JPH11228748A - Flame retardant polyolefin resin composition - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a polyolefin resin composition imparted with excellent flame retardancy by non-halogen flame retardation treatment. SOLUTION: 1 to 200 parts by weight of an organically treated swellable clay mineral, 0.5 to 100 parts by weight of each of the clay mineral and a phosphorus compound or 1 to 200 parts by weight of a polyolefin-based resin is used. Part by weight 0.01 to 20% by weight of metal oxide based on the clay mineral.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polyolefin resin composition.

[0002]

2. Description of the Related Art Many polyolefin resins are inherently flammable resins, and with the expansion of applications in recent years, it has been strongly required that they be flame retardant materials. Is being processed. As a method of making a polyolefin resin flame-retardant, a method of adding a halogen-containing compound is generally employed.

[0003] However, the above-mentioned flame-retarding method certainly has the effect of making the flame-retardant, and the decrease in the moldability and the mechanical strength of the molded article is relatively small. Do not use halogen-containing compounds from the viewpoint of safety, as there is a risk of generating system gas, and the generated gas may corrode the equipment or affect the human body.
A so-called non-halogen flame retardant treatment method is strongly desired.

As one of the non-halogen flame retardant techniques for polyolefin resins, a method has been disclosed in which a metal compound such as aluminum hydroxide, magnesium hydroxide, or basic magnesium carbonate, which does not generate harmful gas during combustion, is added. (Japanese Unexamined Patent Publication No. Sho 57-165439, Japanese Unexamined Patent Publication No. Sho 61-36343). However, in order to impart sufficient flame retardancy to a flammable polyolefin resin, it is necessary to add a large amount of a metal compound, and as a result, the mechanical strength of the obtained molded product is significantly reduced, and There was a problem that it was difficult to provide for.

[0005] As another non-halogen flame retarding technique for polyolefin resins, a method has been proposed in which a phosphorus-based flame retardant is added to the resin to utilize the oxygen barrier effect by forming a surface film during combustion. However, in order to impart sufficient flame retardancy to the flammable polyolefin resin, it is necessary to add a large amount of a phosphorus-based flame retardant, and as a result, the mechanical strength of the obtained molded article is significantly reduced, There was a problem that it was difficult to put it to practical use.

[0006]

SUMMARY OF THE INVENTION An object of the present invention, in view of the above, is to provide a polyolefin-based resin composition provided with excellent flame retardancy by a halogen-free flame retarding treatment.

[0007]

The flame-retardant polyolefin-based resin composition (I) according to the first aspect of the present invention (hereinafter referred to as the first invention) comprises a polyolefin-based resin (10).
0 parts by weight and organically treated swellable clay minerals 1 to 2
It is characterized by comprising 100 parts by weight.

The invention according to claim 2 of the present invention (hereinafter referred to as “second
Flame retardant polyolefin-based resin composition (II)) is 100 parts by weight of a polyolefin-based resin, 0.5 to 100 parts by weight of an organically treated swellable clay mineral, and
It is characterized by comprising 0.5 to 100 parts by weight of a phosphorus compound.

The invention according to claim 3 of the present invention (hereinafter referred to as “third”)
Flame retardant polyolefin resin composition (III)), 100 parts by weight of a polyolefin resin, 1 to 200 parts by weight of an organically treated swellable clay mineral, and the organically treated swellable clay mineral 0.01 to 2
It is characterized by being composed of 0% by weight of a metal oxide.

The flame-retardant polyolefin resin composition (I) of the first invention comprises a polyolefin resin and an organically treated swellable clay mineral.

Examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, a poly (1-butene) resin, and a polypentene resin.

The polyethylene resin may be any of a homopolymer of ethylene (low density, medium density, high density), a copolymer containing ethylene as a main component, and a mixture thereof. Examples of the copolymer include an ethylene-α-olefin copolymer containing ethylene as a main component. As the α-olefin, propylene,
Examples thereof include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, and 1-pentene. Further, as the copolymer other than the α-olefin, an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer may be used.

The above-mentioned polypropylene resin may be any of a propylene homopolymer, a copolymer containing propylene as a main component, and a mixture thereof. Examples of the copolymer include a propylene-α-olefin copolymer containing propylene as a main component. α
-As the olefin, ethylene, 1-hexene, 4-
Methyl-1-pentene, 1-octene, 1-butene, 1
-Pentene and the like.

