JP3193017B2 - Non-halogen flame-retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has the same flame retardancy as a polyvinyl chloride (PVC) composition, and has a specific gravity of PVC.
The present invention relates to a flame-retardant resin composition which is smaller than the composition, can be separated by specific gravity, does not contain halogen, and can be incinerated.

[0002]

2. Description of the Related Art PVC compositions are widely used in wire coatings, tubes, tapes, packaging materials, building materials, etc. because of their good electrical insulation and self-extinguishing flame retardancy. Incidentally, since the PVC composition contains chlorine (Cl) which is a halogen, a corrosive gas such as HCl or a toxic gas such as dioxin is generated during combustion. Therefore, various PVC
There was a problem that when products became waste, they could not be incinerated. Therefore, at present, landfill disposal is performed. However, since a Pb-based stabilizer is used as an additive in the PVC composition, there is also a problem that this is eluted into soil and the like, and it is difficult to dispose of it as industrial waste. It has become to.

[0003]

On the other hand, PVC
If a halogen-free polyethylene (PE) or polypropylene (PP) is used as a resin composition instead of
Since no harmful gas is generated during combustion, incineration is possible. However, these halogen-free resin compositions are made of PVC.
However, there is a drawback that the flame retardancy is inferior to the above. For example, comparing the oxygen index (OI) which is an evaluation scale of the flame retardancy of the resin composition, the OI of PVC is 23 to 40, whereas the OI of PE and PP is inferior to about 17 to 19. You can see that there is.

Therefore, in order to impart flame retardancy to a halogen-free resin composition such as PE or PP, a water-containing inorganic compound such as Mg (OH) ₂ is usually added to these. However, the specific gravity of the water-containing inorganic compound is large, and in order to obtain the same flame retardancy as PVC, it is necessary to add 120 parts by weight or more of the water-containing inorganic compound. The specific gravity of the flame-retardant resin composition containing no is almost the same as that of PVC. For this reason, there has been a problem that the specific gravity of a plastic using water as a specific gravity liquid as described below cannot be separated. That is, in order to recycle the recovered plastic or to remove PVC that generates dioxin during combustion, the plastic is put into uniformly flowing water, and separated according to the difference in specific gravity of the plastic. For example, as shown in FIG.
The olefin-based plastic 1 such as P or PE has a specific gravity lower than that of water (specific gravity of about 0.9), so that it rises to the surface of the water, and PVC2 (specific gravity of about 1.3) having a higher specific gravity than water sinks in the water. Styrene plastic 3 (specific gravity about 1.1)
Follows a different sedimentation trajectory from PVC2 because the specific gravity is greater than water and less than PVC2,
At the bottom of the sorting tank, styrene plastic 3 and PVC2
There are two types of accumulation distributions. Therefore, by utilizing this property, it is possible to separate the above-mentioned three types of plastics. However, since the above-described halogen-free flame-retardant resin composition and PVC have the same specific gravity, There was a disadvantage that it was not possible to separate the.

The present invention has been made in view of the above circumstances, and is a resin which has the same level of flame retardancy as PVC, does not generate harmful gases during incineration, and can be separated from PVC by specific gravity. It is intended to provide a composition.

[0006]

The object of the present invention is to provide a water-insoluble inorganic compound as a flame retardant of 5 to 50 parts by weight and a density of less than 1.5 g / cm ³ with respect to 100 parts by weight of a polyolefin resin. And 1 to 55 parts by weight of a flame-retardant adjuvant having one or both of an action of forming a shell-like heat-insulating layer by combustion and an action of foaming at high temperature to confine steam. Is 1.
14 or less, an oxygen index of 24 or more, a heavy metal content of less than 0.1% by weight, and as the flame-retardant auxiliary, a gum-like silicone oil having a molecular weight of 300,000 to 1,000,000, silicone powder, and silicone-modified From polymers
The non-halogen flame-retardant resin composition is characterized by using one or more selected from the group consisting of:
Further, it is preferable to add 0.1 to 2.0 parts by weight of an antioxidant.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention, a polyolefin-based resin containing no halogen, while adding a hydrous inorganic compound as a flame retardant,
By using a flame-retardant auxiliary in combination, favorable flame retardancy and low specific gravity can be achieved at the same time. The flame-retardant resin composition containing no halogen of the present invention (hereinafter referred to as non-halogen flame-retardant resin composition) has a specific gravity of 1.1.
It is prepared so that the oxygen index (OI) is 4 or less and the oxygen index (OI) is 24 or more. When the specific gravity of the non-halogen flame-retardant resin composition is larger than 1.14, it becomes difficult to separate the specific gravity from the PVC. When the OI of the non-halogen flame-retardant resin composition is 24 or more, flame retardancy equivalent to PVC can be obtained.

