JP2005239795A - Eco-friendly chlorine-containing resin blend - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare an eco-friendly chlorine-containing resin blend which is inexpensive and flame-retardant and in which generation of hydrogen chloride gas, dioxins, smoke and furan is reduced. <P>SOLUTION: This low-hazardous eco-friendly chlorine-containing resin blend comprises (a) at least one particulate filler selected from at least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide each having an average particle size of 1mμ or less, particulate calcium carbonate having an average particle size of 0.1 mμ or less, and particulate silica having an average particle size of 0.1 mμ or less, (b) at least one stabilizer selected from calcium stearate, barium stearate and hydrotalcite, and (c) at least one metallic compound selected from molybdenum oxide, zinc stannate, zinc borate, zinc sulfide and zinc oxide. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to an environment-friendly chlorine-containing resin composition, and more particularly to an environment-friendly chlorine-containing resin composition having improved flame retardancy, low toxicity and low smoke generation.

Conventionally, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, and the like are known as chlorine-containing resins. For example, a polyvinyl chloride compound is mixed with a stabilizer or a plasticizer to improve moldability, It has been done to obtain long-term stability of the resulting product. The vinyl chloride resin product comprising the polyvinyl chloride compound thus obtained is often discarded or incinerated after use, and when incinerated, hydrogen chloride gas, dioxin, In addition to the generation of harmful gases such as dechlorination cyclization during pyrolysis, that is, dehydrochlorination, and the cyclization reaction has the disadvantage that the generation of carbon particles increases the amount of smoke generated. Hydrogen chloride gas, dioxin, furan and the like are not preferable in terms of causing environmental pollution. In the conventional polyvinyl chloride compound, by adding calcium carbonate or mixing calcium carbonate powder and iron oxide powder, it is possible to prevent the production of hydrogen chloride to some extent during combustion, but the production of dioxin We cannot expect big effect to suppress. Recently, a method has been disclosed in which a complex oxide of calcium and iron is dispersed in a chlorine-containing resin to capture toxic hydrogen chloride effectively during combustion (see, for example, Patent Document 1). Furthermore, a flame-retardant vinyl chloride resin molded article in which titanium oxide powder is contained in a vinyl chloride resin to reduce the amount of chlorine gas and hydrogen chloride generated during thermal decomposition is disclosed (for example, see Patent Document 2). Furthermore, the present applicant has found that a low harmful flame retardant composed of vinyl chloride resin and a fumed silica containing a hydrated metal compound, hydrotalcite, calcium carbonate, molybdenum oxide, zinc stannate and zinc oxide and a fumed silica. A basic chlorine-containing resin blend has been disclosed (see, for example, Patent Document 3). On the other hand, halogen-free flame retardant materials have been developed and put into practical use instead (see, for example, Patent Document 4).
JP-A-11-286573 (paragraph 0028) JP 11-323051 A (paragraph 0008) JP2003-64234 (paragraph 0006) JP-A-2002-241545 (Claims)

  Thus, it is described that hydrogen chloride can be prevented from being produced during combustion by adding calcium carbonate to a conventional chlorine-containing resin and mixing calcium carbonate powder and iron oxide powder. However, there is no description about dioxin. Moreover, although the technique described in the said patent document 1 and the patent document 2 can reduce the generation amount of chlorine gas and hydrogen chloride, it is inadequate about adsorption | suction of a dioxin or smoke. In addition, the conventional polyvinyl chloride compound listed as a comparison in the Examples has a reduced amount of HCl generation, but a much larger amount of dioxin, for example, polydichlorodibenzoyl dioxin is 32 ng / g, polydichlorodi The amount of benzoylfuran is as large as 2200 ng / g, and the amount of smoke generated is as high as 450 (specific optical density). Even though the amount of HCl generated can be suppressed to some extent, it is still not sufficient. Furthermore, the technique described in Patent Document 3 was proposed by the applicant, and this composition is effective in suppressing not only hydrogen chloride gas but also dioxin generation as much as possible, improving flame retardancy, and suppressing smoke generation. It is preferable. On the other hand, materials having excellent flame retardancy, oil resistance, and plasticity have been developed without using chlorine-containing resins, but they are still economically expensive and currently lacking demand. Therefore, the present inventors have conducted various studies in view of this point, and as a result, mainly use low-priced chlorine-containing resin blends to suppress the generation amount of dioxins as well as hydrogen chloride gas and improve flame retardancy. In addition, a novel environmentally friendly chlorine-containing resin compound that can suppress the amount of smoke generation and suppress the generation of harmful gases such as furan has been found, and the present invention has been made here.