The organically treated swellable clay mineral is a compound having an organic cation such as a quaternary ammonium salt introduced between layers. Examples of the organic component include an aliphatic or aromatic hydrocarbon group. Can be

The organically treated swellable clay mineral contains a hydrocarbon group in the molecule, so that it has good compatibility with the polyolefin resin and is well dispersed when added to the polyolefin resin. The decrease in the mechanical strength of the product can be reduced. In addition, silanol (Si-OH) groups are present in the swellable clay mineral and cause a dehydration reaction during combustion to form a strong crosslinked body, so that thermal decomposition of the resin is suppressed and the flame retardant effect is reduced. Express.

The swellable clay mineral is not particularly limited as long as it is a clay mineral into which an organic cation can be introduced, and examples thereof include smectite, vermiculite, kaolinite, halosite, mica, and layered silicate. Can be
These may be used alone or in combination of two or more.

Among the above-mentioned swellable clay minerals, smectite has an appropriate charge density between layers, and can easily introduce various organic cations, and can increase the amount of the introduced organic cations. Therefore, the dispersibility of the clay mineral is improved, and the flame retardancy is effectively exhibited. Among the above smectite clay minerals, in particular, montmorillonite and hectorite exhibit maximum flame retardancy.

In the flame-retardant polyolefin resin composition (I), the amount of the organically treated swellable clay mineral is 1 to 100 parts by weight of the polyolefin resin.
To 200 parts by weight, preferably 5 to 100 parts by weight. If the compounding amount is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 200 parts by weight, the mechanical strength of the obtained molded article decreases.

Next, the second invention will be described. The flame-retardant polyolefin resin composition (II) of the second invention comprises a polyolefin resin, an organically treated swellable clay mineral, and a phosphorus compound.

As the polyolefin resin and the organically treated swellable clay mineral, those similar to those of the first invention are used.

In the flame-retardant polyolefin resin composition (II), the amount of the organically treated swellable clay mineral is 0% based on 100 parts by weight of the polyolefin resin for the same reason as in the first invention. 0.5 to 100 parts by weight, preferably 2 to 50 parts by weight. When the compounding amount is 0.
If the amount is less than 5 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 100 parts by weight, the mechanical strength of the obtained molded article decreases.

Examples of the phosphorus compound include red phosphorus, ammonium polyphosphate, and phosphorus compounds represented by the following general formula. These may be used alone,
More than one species may be used in combination.

[0023]

Embedded image

In the formula, R ¹ and R ³ are a hydrogen atom, a carbon atom of 1
Represents an alkyl group or an aryl group of ~ 16, R ² is a hydrogen atom or a hydroxyl group, an alkyl group having 1 to 16 carbon atoms,
Represents an alkoxy group, an aryl group or an aryloxy group, which may be the same or different;

The red phosphorus is preferably one in which the surfaces of the red phosphorus particles are coated with a resin in order to prevent moisture spoilage and to prevent spontaneous ignition when kneaded with the polyolefin resin.

As the above-mentioned ammonium polyphosphate, those having been subjected to surface treatment such as melamine denaturation may be used.

Examples of the phosphorus compound include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butylphosphonic acid, 3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid , Diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, and the like.

In the flame-retardant polyolefin resin composition (II), the amount of the phosphorus compound is 0.5 to 100 parts by weight, preferably 2 to 50 parts by weight, per 100 parts by weight of the polyolefin resin. Parts by weight. If the amount is less than 0.5 parts by weight, sufficient flame retardancy cannot be obtained,
If the amount exceeds 00 parts by weight, the mechanical strength of the obtained molded article is reduced.

Next, the third invention will be described. The flame-retardant polyolefin resin composition (III) of the third invention comprises a polyolefin resin, an organically treated swellable clay mineral, and a metal oxide.

As the polyolefin resin and the organically treated swellable clay mineral, those similar to those of the first invention are used.

The above flame-retardant polyolefin resin composition
In (III), the amount of the organically treated swellable clay mineral is 1 to 200 parts by weight, based on 100 parts by weight of the polyolefin resin, for the same reason as in the first invention.
Preferably it is 5 to 100 parts by weight.

The above-mentioned metal oxide functions as a flame-retardant aid, and significantly improves the flame-retardant effect of the organically treated swellable clay mineral with a relatively small amount of addition.

The metal oxide is preferably an oxide of a metal other than an alkali metal, and the oxidation state of the metal is not particularly limited. As such a metal oxide, for example,
Examples include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. These may be used alone or in combination of two or more.

Among the above metal oxides, copper oxide is particularly preferred because it promotes a crosslinking reaction of the organically treated swellable clay mineral and remarkably improves the flame retardant effect.

The above flame-retardant polyolefin resin composition
In (III), the compounding amount of the metal oxide is 0.01 to 20% by weight, preferably 0.5 to 10% by weight of the organically treated swellable clay mineral. Compounding amount is 0.01
When the amount is less than 20% by weight, the effect of the flame retardant aid is not exerted.