The polyolefin resin used in the present invention includes, for example, linear low density polyethylene (LLDP)
E), very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDP)
E), polyethylene (PE) such as high-density polyethylene (HDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer Combination (EBA), ethylene- propylene rubber (EPR), and olefin-based copolymer are preferred.
An acid-modified polyolefin modified by reacting an unsaturated carboxylic acid such as maleic anhydride or acrylic acid or a derivative thereof during or after polymerization of these polyolefin resins can also be used. These resins are 1
Species may be used alone or as a mixture of two or more. In particular, ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate copolymer (EEA) are preferable because the flame retardancy of the resin itself is relatively high, and these are each used alone or appropriately mixed with other resins. It is preferable to use them. For example, EVA and EP
When R is used as a mixture, the EVA is preferably 80 to 40 (% by weight) and the EPR is preferably 20 to 60 (% by weight). When EVA or EEA is used, it is particularly preferable that the content of the comonomer (VA, EA) used for copolymerization with ethylene is 15 to 40% by weight. When the content of the comonomer is less than this, the flame retardancy is inferior, and when it is more than this, the pellets stick together due to stickiness (adhesion) and the workability at the time of extrusion is unfavorably deteriorated.

The hydrated inorganic compound used in the present invention may be any compound which decomposes into oxides and water vapor during combustion to exhibit flame retardancy. For example, magnesium hydroxide (Mg (O
H) ₂ ) and aluminum hydroxide are preferably used. Particularly, magnesium hydroxide is preferable, and magnesium hydroxide surface-treated with stearic acid, an oxalate anion, a silane coupling agent, or the like is more preferably used for reasons such as an improvement in affinity with a resin and thermal decomposition characteristics. For example, when magnesium hydroxide (Mg (OH) ₂ ) is added to a polyolefin resin, magnesium hydroxide is decomposed into an oxide and water vapor during combustion, thereby lowering the temperature and reducing the temperature of the burned part due to the generated water vapor. Reduce the supply of oxygen. Further, it is possible to prevent the flame from spreading to a new resin surface due to the attachment of the oxide to the burned portion.

[0010] The amount of the water-containing inorganic compound to be added is in the range of 5 parts by weight or more and less than 50 parts by weight based on 100 parts by weight of the polyolefin resin. If the amount of the water-containing inorganic compound is too small, favorable flame retardancy cannot be obtained. If the amount is too large, the specific gravity of the obtained halogen-free flame-retardant resin composition becomes too large, so that the specific gravity cannot be separated from PVC. When magnesium hydroxide is used alone as the water-containing inorganic compound, the amount of magnesium hydroxide is preferably 5 parts by weight or more and less than 50 parts by weight, more preferably 30 parts by weight or more, based on 100 parts by weight of the polyolefin resin. 5
Less than 0 parts by weight. When a molybdenum compound described below is coated on a water-containing inorganic compound and used, the amount of the water-containing inorganic compound added can be 5 to 40 parts by weight. In particular, aluminum hydroxide, calcium carbonate and magnesium hydroxide treated with ammonium molybdate exhibit good results.

The flame-retardant auxiliary used in combination with the water-containing inorganic compound has a density of less than 1.5 g / cm ³ and, when used in combination with the water-containing inorganic compound, improves the flame-retardancy by adding a small amount. Any of organic and inorganic substances may be used as long as they contribute. Further, those not containing heavy metals such as Pb are preferable. Further, such a flame retardant aid forms a heat insulating layer in the form of a shell due to a high temperature (500 ° C. or more) due to combustion, and remarkably foams at a high temperature (400 ° C.) to contain water vapor (water) therein. Are those that produce the effect of confining or that simultaneously produce those effects. The addition amount of the flame retardant auxiliary is set so that the specific gravity of the non-halogen flame retardant resin composition does not exceed 1.14 when used in combination with the water-containing inorganic compound, and is preferably based on 100 parts by weight of the polyolefin resin. 1 part by weight or more 5
Not more than 5 parts by weight.

