A2) layer adhered to its surface. (B11) Ammonium polyphosphate or melamine-modified ammonium polyphosphate, (B2) at least one selected from the following group: (B21) The following reaction product At least one reaction product selected from the group consisting of: a product group resulting from a reaction of formaldehyde with a cyclic ketone comprising a 5- or more-membered heterocyclic ring containing a nitrogen atom in the ring; (B22) One or more reaction products selected from a reaction product group, wherein the reaction between formaldehyde and a cyclic thioketone composed of a 5- or more-membered heterocyclic ring containing two or more nitrogen atoms in the ring. Or (B23) a group of 1,3,5-triazine derivatives having a structure represented by the following general formula [Chemical Formula 1] [wherein X is a morpholino group or a piperidino group, and Y is a piperazine The divalent group derived and n represents a number from 2 to 50]. Embedded image 2. The flame retardant component (B1) comprising (B11) and (B11)
2) and the ratio (B11 / B2) is 1/1 to 7/1 on a weight basis.
The flame-retardant polyolefin resin composition suitable for extrusion molding according to claim 1 in the range of: 3. A melt flow index MI (190 ° C .; 2.16 kg) of an olefin polymer (A2) for coating a flame retardant component (B1).
The flame-retardant polyolefin resin composition suitable for extrusion molding according to claim 1, wherein f) or MFR (230 ° C; 2.16 kgf) is not less than the flow index of the olefin polymer (A1) serving as a matrix + 5 g / 10 min or more. 4. An extruder provided with a plurality of inlets in a multistage manner from upstream to downstream of an extrusion barrel, wherein an ammonium polyphosphate or a melamine-modified ammonium polyphosphate as a flame retardant component is supplied from a first supply port. The weight ratio of the olefin polymer (A2) to the flame retardant component (B1) comprising a mixture of (B11) and one or more selected from the nitrogen-containing heterocyclic organic compounds (B2) (A2 / B1) 1 / 99-25 / 75
To coat the surface of the flame retardant component (B1) with an olefin polymer, and at the stage when the coating is completed, the polyolefin resin for matrix (A
A method for producing a flame-retardant polyolefin resin composition, comprising melt-kneading while supplying 1).