The flame-retardant polyolefin resin composition of the present invention includes, for example, phenol-based, amine-based, sulfur-based antioxidants; stabilizers; hydrocarbons, fatty acids, higher alcohols, amides, and the like. A lubricant such as an ester or a metal soap may be added.

The flame-retardant polyolefin resin composition is obtained by uniformly mixing the components with a kneading device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, or a roll. .

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 5) Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight of the organically treated montmorillonite (“ESVEN N-40” manufactured by Toyshun Mining Co., Ltd.)
0 "," Esven D ", and" Esven X ") were supplied to Labo Plastomill, melt-kneaded at 140 ° C, and then the obtained flame-retardant polyethylene resin composition was compression-molded at 140 ° C to prepare a plate sample. Was prepared.

(Comparative Examples 1 to 5) Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight, a predetermined amount of montmorillonite ("Bengel A", "Bengel D15" manufactured by Toyshun Mining Co., Ltd.) and a flame retardant ("AFR" decabromodiphenyl oxide "AFR" manufactured by Asahi Glass Co.) -1021 ", antimony trioxide manufactured by Otsuka Chemical Co., Ltd., and ammonium polyphosphate" AP422 "manufactured by Hoechst) were supplied to Labo Plastomill and melt-kneaded at 140 ° C. A plate sample was prepared by compression molding at 140 ° C.

With respect to the plate samples obtained in the above Examples and Comparative Examples, the following performance evaluations were performed.
And 2.

(1) Combustion test A test specimen (100 mm length × 100 mm width × 3) was prepared in accordance with ASTM E1354 (a method for testing the flammability of building materials).
mm thickness), 50 kW /
m ² of heat, and the maximum heat generation rate (a value representing the heat generation during combustion; the smaller the value, the more the combustion is suppressed and the more flame-retardant) is used as an index of flame retardancy. did.

(2) Elongation at break test JIS K 7113 (Plastic tensile test method)
The elongation at break of a dumbbell specimen (parallel portion 10 mm, width 2.5 mm, thickness 1 mm) was measured under the conditions of a temperature of 23 ° C., a relative humidity of 50%, and a tensile speed of 200 mm / min.

[0044]

[Table 1]

[0045]

[Table 2]

A comparison between the examples and the comparative examples shows that in the examples to which the organically treated montmorillonite was added, the maximum heat generation rate was greatly reduced even though the amount of addition was small (10 to 20 parts by weight). A halogen-based flame retardant of Comparative Example 2,
It can be seen that, compared to the phosphorus-based flame retardant of Comparative Example 3, a very high flame retardant effect is exhibited. In addition, in the montmorillonite without the organic treatment of Comparative Examples 4 and 5, such a flame retardant effect was hardly exhibited, and the importance of the organic treatment was recognized. Furthermore, in the resin composition to which the organically treated montmorillonite is added, since the dispersibility is good, the elongation at break is only slightly lower than the elongation of the polyethylene resin alone, and the decrease in elongation at break is suppressed.

(Examples 6 and 7) Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight of a predetermined amount of organically treated montmorillonite ("ESVEN X" manufactured by Toyshun Mining Co., Ltd.) and a phosphorus compound (ammonium polyphosphate "AP422" manufactured by Hoechst Co., Ltd.) A phenylphosphonic acid (manufactured by Kagaku Co.) was supplied to Labo Plastomill and melt-kneaded at 140 ° C., and then the obtained flame-retardant polyethylene resin composition was compression-molded at 140 ° C. to prepare a plate sample.

(Comparative Examples 6 to 8) Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight of the phosphorus compound (ammonium polyphosphate “AP42” manufactured by Hoechst) in a predetermined amount shown in Table 1.
2 ") and a flame retardant (Decabromodiphenyl oxide" AFR-1021 "manufactured by Asahi Glass Co., Ltd .; antimony trioxide manufactured by Otsuka Chemical Co., Ltd.) to Labo Plastmill and supplied to 140 [deg.] C.
After melt-kneading at 140 ° C., the obtained flame-retardant polyethylene-based resin composition was compression-molded at 140 ° C. to produce a plate sample.

With respect to the plate samples obtained in Examples 6 and 7 and Comparative Examples 6 to 8, (1)
Performance evaluation was performed for the combustion test and (2) elongation at break test, and the results are shown in Table 3.

[0050]

[Table 3]

Comparing Examples 6 and 7 with Comparative Examples 6 to 8, it was found that in Examples 6 to 8 to which the organically treated montmorillonite was added, the maximum heat was generated despite the small amount (10 parts by weight). It can be seen that the speed is greatly reduced, and a very high flame retardant effect is exhibited as compared with the halogen-based flame retardant of Comparative Example 7 and the phosphorus-based flame retardant of Comparative Example 8. Furthermore, in the resin composition to which the organically treated montmorillonite is added,
Since the dispersibility is good, the elongation at break is only slightly lower than the elongation of the polyethylene resin alone, and the decrease in elongation at break is suppressed.