As an example of the flame retardant auxiliary in the present invention, a silicone compound can be mentioned. Preferred examples of the silicone compound include gum-like silicone oil and silicone powder. Silicone powder is an organopolysiloxane polymer having a methyl group and a phenyl group. The gum silicone oil has a high viscosity of about 300,000 to 1,000,000 in molecular weight. These silicone compounds form a shell-like heat-insulating layer by combustion and improve flame retardancy. Also, since the density of gum-like silicone oil and silicone powder is smaller than that of magnesium hydroxide, the amount of magnesium hydroxide added is reduced, and instead the addition of gum-like silicone oil and / or silicone powder results in low specific gravity and high density. It is possible to simultaneously achieve flame retardancy.
In particular, since gum-like silicone has a lower specific gravity than silicone powder, it is possible to increase the amount of magnesium hydroxide or the like by using the same, so that a resin composition having low specific gravity and high flame retardancy can be obtained. It is effective for On the other hand, silicone powder is a powder and can be dispersed in other powder materials in advance, and is easier to disperse than gum-like silicone oil, which is advantageous in that kneading time can be shortened. is there.

When adding a gum-like silicone oil,
The preferable addition amount is 1 part by weight or more and 40 parts by weight or less based on 100 parts by weight of the polyolefin resin, and when silicone powder is added, the preferable addition amount is 3 parts by weight or more based on 100 parts by weight of the polyolefin resin. 55 parts by weight or less. In addition, gum-like silicone oil and silicone powder can be used in combination. If the added amount of the gum-like silicone oil and / or the silicone powder is too small, the effect of adding the flame retardant is not obtained. I can not expect much.

Further, as a silicone compound other than the above gum-like silicone oil and / or silicone powder, there is a silicone-modified polymer. Specific examples include silicone-modified polyethylene, silicone-modified ethylene-vinyl acetate copolymer, silicone-modified ethylene-ethyl acrylate copolymer, and silicone-modified ethylene-methyl methacrylate copolymer. The preferable addition amount of such a silicone-modified polymer is 3 parts by weight or more and 30 parts by weight with respect to 100 parts by weight of the polyolefin resin.
It is at most 5 parts by weight, particularly preferably at least 5 parts by weight and at most 20 parts by weight. If the addition amount of these silicone-modified polymers is too small, the effect of adding flame retardancy cannot be obtained, and if the addition amount exceeds the above range, the cost of raw materials increases but the improvement of flame retardancy cannot be expected much.

Further, there is a molybdenum compound as an inorganic flame retardant aid. Specific examples include oxides such as molybdenum trioxide, sulfides such as molybdenum disulfide, and molybdates such as ammonium dimolybdate, calcium molybdate, zinc molybdate, potassium molybdate, and sodium molybdate. . These may be used alone or in combination of two or more. Further, it is preferable that these compounds are coated on the surface of a hydrous inorganic compound.

It is preferable to further add an antioxidant. The anti-aging agent is not particularly limited, but for example, phenol-based and amine-based agents can be preferably used. If the amount of the antioxidant is too small, the effect of the addition cannot be obtained. If the amount is too large, blooming or bleed out may occur.
It is preferably from 0.1 part by weight to 2.0 parts by weight based on part by weight.

In the present invention, a water-containing inorganic compound is added to a polyolefin resin, and the molecular weight is from 300,000 to 10
100,000 gum-like silicone oil, silicone powder,
And selected from the group consisting of silicone-modified polymers
By adding at least one flame retardant auxiliary as an essential component, low specific gravity and high flame retardancy are simultaneously achieved, and when used as a coating material for electric wires, cables or similar products, the Electric Appliance and Material Control Law, UL standard, IEEE standard 383,
And a non-halogen flame-retardant resin composition having a low specific gravity that passes at least one of the combustion tests specified in IEC Standard 332-1. According to the present invention, more preferably, the Electric Appliance and Material Control Law and U
It is possible to obtain a non-halogen flame-retardant resin composition having low specific gravity and high flame retardancy, which passes both tests of the L standard, and more preferably all flame tests.

In addition to the above-mentioned compounding agents, ultraviolet absorbers, crosslinking agents, copper damage inhibitors, pigments, dyes and other coloring agents,
A suitable additive such as a small amount of inorganic fine powder such as talc or the like can be blended according to the intended use. The additive is selected from those that do not contain halogen or, particularly, lead (Pb). Further, it is preferable that harmful heavy metals such as cadmium (Cd) are not contained as much as possible, and it is preferable that the content of harmful heavy metals in the non-halogen flame-retardant resin composition of the present invention is suppressed to less than 0.1% by weight. As a crosslinking agent, dicumyl peroxide (DPC), vinyltrimethoxysilane, or the like can be preferably used . Furthermore, when the non-halogen flame-retardant resin composition of the present invention is used as an insulating material, the volume resistivity is preferably set to 1 × 10 ¹³ (Ω · cm) or more. When heat resistance is required, the non-halogen flame-retardant resin composition may be cross-linked by irradiating it with an electron beam as needed.

According to the non-halogen flame-retardant resin composition of the present invention, a resin composition having the same self-extinguishing flame retardancy as PVC can be obtained. This non-halogen flame-retardant resin composition hardly burns in a fire and emits a small amount of smoke. Also, because it does not contain halogen, it does not generate toxic gases such as dioxin and halogen gas during combustion, so it can be incinerated.
No toxic gas is emitted in case of fire. In addition, since the specific gravity is smaller than that of PVC, it can be easily separated from PVC by specific gravity separation using flowing water as a specific gravity liquid. Therefore, it is possible to recycle by separating and collecting, and it is possible to recover heat as fuel or reuse as material. Furthermore, since it does not contain a phosphorus compound, it is environmentally preferable, and since there is no elution of lead, landfill disposal is possible. When a silicone compound is added, the weather resistance of the resin can be improved. It has been widely known that carbon black is added to improve the weather resistance of a resin.
When carbon black is added, the resin composition is colored black, so that it becomes difficult to color the resin composition to another color tone. On the other hand, if a silicone compound is added, weather resistance can be improved, and a resin composition having good coloring properties can be obtained because the resin does not become dark.

The non-halogen flame-retardant resin composition of the present invention includes, for example, insulated wires, electronic device wiring wires, automobile wires, device wires, power cords, outdoor distribution insulated wires, power cables, control cables, Insulation materials, sheath materials, tapes, and inclusions for various cables and cables such as communication cables, instrumentation cables, signal cables, transfer cables, and ship cables, as well as wires and cables for cases, plugs, and tapes. Cable accessories (specifically, shrink tubing, rubber stress relief cones, etc.), electrical materials such as conduits, wiring ducts, and bus ducts, as well as agricultural seats, water hoses, gas pipe coverings, and building interiors It is suitable for materials, furniture materials, toy materials, floor materials and the like. In particular, when the halogen-free flame-retardant resin composition of the present invention is used for electric wires and power cords, a product having excellent flexibility, good plug bending characteristics, and excellent plug portion tracking resistance can be obtained. .

[0021]

EXAMPLES Hereinafter, the effects of the present invention will be clarified by showing specific examples. As examples and comparative examples of the present invention,
Various components were blended in the blending ratios (units: parts by weight) shown in Tables 1 and 2 below, and kneaded with a kneader to obtain a resin composition. Although not described in the table, in Example 11, 1 part by weight of DCP was used as a crosslinking agent, and in Example 12, DCP was used.
0.1 parts by weight of P and 1.8 parts of vinyltrimethoxysilane
Parts by weight were added. In order to conduct a combustion test, the resin composition after kneading was coated on a 2 mm ² conductor with a thickness of 0.8 mm using an extruder to produce an electric wire. Examples 11 and 12
Regarding the above, after coating with the resin composition, electron beam irradiation was performed to crosslink. The combustion test is performed using this electric wire by using a 60 ° inclined combustion test established by the Electricity Control Law combustion test, a vertical combustion test established by UL standard VW-1, and an IEC standard 33
The test was performed according to the vertical tray combustion test defined in 2-1 and IEEE Standard 383, respectively. The results are shown in the table. Further, the oxygen index (OI) according to the test method of JIS K7201, the tensile strength, the elongation, and the specific gravity of the resin composition according to the method described in JIS K7113 were measured. The results are shown in the table. Evaluation of tensile strength is 1k
gf / mm ² or more was indicated as OK and 1 kgf / mm ^{2 or} less as NG. For elongation, OK is 250%
NG was less than 150%.

[0022]

[Table 1]

[0023]

[Table 2]

In the above Examples and Comparative Examples, the following were used as the respective resins and compounding agents. EVA: Melt flow rate (hereinafter referred to as MFR)
2.5, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 19% EEA: MFR = 0.5, an ethyl acrylate content of 2
0% ethylene-ethyl acrylate copolymer EPR: ethylene-propylene rubber, EP manufactured by Mitsui Chemicals, Inc.
T # 3045 Magnesium hydroxide: stearic acid surface-treated magnesium hydroxide, density 2.36 g / cm ³ Molybdenum compound: manufactured by Kikuchi Color Co., Ltd., Bowen 803 Silicone gum: gum-like silicone oil, manufactured by Shin-Etsu Silicone Co., density 0.985 g / cm ³ silicone powder: DC4-7081, manufactured by Dow Corning Toray Silicone Co., Ltd., density 1.20 g / cm ³ antioxidant (antiaging agent): manufactured by Ciba Geigy, Ir
ganox1010

[0025]

As described above, according to the present invention, P
A non-halogen flame-retardant resin composition having the same flame retardancy as VC and containing no halogen can be incinerated. Further, since it contains almost no heavy metal, it can be landfilled, and since it contains no phosphorus-based compound, it is environmentally preferable. Further, since the non-halogen flame-retardant resin composition of the present invention has a specific gravity of 1.14 or less, it can be separated from PVC by specific gravity separation. Further, the halogen-free flame-retardant resin composition obtained by adding a gum-like silicone oil and / or a silicone powder as a flame-retardant auxiliary has excellent weather resistance and good coloring properties. According to the present invention, when used as a covering material for electric wires, cables or the like, the Electric Appliance and Material Control Law, UL
Standards, IEEE Standard 383, and IEC Standard 332-
Thus, a non-halogen flame-retardant resin composition having high practicability can be passed, because it can pass one or more of the combustion tests respectively defined in No. 1.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a sedimentation trajectory of plastic in a water flow.

[Explanation of symbols]

1: olefin plastic, 2: polyvinyl chloride,
3: Styrene-based plastic

──────────────────────────────────────────────────続 き Continuing from the front page (72) Takashi Shinmoto, Inventor Fujikura Ltd., 1-1-1, Kiba, Koto-ku, Tokyo (72) Inventor Koichi Iinuma 1-1-1, Kiba, Koto-ku, Tokyo, Japan Stock Company Inside Fujikura (72) Inventor Takashi Edo 1-5-1 Kiba, Koto-ku, Tokyo Inside Fujikura Corporation (72) Inventor Jun Suzuki 1-1-5-1 Kiba, Koto-ku, Tokyo Fujikura Inside (72) Invention Person Hiroshi Matsui 1-5-1, Kiba, Koto-ku, Tokyo Inside Fujikura Co., Ltd. (56) References JP-A 5-262926 (JP, A) JP-A 7-238178 (JP, A) JP-A 5- 295266 (JP, A) JP-A-5-194795 (JP, A) JP-A-2-261844 (JP, A) JP-A-63-159473 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08 L 23/00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] Respect 1. A polyolefin resin 100 parts by weight, the water-containing inorganic compound 5 parts by weight or more but less than 50 parts by weight as flame retardant, and density less than 1.5 g / cm ^3, and shell-like thermal insulation by combustion A flame-retardant adjuvant having one or both of the function of forming a layer and the function of foaming at high temperatures to trap water vapor is mixed in an amount of 1 part by weight or more and 55 parts by weight or less. Is a halogen-free flame-retardant resin composition having a content of heavy metal of less than 0.1% by weight and having a molecular weight of from 300,000 to 1,000,000, silicone powder and silicone powder as the flame-retardant auxiliary. , And Siri
A non-halogen flame-retardant resin composition comprising at least one selected from the group consisting of cone-modified polymers . 2. The non-halogen flame-retardant resin composition according to claim 1, further comprising 0.1 to 2.0 parts by weight of an antioxidant.