  Accordingly, the first problem to be solved by the present invention is that it is inexpensive, increases the reaction efficiency between harmful substances and compounding agents during combustion, promotes flame retardancy, and reduces the amount of hydrogen chloride gas and dioxin generated. An object of the present invention is to provide a low harmful environment-friendly chlorine-containing resin composition that can reduce the amount of smoke generated. In addition, the second problem to be solved by the present invention is inexpensive, flame retardant, can reduce the generation amount of hydrogen chloride gas and dioxin, and can suppress the generation amount of smoke, and further, the generation amount of furan. It is an object of the present invention to provide a low-hazardous environment-friendly chlorine-containing resin compound capable of suppressing the above-described problems.

The above-described problems of the present invention are achieved by the following inventions.

The above-described problems of the present invention are achieved by the following inventions.
(1) A low-hazardous environment characterized in that the chlorine-containing resin contains (a) a low-hazardous flame retardant, and further includes a combination of (b) and (c) with a flame-retardant and less fuming property. Corresponding chlorine-containing resin compound.
(A) At least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and fine particles having an average particle size of 0.1 mμ or less At least one particulate filler selected from silica (b) at least one stabilizer selected from calcium stearate, barium stearate and hydrotalcite (c) molybdenum oxide, zinc stannate, zinc borate, zinc sulfide and At least one metal compound selected from zinc oxide (2) In proportion to 100 parts by weight of chlorine-containing resin, (a) a low-hazardous flame retardant, and (b) and (c) flame retardancy and fuming A low-hazardous, environmentally friendly chlorine-containing resin compound characterized by containing a compounding agent with low properties.
(A) At least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and fine particles having an average particle size of 0.1 mμ or less 5 to 200 parts by weight of at least one fine particle filler selected from silica (b) at least one stabilizer selected from calcium stearate, barium stearate and hydrotalcite (c) molybdenum oxide, 0.5 to 20 parts by weight of at least one metal compound selected from zinc stannate, zinc borate, zinc sulfide and zinc oxide. (3) As a low harmful flame retardant, (d) nanofillers or EVA and montmorillonite. The environmentally friendly salt according to item 1 or 2, characterized by containing the nanocomposite MB of Containing resin blend.
(4) The low-hazardous flame retardant contains (e) an aromatic compound selected from a novolak phenol resin or an aromatic phosphorus compound, according to any one of items 1 to 3 above. Environment-friendly chlorine-containing resin compound.
(5) (d) Environment-friendly chlorine according to item 3 or 4 above, containing 0.4 to 6.0 parts by weight of nanofillers or EVA and montmorillonite nanocomposite MB Containing resin formulation.
(6) Environmental support according to any one of items 3 to 5 above, which contains 1 to 50 parts by weight of an aromatic compound selected from (e) a novolak phenol resin or an aromatic phosphorus compound. Type chlorine-containing resin compound.
(7) The component of the low harmful flame retardant is aluminum hydroxide having an average particle size of 1 mμ or less, fine particle calcium carbonate having an average particle size of 0.1 mμ or less, fine particle silica having an average particle size of 0.1 mμ or less, nanofiller MB, novolak The above-mentioned items 3 to 6, characterized in that they comprise a combination of phenolic resins, the ingredients of the compounding agent are calcium stearate and barium stearate, and the metal compound is a combination of molybdenum oxide and zinc stannate. The environmentally friendly chlorine-containing resin blend according to any one of the above.

  According to the environment-friendly chlorine-containing resin composition described in item 1 of the present invention, the chlorine-containing resin contains (i) a low harmful flame retardant, and (b) and (c) flame retardancy; By including a compound with low fuming properties, these synergistic effects are demonstrated, reducing the amount of chlorinated dioxins, reducing the amount of hydrogen chloride gas generated, reducing the amount of fuming, and further improving flame retardancy This is an excellent effect that can be achieved. In addition, the environment-friendly chlorine-containing resin composition described in item 2 of the present invention is optimally generated with respect to the generation amount of hydrogen chloride gas and dioxin by defining the component ratio in the invention described in item 1. Can be reduced, the amount of smoke generated can be suppressed, and the flame retardancy can be further improved. Further, the environment-friendly chlorine-containing resin composition described in item 3 of the present invention is the (d) nanofillers, or the low harmful flame retardant, in the invention described in item 1 or 2. By containing the nanocomposite MB of EVA and montmorillonite, it is possible to further reduce the generation amount of hydrogen chloride gas and dioxin, suppress the smoke generation amount, and further improve the flame retardancy. The environment-friendly chlorine-containing resin composition described in item 4 of the present invention described above is the (v) novolak phenol resin or aromatic as a low-hazardous flame retardant in the invention described in item 1 or 2. By containing an aromatic compound selected from phosphorus compounds, the amount of hydrogen chloride gas and dioxin generated can be further reduced, the amount of smoke generated can be suppressed, and the flame retardancy can be further improved. The environment-friendly chlorine-containing resin composition described in the fifth aspect of the present invention is the invention described in the third or fourth aspect, wherein (d) the nanofiller or the nanocomposite MB of EVA and montmorillonite is used. By limiting the addition ratio, the generation amount of hydrogen chloride gas and dioxin can be reduced more appropriately, the smoke generation amount can be suppressed, and the flame retardancy can be further improved. The environmentally friendly chlorine-containing resin composition described in item 6 of the present invention is selected from (e) a novolak phenol resin or an aromatic phosphorus compound in the invention described in any one of items 3 to 5. By limiting the ratio of the aromatic compound added, the generation amount of hydrogen chloride gas and dioxin can be reduced more appropriately, the smoke generation amount can be suppressed, and the flame retardancy can be further improved. The environment-friendly chlorine-containing resin composition according to Item 7 of the present invention is the invention according to any one of Items 3 to 6, wherein the component of the low harmful flame retardant has an average particle size of 1 mμ. It consists of a combination of the following aluminum hydroxide, fine particle calcium carbonate having an average particle size of 0.1 mμ or less, fine particle silica having an average particle size of 0.1 mμ or less, nanofiller MB, and novolak phenol resin, and the component of the compounding agent is calcium stearate Barium stearate, the metal compound consisting of a combination of molybdenum oxide and zinc stannate, most preferably reduces the amount of hydrogen chloride gas and dioxin generated, suppresses smoke generation, and further improves flame retardancy Can be made.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment.

The environment-friendly chlorine-containing resin composition described in item 1 of the present invention described above contains (i) a low-hazardous flame retardant in the chlorine-containing resin, and (b) and (c) flame retardancy. It consists of a compound containing a compounding agent with low smoke generation. Here, the low harmful flame retardant means a compound such as a hydrated metal compound or calcium carbonate that does not generate a harmful gas such as a halogen-based gas, a sulfur-based gas, or a phosphine gas during combustion.
(A) At least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and fine particles having an average particle size of 0.1 mμ or less At least one fine particle filler selected from silica (b) At least one organic fatty acid metal salt selected from calcium stearate, barium stearate and hydrotalcite (c) Molybdenum oxide, zinc stannate, zinc borate, sulfide At least one metal compound selected from zinc and zinc oxide Here, the chlorine-containing resin compound is usually used in appropriate technical fields as a compound used for various applications. The chlorine-containing resin used in the present invention includes polyvinyl chloride, ABS-modified polyvinyl chloride, vinyl chloride-acrylic acid copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinyl acetate copolymer, chlorinated polyethylene. , Vinylidene chloride, chlorinated polyethylene, copolymers with vinylidene chloride, and the like are mentioned, but the present invention is not limited to these, but polyvinyl chloride is particularly preferably used from the viewpoints of quantity and price.