Examples 8 to 19 Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight, a predetermined amount of organically treated montmorillonite (“Sven X” manufactured by Toyshun Mining Co., Ltd.) and a metal oxide [silicon dioxide “MC-90” manufactured by Asahi Glass Co., Ltd .; Magnesium oxide (heavy), aluminum oxide, calcium oxide, titanium oxide (IV), manganese oxide (IV), iron oxide (III), cobalt oxide (II), nickel oxide (II), copper oxide ( I), copper (II) oxide, zinc oxide] to Labo Plastomill
After melt-kneading at 40 ° C., the obtained flame-retardant polyethylene resin composition was compression-molded at 140 ° C. to prepare a plate sample.

(Comparative Examples 9 to 11) Polyethylene resin (manufactured by Mitsubishi Chemical Corporation, density: 0.92 g / cm ³ , MI = 3.
4) 100 parts by weight and a predetermined amount of a flame retardant shown in Table 5 (Aca-Glass Inc., decabromodiphenyl oxide “AFR-
1021 ", antimony trioxide manufactured by Otsuka Chemical Co., Ltd., and ammonium polyphosphate" AP422 "manufactured by Hoechst) were supplied to Labo Plastomill and melt-kneaded at 140 ° C. A plate sample was prepared by compression molding at ℃.

With respect to the plate samples obtained in Examples 8 to 19 and Comparative Examples 9 to 11, (1)
Performance evaluation was performed for the combustion test and (2) elongation at break test, and the results are shown in Tables 4 and 5.

[0055]

[Table 4]

[0056]

[Table 5]

Comparison between Examples 8 to 19 and Comparative Examples 9 to 11 shows that in Examples 8 to 19 in which the organically treated montmorillonite and metal oxide were added, the total amount of addition was small (11 parts by weight). Nevertheless, it can be seen that the maximum heat generation rate is greatly reduced, and a very high flame retardant effect is exhibited as compared with the use of the halogen-based flame retardant of Comparative Example 10 and the phosphorus-based compound of Comparative Example 11. Among metal oxides, especially copper oxide has a remarkable effect as a flame retardant aid. Furthermore, in the resin composition to which the organically treated montmorillonite is added, since the dispersibility is good, the elongation is slightly lower than the elongation of the polyethylene-based resin alone, and the decrease in elongation is suppressed.

[0058]

The polyolefin resin composition of the present invention has the above-mentioned constitution, has excellent flame retardancy and elongation at break, and does not generate a halogen-based gas at the time of combustion or molding. Since it can be easily manufactured, it can be used for a wide range of applications requiring flame retardancy.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 3:02 3:32 5:51) (C08K 13/06 9:04 3:22)

Claims (7)

[Claims] 1. A flame-retardant polyolefin resin composition comprising 100 parts by weight of a polyolefin resin and 1 to 200 parts by weight of an organically treated swellable clay mineral. 2. A flame retardant composition comprising 100 parts by weight of a polyolefin resin, 0.5 to 100 parts by weight of an organically treated swellable clay mineral, and 0.5 to 100 parts by weight of a phosphorus compound. Polyolefin resin composition. 3. 100 parts by weight of a polyolefin resin, 1 to 200 parts by weight of an organically treated swellable clay mineral, and
0.01 to the organically treated swelling viscosity mineral
A flame-retardant polyolefin-based resin composition comprising 20% by weight of a metal oxide. 4. The flame-retardant polyolefin-based resin composition according to claim 1, wherein the swellable clay mineral is smectite. 5. The flame-retardant polyolefin resin composition according to claim 4, wherein the smectite is at least one selected from montmorillonite and hectorite. 6. The flame-retardant polyolefin-based compound according to claim 2, wherein the phosphorus-based compound is at least one selected from red phosphorus, ammonium polyphosphate, and a phosphorus compound represented by the following general formula. Resin composition. Embedded image (Wherein, R ¹ and R ³ represent a hydrogen atom, an alkyl group or an aryl group having 1 to 16 carbon atoms, and R ² represents a hydrogen atom or a hydroxyl group, an alkyl group having 1 to 16 carbon atoms or an alkoxy group. , An aryl group or an aryloxy group, which may be the same or different) 7. The method according to claim 7, wherein the metal oxide is magnesium oxide,
Aluminum oxide, silicon oxide, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide,
The flame-retardant polyolefin resin composition according to claim 3, wherein the composition is at least one selected from iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide.