JPH101583A - Flame-retardant halogen-containing resin composition for transparent molded products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent flame retardancy by blending a halogenated resin with an Sb2 O5 powder having a mean particle diameter below a specified value and a β-diketone compound or a metal salt thereof. SOLUTION: A halogenated resin such as a vinyl chloride resin in an amount of 100 pts.wt. is blended with 1.0-10 pts.wt. Sb2 O5 powder having a mean particle diameter of at most 30μm and 0.01-5 pts.wt. β-diketone compound or zinc salt thereof, such as dibenzoylmethane or zinc salt thereof. If necessary, this mixture is blended with a plasticizer such as tricresyl phosphate, a Ba-Zn composite stabilizer, an antioxidant, an antistatic agent, an anti-fogging agent, etc., each in a specified amount, and the blend is kneaded with, e.g. a hot roll to give a flame-retardant halogenated resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-containing resin used for various molded products including various sheets, films, coating materials, or load-bearing structural materials.

[0002]

2. Description of the Related Art Halogen-containing resins, such as polyvinyl chloride resin and vinyl chloride / vinyl acetate copolymer resin, can easily adjust their physical properties from hard to soft by adjusting the amount of plasticizer added. Because of its properties, it is widely used for floor sheets, wire covering materials and the like. Further, because of its good transparency, it is widely used for packaging containers, agricultural films and the like in which the contents are visible.

However, wall materials, ceiling materials, automobile interior materials,
In applications where flame retardancy is required for wire covering materials and the like, a flame retardant plasticizer composed of a phosphate ester-based compound and a halogen-containing compound is selected as a plasticizer to be added. In applications requiring even higher flame retardancy, an inorganic filler-based flame retardant such as antimony trioxide (Sb ₂ O ₃ ) or aluminum hydroxide is added.

However, the addition of these inorganic filler-based flame retardants impairs the transparency of the halogen-containing resin.
Antimony trioxide, which has particularly excellent flame retardancy, has strong hiding properties and coloring properties. Further, when the addition amount of the phosphoric ester-based or halogen-containing flame-retardant plasticizer is increased to such an extent that the flame retardancy is improved, there arises a problem that they bleed on the surface of the molding resin. Therefore, it was difficult to obtain a halogen-containing resin composition excellent in both flame retardancy and transparency.

For the purpose of solving this problem, the use of finely ground antimony pentoxide as a flame retardant has been recently developed, and commercialization of finely ground antimony pentoxide for this purpose has been started (manufactured by Nissan Chemical Industries, Ltd.). , Trade name Sun Epoque NA-
3080, average particle size 18 μm). In fact, when this is used as a flame retardant, a halogen-containing resin molded product having excellent flame retardancy and a certain degree of transparency can be obtained.

[0006]

However, when molding is carried out under practical molding conditions using the above-mentioned method, a colorless and transparent molded product cannot be obtained, but it is colored yellow and transparent. Properties, ie, see-through properties and light transmittance. Coloring also impairs decorativeness.

The present invention has been made in view of the above problems, and provides a halogen-containing resin composition which is excellent in flame retardancy and can provide a product having excellent transparency even when molded under industrial molding conditions. .

[0008]

The halogen-containing resin composition according to the first aspect of the present invention comprises an antimony pentoxide powder having an average particle diameter of 30 μm or less per 100 parts by weight of the halogen-containing resin. 0 to 10 parts by weight, and 0.01 to 5 parts by weight of a β-diketone compound or a metal salt thereof.

The above composition provides a resin composition capable of industrially producing a halogen-containing resin molded article having excellent flame retardancy and transparency.

A second aspect of the present invention is a halogen-containing resin composition according to the first aspect, wherein the halogen-containing resin is a vinyl chloride resin.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The halogen-containing resin of the present invention is typically a vinyl chloride resin. As the vinyl chloride resin, a polyvinyl chloride resin or a vinyl chloride copolymer resin can be used as long as it is a general resin,
A partially crosslinked product is also used. Examples of vinyl chloride copolymer resins include vinyl chloride / vinyl acetate copolymer resins, ethylene / vinyl chloride copolymer resins, and ethylene / vinyl chloride copolymer resins.
Examples include a terpolymer resin obtained by grafting vinyl chloride to a vinyl acetate copolymer, a vinyl chloride-vinylidene chloride copolymer, a vinyl chloride-propylene copolymer, or an internally plasticized polyvinyl chloride resin.

Antimony pentoxide (Sb ₂ O ₅ ) used in the present invention
Is obtained by finely pulverizing an ordinary commercial product by an ordinary method, and requires no special treatment other than pulverization. In addition, the above-mentioned commercially available finely pulverized product (Sun-Epoque NA-308 manufactured by Nissan Chemical Industries, Ltd.)
0, average particle size 18 μm) can be used as it is or after further pulverization.

The average particle size of the antimony pentoxide powder used in the present invention is 30 μm or less, preferably 25 μm or less, more preferably 22 μm or less. When the average particle size is larger than 30 μm, milky white haze is observed in the resin product obtained by molding, and a decrease in light transmittance is observed. For ordinary thin sheets and films,
Although practically transparent when the average particle size is less than 30 μm,
When the thickness is 25 μm or less, even a thick sheet is sufficiently transparent. When the average particle size is 22 μm or less, sufficient transparency can be obtained even in a bulk molded product. What actually hinders the transparency of the resin is that the particle size in the particle size distribution is about 70μ.
It is considered to be a part of m or more or 100 μm or more. However, when a normal pulverization method is applied, it is known that the average particle size and the content in the above range are correlated. Almost not included. Therefore, it is possible to obtain a material which hardly contains the above-mentioned particle size portion obstructing the transparency by a special method, and even if the average particle size exceeds 30 μm, it can be considered to be included in the technical scope of the present invention.

The measurement of the average particle diameter can be carried out by a sieving method, but it can be easily carried out by making the suspension into a suspended state and measuring with a machine such as a Coulter counter. The average particle size referred to here substantially corresponds to a volume average or weight average particle size.

The amount of antimony pentoxide used in the present invention is 1.0 to 10 parts by weight, preferably 2.0 to 5 parts by weight, based on 100 parts by weight of the base resin.

If the amount of antimony pentoxide is less than 1.0 part by weight, the flame retardancy is insufficient. If the amount of antimony pentoxide exceeds 10 parts by weight, the formed product gradually becomes cloudy and loses transparency as the amount of antimony pentoxide increases. It is considered that the excessive addition of the antimony pentoxide causes secondary aggregation. If the amount is 2.0 parts by weight or more, sufficient flame retardancy can be obtained.

The addition of antimony pentoxide provides the same flame retardancy as the addition of antimony trioxide, but it is necessary to slightly increase the amount of addition to obtain the same flame retardancy. The performance of antimony oxide-based flame retardants seems to be correlated with the amount of elemental antimony.

The antimony pentoxide powder product may contain a dispersing agent, a grinding aid and other substances which do not significantly affect the properties of the resin composition. It is sufficient that the content is in the above range in terms of antimony pentoxide as a pure component. The addition of a suitable dispersant aids in uniform mixing into the base resin. However, if the content of pure antimony pentoxide in the antimony pentoxide powder product is not at least 55% or more, the amount of the additive may be excessive, which is not preferable.

When industrially pulverizing antimony pentoxide, it is considered essential to add a suitable pulverizing aid.
It is presumed that an organic compound having surface activity or dispersibility, such as a polyalkylene oxide-based or polyamide-based compound, is added to prevent secondary aggregation during pulverization.

The β-diketone compound used in the present invention includes dehydrobenzoylacetic acid, dimedone, 2-benzylcyclohexane-1,3-dione, stearoyltetralone, 2
-Benzoylcyclohexanone, bis (4-methylbenzoyl) methane, tribenzoylmethane, stearoyl benzoylmethane, palmitoyl benzoylmethane, lauroyl benzoylmethane, dibenzoylmethane, benzoyl acetyl octyl methane, benzoyl acetyl phenyl methane, Bis (4-t-butylbenzoyl)
Methane, benzoyl acetylethyl methane, stearoyl acetyl methane, benzoyl formyl methane,
Benzoyl phenylacetylmethane, bis (cyclohexanoyl) methane, dipivaloylmethane and the like can be mentioned. Further, metal salts of these compounds are also useful, and as the metal constituting the metal salt, lithium, sodium, potassium, magnesium, calcium, barium,
Strontium, zinc, aluminum, zirconium,
Tin and the like.

The amount of the above-mentioned β-diketone compound or its metal salt is 0.1 to 100 parts by weight of the vinyl chloride resin.
The amount is from 0.01 to 5 parts by weight, preferably from 0.05 to 2.0 parts by weight. If the addition amount is less than 0.01 parts by weight,
Even if the molding conditions are mild, yellow coloring is observed in the molded resin product. When the amount of the β-diketone compound is 0.05 parts by weight, the coloring of the molded product is negligible even when molded under relatively severe conditions.
Further, even when the molding conditions were much harsher than usual, the addition of 2.0 parts by weight or more hardly increased the anti-coloring property. On the other hand, an excessive amount exceeding 5 parts by weight is not preferable because it causes an increase in cost.

Examples of the plasticizer used in the resin composition of the present invention include phthalic acid esters such as di-2-ethylhexyl phthalate (DOP), diisononyl phthalate, diisodecyl phthalate, tri-2-ethylhexyl trimellitate, and triisononyl. Trimellitate ester such as trimellitate, phosphate ester such as tricresyl phosphate (TCP), cresyl diphenyl phosphate,
Chlorine-based such as chlorinated paraffin, epoxy-based, polyester-based and the like can be mentioned. However, it is not preferable to use a phosphate plasticizer, a chlorine-containing plasticizer, and an epoxy plasticizer, which are flame-retardant plasticizers, because the plasticizer bleeds to the surface of the molded article.

These plasticizers that easily cause bleeding are used in combination with phthalate-based, trimellitate-based, polyester-based, and fatty acid-ester-based plasticizers that are less likely to cause bleeding. The bleeding-prone plasticizer hardly causes the problem of bleeding when the ratio of the necessary amount of the plasticizer in the total amount is less than a certain level. Since all of the flame-retardant plasticizers are liable to bleed, they are appropriately used in combination with the above-mentioned plasticizer which does not easily cause bleed depending on the required flame-retardant level and the like.

As the stabilizer used in the resin composition of the present invention, a metal soap-based stabilizer, an organotin compound-based stabilizer, and a Ba-Zn-based or Ca-Zn-based composite stabilizer can be appropriately added. . Any resin can be used as long as it does not impair the transparency of the resin.

An antioxidant, an antistatic agent, and an antifogging agent can be appropriately added to the resin composition of the present invention.

For example, when manufacturing a see-through partition plate for use in a ticket window of a station, a shield of a driver's seat of a vehicle, and the like, it is desirable to add a suitable antifogging agent and an antistatic agent to the composition. As the antifogging agent, various ones containing nonionic, cationic, and amphoteric surfactant components as main components can be used. As the antistatic agent, for example, quaternary ammonium salts, amines, imidazolines, or various polyoxyethylene compounds can be selected and used.

[0027]

The present invention will be described below with reference to the following examples and comparative examples.

<Examples 1 to 11> In Examples 1 to 11, the composition of the polyvinyl chloride resin composition and the transparency
Tables 1 and 2 collectively show the flame retardant performance. All compositions in the table are parts by weight added to 100 parts by weight of the polyvinyl chloride resin.

[0029]

[Table 1]

[Table 2] For 100 parts by weight of polyvinyl chloride resin (Kanevinyl S1001N manufactured by Kanegafuchi Chemical Co., Ltd.) having an average degree of polymerization of about 1000,
As a β-diketone compound, 0.02 to 5.0 parts by weight of dibenzoylmethane, stearoylbenzoylmethane or dibenzoylmethane zinc salt, and as an antimony pentoxide finely pulverized product, San-Epoque NA-3080 manufactured by Nissan Chemical Industries, Ltd. 2.0 to 10 parts by weight were added. In addition, after fixing the total amount of the plasticizer to 45 parts by weight, the non-flame-retardant plasticizer
2-ethylhexyl phthalate (DOP) 35-45
By weight, tricresyl phosphate (TCP) or chlorinated paraffin (chlorinated paraffin manufactured by Ajinomoto Co., chlorine content: 50%) was added as a flame retardant plasticizer. Further, 3.0 parts by weight of a Ba-Zn composite powder (PSL-610 manufactured by Kosei Co., Ltd.) was added as a stabilizer and a lubricant.

The composition was heated for 5 minutes on a hot roll at about 170 ° C.
After kneading for 1 minute, sheets having a thickness of 1 mm and 3 mm were prepared by press working at a hot plate temperature of about 170 ° C.

The evaluation of the flame retardancy was made by measuring the oxygen index based on JIS K7201 using a sheet having a thickness of 3 mm.
The evaluation of the transparency performance was carried out by using a sheet having a thickness of 1 mm and comparing the degree of see-through property and the degree of non-yellowing (non-yellowing) with the naked eye. ○
× is classified into three stages, ○ is good, △ is on the borderline,
X is bad. Regarding the determination of bleeding,
This was performed by visual observation of a sheet having a thickness of 1 mm, and the results are shown at the lower end of the table.

Each of the sheet molded products of Examples 1 to 5 and 7 to 13 had good transparency, and no coloring or white turbidity was observed. The amount of antimony pentoxide fine powder is 10
For Example 6, which was part by weight, slight cloudiness was observed.

Each of the obtained products has an oxygen index of 2
It exceeded 5.0, and was determined to have the required flame retardancy.

As shown in Table 1, even when only a non-flame retardant plasticizer is used as the plasticizer, when the addition amount of the antimony pentoxide fine powder is 3.0 parts by weight, the oxygen index is 25.0 parts by weight.
When the self-extinguishing reference value of 0 was exceeded (Example 1) and 10 parts by weight of the flame-retardant plasticizer (TCP and chlorinated paraffin respectively) were used, the oxygen index was slightly further improved (Example 2). And 3). In the same composition as in Example 2, when the addition amount of the antimony pentoxide fine powder was changed in the range of 2.0 to 10 parts by weight, a slight increase was observed in the oxygen index due to the increase in the addition amount, but the difference was large. No (Example 4
~ 6).

Further, even if stearoylbenzoylmethane or zinc salt of dibenzoylmethane was used as the β-diketone compound in place of dibenzoylmethane used in all of the other examples, no influence on the performance of the molded sheet was observed (see Table 1). 1, Examples 7 to 8), when the amount of addition was changed in the range of 0.02 to 5.0 parts by weight (Examples 9 to 11 in Table 2)
The same was true for. The same was true even when the type and amount of the stabilizer were slightly changed (Examples 12 to 14 in Table 2).

<Comparative Examples 1 to 6>
Table 3 summarizes the composition of the composition and the performance obtained. These were determined to be poor in any of the transparent performance and the flame retardant performance.

[0037]

[Table 3] In Comparative Examples 1 and 2, the added amount of the β-diketone compound was 0 and 0.005 parts by weight, and in Comparative Examples 3 and 4, the added amount of the finely ground antimony pentoxide was 0 and 0.5 parts by weight, respectively. In Comparative Example 5, antimony pentoxide powder having an average particle size of 50 μm was used. In Comparative Example 6, 3.0 parts by weight of antimony trioxide was added instead of antimony pentoxide. In these comparative examples, the other compositions were exactly the same as in Example 2. In Comparative Examples 1 and 2, yellowing was observed and the see-through property was insufficient, and in Comparative Examples 3 and 4, the oxygen index was the reference value 2
Since it was less than 5.0, the flame retardancy was considered to be insufficient. Comparative Example 5
In Nos. 6 to 6, the molded product was cloudy and the see-through property was poor.

<Comparative Examples 7 to 9> Only 45 parts by weight of a flame-retardant plasticizer was used as a plasticizer. Excellent flame retardancy was also obtained when using a large amount of TCP or chlorinated paraffin without using antimony pentoxide (Comparative Examples 7 to 8). However, the molded product was determined to be defective because bleeding was observed. Bleeding was also observed when 3.0 parts by weight of antimony pentoxide fine powder was added (Comparative Example 9).

[0039]

[Table 4]

[0040]

According to the present invention, there is provided a halogen-containing resin composition which is excellent in flame retardancy, has no bleeding of a plasticizer, and provides a molded article having excellent transparency.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Keiichi Murakami, Inventor Keiichi Murakami 2-3-1, Iwata-cho, Higashiosaka-shi, Osaka Inside Tatsuta Electric Wire Co., Ltd. No. 6-3 Koshonai Co., Ltd. (72) Inventor Junichi Mihara 1228 Nakayamacho, Midori-ku, Yokohama-shi, Kanagawa Prefecture Nitto Kasei Kogyo Co., Ltd. (72) Inventor Toru Iwase 1228 Nakayamacho, Midori-ku, Yokohama-shi, Kanagawa Nitto Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) 100 parts by weight of a halogen-containing resin,
A transparent molded article comprising 1.0 to 10 parts by weight of antimony pentoxide powder having an average particle diameter of 30 μm or less and 0.01 to 5 parts by weight of a β-diketone compound or a metal salt thereof. Flame-retardant halogen-containing resin composition for use. 2. A flame-retardant halogen-containing resin composition for a transparent molded article according to claim 1, wherein said halogen-containing resin is a vinyl chloride resin. Stuff.