  The chlorine-containing resin used in the present invention contains a plasticizer. However, the plasticizer is not particularly limited, and examples thereof include dibutylyl phthalate, dioctyl phthalate, didecyl phthalate, and phosphate esters (for example, , Tricresyl phosphate, etc.). As the stabilizer used in the present invention, usually hydrotalcite, fatty acid calcium, fatty acid barium, fatty acid zinc and the like are preferable, and examples of the fatty acid include stearic acid and the like. Moreover, as a low hazard flame retardant, it is a component of (a), and, thereby, a low hazard effect is acquired. As the component (a), a fine particle filler is preferable. Specifically, a hydrated metal compound is used. For example, aluminum hydroxide having an average particle size of 1 mμ or less, magnesium hydroxide having an average particle size of 1 mμ or less, and the like are preferable. Further, it is at least one fine particle filler selected from fine particle calcium carbonate having an average particle size of 0.1 mμ or less and fine particle silica having an average particle size of 0.1 mμ or less, and the addition ratio of these fine particle fillers is 100 wt. (A) at least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and an average particle size of 0 The amount of at least one fine particle filler selected from fine particle silica of 1 μm or less is 5 to 200 parts by weight, preferably 10 to 150 parts by weight. More preferably, it is 10 to 100 parts by weight. If the amount added is less than 5 parts by weight, there is no sufficient flame-retardant effect, and the amount of hydrogen chloride gas and chlorinated dioxin that are harmful gases cannot be suppressed. Moreover, when the addition amount of the fine particle filler exceeds 200 parts by weight, it is not preferable from the viewpoint of cost as well as adversely affecting the properties of the chlorine-containing resin. Moreover, (b) at least one organic fatty acid metal salt selected from calcium stearate, barium stearate and hydrotalcite is 5 to 30 parts by weight. If this amount is less than 5 weights, the flame retardant effect is poor, and if it exceeds 30 parts by weight, the moldability is adversely affected. Further, at least one metal compound selected from molybdenum oxide, zinc stannate, zinc borate, zinc sulfide and zinc oxide is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight. If this amount is less than 0.5 weight, the low smoke generation effect is insufficient, and if this amount exceeds 20 parts by weight, the moldability is adversely affected.

  The fine particle silica having an average particle size of 0.1 mμ or less used in the present invention is also called fumed silica or fumed silica, and is composed of very fine silica particles, which are decomposed from a low harmful chlorine-containing resin compound. Gas, harmful gas, etc. are adsorbed, and therefore, an excellent effect that hydrogen chloride gas and dioxins such as chlorinated dioxins and smoke generation can be suppressed is exhibited. The amount of the fumed silica is 0.5 to 50 parts by weight, preferably 5 to 30 parts by weight. If the amount of fumed silica is less than 0.5 weight, it is difficult to reduce the amount of dioxin and smoke, and even if the amount exceeds 50 parts by weight, the effect of reducing the amount of dioxin and smoke does not change. There is no point in adding any more.

Furthermore, in this invention, it is preferable that fumed silica has adsorb | sucked high molecular weight silicone oil and / or a silicone type flame retardant. Here, when a high molecular weight silicone oil and / or a silicone flame retardant is adsorbed and used on fumed silica, the high molecular weight silicone oil and the silicone flame retardant may be adsorbed alone, respectively, A mixture of silicone oil and silicone flame retardant may be adsorbed and used. Examples of the silicone-based flame retardant include Si balter DC4-7105 (white powder, non-functional group, manufactured by Toray Dow Silicone), DC 4-7051 (white powder, methallyl group-containing, manufactured by Toledo Silicone), silicone compound , XC99-B5664 (granular, flame retardant temperature 85-105 ° C., silicone polymer having aromatic group, manufactured by GE Toshiba Silicone), FRX-02 (white powder, bulk specific gravity 0.4, active ingredient) 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are all known in this technical field. Si balter DC4-7105 or DC4-7051 is preferable. In the present invention, these high molecular weight silicone oils and / or silicone flame retardants are adsorbed and used on fumed silica, so that the high molecular weight silicone oils and / or silicone flame retardants are usually compatible with chlorine-containing resins. Although it is not good, when adsorbed in fumed silica, it can be dispersed relatively uniformly in the chlorine-containing resin, thus reducing not only dioxins and smoke but also HCl generation. it can.
The environment-friendly chlorine-containing resin composition described in item 3 of the present invention is a (2) nanofillers as a low-hazardous flame retardant to the chlorine-containing resin compound described in item 1 or item 2. Alternatively, it contains a nanocomposite MB of EVA and montmorillonite (MB stands for master batch).
The nanofiller used in the present invention refers to substances such as clay and graphite having fine particles having an average particle diameter of 100 nm or less. As for the addition amount of the nano filler with respect to 100 weight part of chlorine containing resin, 0.1-15 weight part is preferable. The above montmorillonite is a kind of clay and is said to have a slightly flat structure with a thickness of 1 nm and a length of 10 nm. Nanofillers usually exhibit strong mechanical properties when finely dispersed in a polymer material, so that they are used as high-rigidity materials, and are also used as gas barriers because of their low gas permeability. In addition, the nanofiller has only a small amount of 1 to 10 parts by weight added to the combustible material, and the combustion residue generated with the progress of combustion exhibits an excellent oxygen blocking effect and heat insulating effect, and exhibits an excellent flame retardant effect. . Methods for producing such a nanocomposite by dispersing such nanofillers in a polymer material can be broadly divided into a polymerization method and a direct mixing method, but the polymerization method is expensive and has difficulty in practical use. In the present invention, the latter direct mixing method is used.
In addition, the environment-friendly chlorine-containing resin composition described in item 4 of the present invention described above is an (e) novolak phenol resin or aroma as a low-hazardous flame retardant in the invention described in item 1 or 2. It contains an aromatic compound selected from group phosphorus compounds.
The environment-friendly chlorine-containing resin composition described in the fifth aspect of the present invention is the invention described in the third or fourth aspect, wherein (d) the nanofiller or the nanocomposite MB of EVA and montmorillonite is used. The addition ratio depends on the ratio of EVA and montmorillonite with respect to 100 parts by weight of the chlorine-containing resin, but preferably contains 0.4 to 60 parts by weight. Thereby, the generation amount of hydrogen chloride gas and dioxin can be reduced more appropriately, the smoke generation amount can be suppressed, and the flame retardancy can be further improved. The environmentally friendly chlorine-containing resin composition described in item 6 of the present invention is selected from (e) a novolak phenol resin or an aromatic phosphorus compound in the invention described in any one of items 3 to 5. The added ratio of the aromatic compound is 1 to 50 parts by weight with respect to 100 parts by weight of the chlorine-containing resin. Thereby, the generation amount of hydrogen chloride gas and dioxin can be reduced more appropriately, the smoke generation amount can be suppressed, and the flame retardancy can be further improved.

    (Operation) In the present invention, the hydrated metal oxide and the fine particle calcium carbonate play a role of adsorbing harmful gas, HCl gas, dioxin and the like generated during combustion. Furthermore, the flame retardant effect by the endothermic reaction by the hydrated metal oxide is exhibited. That is, particulate aluminum hydroxide, which is a hydrated metal oxide, suppresses combustion by an endothermic reaction, and the produced aluminum oxide acts as a low smoke generation effect. Furthermore, there is a dioxin adsorption effect. The particulate calcium carbonate reacts with HCl gas to convert to calcium chloride and exhibits a low HCl gas effect. Molybdenum oxide exhibits a low smoke generation effect. Since fumed silica has an active OH group on the surface and a porous surface structure, it has an action of effectively absorbing cracked gas, smoke, dioxin and the like. Further, an inorganic incombustible layer having hard —Si—O— bonds is formed by combustion, and this acts as a heat insulating layer. Furthermore, zinc borate has the effect of blocking oxygen by melting to form a glass layer. Furthermore, the nanofiller has only a small amount of 1 to 10 parts by weight added to the combustible material, and the combustion residue generated with the progress of combustion exhibits an excellent oxygen blocking effect and heat insulating effect, and exhibits an excellent flame retardant effect. . In the present invention, there are various uses such as various films, gaskets, wire and cable coatings, pipes, wallpaper, toys, agricultural sheets, waterproofing equipment and the like as applications that exhibit such effects.

  In this invention, it is thought that a synergistic effect is exhibited as follows by mix | blending such each component. The HCl gas generated at the time of combustion acts on the fine particle calcium carbonate to be converted into calcium chloride and adsorbed. At the same time, dioxins are mainly adsorbed by aluminum hydroxide, and fumed silica supplements the adsorption. The generated smoke is reduced by oxidizing soot (particulate carbon) mainly composed of a molybdenum compound, and aluminum hydroxide becomes aluminum oxide to help reduce soot. Furthermore, fumed silica adsorbs smoke. Furthermore, the flame retardant effect is that fumed silica adsorbing high molecular weight silicone oil and / or silicone flame retardant combusts and solidifies the inorganic combustion residue (inorganic non-combustible layer with —Si—O— bond) to produce chlorine. It is considered that a non-flammable and stable barrier is formed on the surface of the containing resin gasket, and oxygen blocking and heat insulating effects are exhibited. Therefore, the chlorine-containing resin gasket exhibits more excellent flame retardancy and low harmful gas effect due to the combined effect of each component. In addition, fumed silica has active OH groups on its surface, so it strongly adsorbs high molecular weight silicone oil and / or silicone flame retardant and is present in chlorine-containing resin and deposits on the surface of chlorine-containing resin gaskets. It plays a role to prevent In this way, the presence of fumed silica creates a hard, hard-to-burn coating on the surface during combustion, so that the adsorbed dioxin and calcium chloride are contained inside and confined in the combustion residue. Therefore, after combustion, only a small amount of combustion residue is specially treated so as not to adversely affect the environment.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
[Example 1]
In a compound containing 100 parts by weight of polyvinyl chloride (degree of polymerization 1100) and 50 parts by weight of dioctyl phthalate as a plasticizer, 50 parts by weight of aluminum hydroxide (fine particles having an average particle size of 1 mμ), 2 parts by weight of calcium stearate as a stabilizer, and Low harmful flame retardant comprising 2 parts by weight of barium stearate, 50 parts by weight of fine calcium carbonate (average particle size 1 mμ), 10 parts by weight of fumed silica, 5 parts by weight of molybdenum oxide and 5 parts by weight of zinc oxide, and fumed silica 10 parts by weight were blended and mixed uniformly. Using the obtained environment-friendly chlorine-containing resin blend as a sample, the amount of hydrogen chloride gas generated, the amount of chlorinated dioxin generated, the amount of chlorinated furan generated, the amount of smoke generated, and the oxygen index were measured. The obtained results are shown in Table 1.
[Example 2]
In a compound containing 100 parts by weight of polyvinyl chloride (degree of polymerization 1100) and 50 parts by weight of dioctyl phthalate as a plasticizer, 50 parts by weight of aluminum hydroxide (fine particles having an average particle size of 1 mμ), 2 parts by weight of calcium stearate as a stabilizer, and Low harmful flame retardant and fumed silica 10 comprising 2 parts by weight of barium stearate, 50 parts by weight of fine calcium carbonate (average particle size 1 mμ), 10 parts by weight of fumed silica, 5 parts by weight of molybdenum oxide and 5 parts by weight of zinc oxide Part by weight was blended, and further 20 parts by weight of nanofiller MB was blended and mixed uniformly. Using the obtained environment-friendly chlorine-containing resin blend as a sample, the amount of hydrogen chloride gas generated, the amount of chlorinated dioxin generated, the amount of chlorinated furan generated, the amount of smoke generated, and the oxygen index were measured. The obtained results are shown in Table 1. As nanofiller MB, nanocomposite MB is montmorillonite obtained by grafting EVA with maleic anhydride and intercalating an organic amide compound (a twin-screw extruder manufactured by Kunipia G, F-Kunimine Kogyo Co., Ltd.). Grafted with maleic anhydride (some commercial products are intercalated) were extruded and dispersed at 170-180 ° C. with a twin screw extruder to produce a nanocomposite.
Example 3
In a compound containing 100 parts by weight of polyvinyl chloride (degree of polymerization 1100) and 50 parts by weight of dioctyl phthalate as a plasticizer, 50 parts by weight of aluminum hydroxide (fine particles having an average particle size of 1 mμ), 2 parts by weight of calcium stearate as a stabilizer, and Low harmful flame retardant and fumed silica 10 comprising 2 parts by weight of barium stearate, 50 parts by weight of fine calcium carbonate (average particle size 1 mμ), 10 parts by weight of fumed silica, 5 parts by weight of molybdenum oxide and 5 parts by weight of zinc oxide Further, 20 parts by weight of nanofiller MB and 5 parts by weight of novolak phenol resin were blended and mixed uniformly. Using the obtained environment-friendly chlorine-containing resin blend as a sample, the amount of hydrogen chloride gas generated, the amount of chlorinated dioxin generated, the amount of chlorinated furan generated, the amount of smoke generated, and the oxygen index were measured. The obtained results are shown in Table 1.
[Comparative Example 1]
As a conventional formulation, 100 parts by weight of polyvinyl chloride (degree of polymerization 1100), 50 parts by weight of dioctyl phthalate as a plasticizer, 2 parts by weight of calcium stearate and 2 parts by weight of barium stearate as stabilizers, and aluminum hydroxide (fine particle type) Samples of chlorine-containing resin composition consisting of 50 parts by weight, 50 parts by weight of calcium carbonate (2 μm particle size) and 50 parts by weight of clay, hydrogen chloride gas generation amount, chlorinated dioxin generation amount, chlorinated furan generation The amount, smoke generation and oxygen index were measured. The obtained results are shown in Table 1.

表１から明らかなように、比較例１では、ＨＣｌガス発生量が４２０ｍｇ／ｇ、塩素化ダイオキシン発生量が３２ｎｇ／ｇであり、特に塩素化フランが２０００ｎｇ／ｇと多く、また発煙量（比光学密度）も５４０と多い。更に酸素指数は２９である。これに対して、実施例１では、ＨＣｌガス発生量は、４０ｍｇ／ｇとはるかに減少している。またダイオキシン発生量は、塩素化ダイオキシンが３ｎｇ／ｇ、塩素化フランが１７０ｎｇ／ｇと極めて少なくなっている。また発煙量も２５０と減少している。更に実施例２及び３では、塩化水素ガスの発生量が更に少なくなっている。また塩素化フランの発生量はそれぞれ少なくなっている。更に発煙量も同様に減少している。したがって、本発明では、従来のものより各特性が格段に優れた値を示していることがわかる。
〔実施例４〕
実施例３及び比較例１で配合した環境対応型塩素含有樹脂配合物を用いてそれぞれガスケットを作製した。これらのガスケットの物性として、機械的特性、熱劣化及び体積固有抵抗を測定した。得られた結果を表２に示す。

As is apparent from Table 1, in Comparative Example 1, the amount of HCl gas generated was 420 mg / g, the amount of chlorinated dioxin generated was 32 ng / g, particularly chlorinated furan was as high as 2000 ng / g, and the amount of smoke generated (ratio) The optical density is also as high as 540. Furthermore, the oxygen index is 29. On the other hand, in Example 1, the amount of HCl gas generation is much reduced to 40 mg / g. In addition, the amount of dioxins generated is extremely low at 3 ng / g for chlorinated dioxins and 170 ng / g for chlorinated furans. In addition, the amount of smoke is reduced to 250. Furthermore, in Examples 2 and 3, the amount of hydrogen chloride gas generated is further reduced. In addition, the amount of chlorinated furan generated is decreasing. Furthermore, the amount of smoke emitted has also decreased. Therefore, it can be seen that in the present invention, each characteristic shows a value significantly superior to the conventional one.
Example 4
Gaskets were prepared using the environmentally friendly chlorine-containing resin blends blended in Example 3 and Comparative Example 1, respectively. As physical properties of these gaskets, mechanical properties, thermal degradation and volume resistivity were measured. The obtained results are shown in Table 2.

Claims (7)

A low-hazardous environment-friendly chlorine characterized in that the chlorine-containing resin contains (a) a low-hazardous flame retardant, and (B) and (c) a combination of flame-retardant and less fuming. Containing resin formulation.
(A) At least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and fine particles having an average particle size of 0.1 mμ or less At least one particulate filler selected from silica (b) at least one stabilizer selected from calcium stearate, barium stearate and hydrotalcite (c) molybdenum oxide, zinc stannate, zinc borate, zinc sulfide and At least one metal compound selected from zinc oxide Low hazard, characterized in that it contains (b) a low hazard flame retardant, and (b) and (c) a compound with low flame retardant and smoke generation, in proportion to 100 parts by weight of the chlorine-containing resin. Environmentally friendly chlorine-containing resin blend.
(A) At least one hydrated metal compound selected from aluminum hydroxide and magnesium hydroxide having an average particle size of 1 mμ or less, fine calcium carbonate having an average particle size of 0.1 mμ or less, and fine particles having an average particle size of 0.1 mμ or less 5 to 200 parts by weight of at least one fine particle filler selected from silica (b) at least one stabilizer selected from calcium stearate, barium stearate and hydrotalcite (c) molybdenum oxide, 0.5 to 20 parts by weight of at least one metal compound selected from zinc stannate, zinc borate, zinc sulfide and zinc oxide The environment-friendly chlorine-containing resin composition according to claim 1 or 2, characterized by containing (d) nanofillers or EVA and montmorillonite nanocomposite MB as a low-hazardous flame retardant. The environment-friendly chlorine according to any one of claims 1 and 3, comprising an aromatic compound selected from (e) a novolak phenol resin or an aromatic phosphorus compound as a low-hazardous flame retardant. Containing resin formulation. (D) 0.4 to 60 parts by weight of nanofillers or EVA and montmorillonite nanocomposite MB is contained, and the environment-friendly chlorine-containing resin composition according to claim 3 or 4. 6. The environmentally friendly chlorine-containing resin according to claim 3, which contains 1 to 50 parts by weight of an aromatic compound selected from a novolak phenol resin or an aromatic phosphorus compound. Formulation. The components of the low harmful flame retardant are aluminum hydroxide having an average particle size of 1 mμ or less, fine particle calcium carbonate having an average particle size of 0.1 mμ or less, fine particle silica having an average particle size of 0.1 mμ or less, nanofiller MB, and novolak phenol resin. 7. The composition according to any one of claims 3 to 6, further comprising a combination, wherein the components of the compounding agent are calcium stearate and barium stearate, and the metal compound is a combination of molybdenum oxide and zinc stannate. The environmentally friendly chlorine-containing resin blend described.