JPH08311283A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE: To obtain a flameproof vinyl chloride resin composition which gives a gasket sufficiently effective in fire blocking and in preventing fire spreading by incorporating a flame-retardant plasticizer and silicon oxide into a vinyl chloride resin. CONSTITUTION: 100 pts.wt. vinyl chloride resin is compounded with 50-200 pts.wt. plasticizer ingredient comprising at least 20wt.% flame-retardant plasticizer (a) and 5-100 pts.wt. silicon oxide to produce a flame-retardant vinyl chloride resin composition. Examples of the plasticizer (a) include phosphoric esters, chlorinated paraffins, and chlorinated fatty acids. The plasticizer (a) is used preferably in an amount of 20-50wt.% based on the whole plasticizer ingredient, together with DOP, etc. The silicon oxide has an average particle diameter of 50μm or smaller, preferably 30μm or smaller. According to need, other additives can be incorporated into the composition. Upon carbonization, the composition containing a zinc borate as a flame retardant gives a solid mass which retains sealing performance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant vinyl chloride resin composition which has excellent flame resistance and is suitable for use as a fire-resistant gasket.

[0002]

2. Description of the Related Art In recent years, airtight materials for construction, such as gaskets, have been required to have high flame retardancy, flame spread resistance, and flame shielding property. The soft vinyl chloride resin composition is easily molded, has flexibility, and is highly elastic, and thus is often used as a material for gaskets. In order to increase the flame retardancy of the composition, phosphorus, antimony, The oxygen index is increased by adding compounds such as boron, aluminum, magnesium, molybdenum and halogen.

However, when such a composition is exposed to high heat at the time of fire, it is melted and undergoes remarkable deformation, and the components contained in the composition undergo contraction and foaming due to volatilization and ashing. When the composition was disintegrated, the volatilized plasticizer was ignited, etc., and the molded product was used as a gasket, the airtightness was lost, the flame was shielded and the spread of fire was not sufficiently prevented.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that the composition of the present invention is a composition in which the volatility of a plasticizer is reduced and which is excellent in flame retardance, and does not ignite even when used as a gasket and is airtight. As a result of diligent studies to develop a composition conforming to the JIS A5576 architectural gasket standard that does not impair the properties, it was found that the above object can be achieved by using a flame retardant plasticizer in combination with silicon oxide. Came to complete. That is, the object of the present invention is JIS A57.
(EN) Provided is a vinyl chloride resin composition suitable as a molding material for a fire-resistant gasket that complies with 56 building gasket standards.

[0005]

The gist of the present invention is that 100 parts by weight of vinyl chloride resin, 2 flame retardant plasticizers are used.
A vinyl chloride resin composition containing 50 to 200 parts by weight of a plasticizer containing 0% by weight or more and 5 to 100 parts by weight of silicon oxide as main components, and a gasket formed by molding the composition.

To explain the present invention in detail, the vinyl chloride resin which is the resin component of the present invention is a suspension polymerization method or a bulk polymerization method of vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith. Any of those produced by a usual method such as a fine suspension polymerization method or an emulsion polymerization method can be used. Examples of comonomers include vinyl acetates such as vinyl acetate, vinyl propionate and vinyl laurate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, dibutyl. Maleates such as maleate and diethyl maleate, fumarates such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, and cyan such as acrylonitrile and methacrylonitrile. Vinyl chloride, α-olefins such as ethylene, propylene and styrene, vinylidene chloride,
Vinylidene halides or vinyl halides other than vinyl chloride such as vinyl bromide, and polyfunctional monomers such as diallyl phthalate and ethylene glycol dimethacrylate may be mentioned. Of course, the comonomer is limited to those mentioned above. is not. The comonomer content is 30% by weight or less, preferably 20% by weight or less in the constituent components of the vinyl chloride resin.

Further, the category of vinyl chloride resin also includes a chlorinated vinyl chloride resin obtained by post-chlorinating the vinyl chloride resin produced as described above. A polymer compound compatible with the vinyl chloride resin can be added to these vinyl chloride resins. Examples of such polymer compounds include ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, ethylene-vinyl acetate-carbon monoxide copolymers, acrylonitrile-butadiene rubbers, chloroprene rubbers, chlorinated compounds. Polyethylene, methacrylic acid ester copolymer and the like can be mentioned. 150 parts by weight or less per 100 parts by weight of vinyl chloride resin,
It is preferably added in an amount of 100 parts by weight or less.

The plasticizer used in the composition of the present invention is not particularly limited as long as it is usually used for vinyl chloride resins, and examples thereof include dibutyl phthalate (DBP), dihexyl phthalate and di-2-ethylhexyl phthalate ( DOP), di-n-octyl phthalate, diisodecyl phthalate, and other phthalate plasticizers; dioctyl adipate, diisodecyl adipate, dioctyl sebacate, and other dibasic acid ester plasticizers; trioctyl trimellitate (TOTM) Trimellitate phosphate (TCP), triphenyl phosphate, trixylyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate , Tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (bromochloropropyl) phosphate , Bis (2,3-dibromopropyl)
Phosphate ester plasticizers such as -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate, and halogen-containing polyphosphates; polyester polymer plasticizers, epoxidized soybean oil, epoxidized linseed oil, liquid epoxy Examples include epoxy plasticizers such as resins; chlorinated paraffins; chlorinated fatty acid esters such as alkyl pentachloride stearates. The plasticizer exerts the effects of imparting flexibility to the composition and the gasket obtained from the composition and maintaining the airtightness of the gasket.

In the composition of the present invention, it is essential to add at least one of so-called flame retardant plasticizers such as phosphoric acid ester plasticizers, chlorinated paraffins or chlorinated fatty acid esters among these. The amount of flame retardant plasticizer is
It is necessary to contain 20% by weight or more, preferably 20 to 50% by weight, of the total amount of the plasticizer compounded in the composition. The amount of the plasticizer compounded in the composition is preferably 30 to 200 parts by weight, and more preferably 50 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Addition of the flame-retardant plasticizer has the effect of preventing the ignition of the plasticizer that volatilizes in high heat. It is difficult to prevent the ignition of the plasticizer, and the spread of fire cannot be prevented. Further, since only the flame retardant plasticizer has poor plasticization efficiency, it is desirable to use a plasticizer having good plasticization efficiency, such as DOP.

Silicon oxide, which is an essential component of the composition of the present invention, is a commercially available fine particle, particularly an average particle size of 50.
Anhydrous silicon oxide (anhydrous silica) having a thickness of less than or equal to μm, preferably less than or equal to 30 μm is desirable. Average particle size is 50 μm
If it is larger than this, the surface smoothness of the molded gasket tends to be poor. The amount of silicon oxide added is 5 to 100 parts by weight, preferably 1 part by weight, based on 100 parts by weight of the vinyl chloride resin.
A range of 0 to 70 parts by weight is suitable. Silicon oxide has a function of preventing the gasket produced from the composition of the present invention from being deformed and disintegrated when exposed to high temperature, and when the amount of addition is less than 5 parts by weight, it prevents deformation and disintegration. If the effect is insufficient, on the other hand, if the amount is more than 100 parts by weight, the processability of the composition is reduced and molding into a gasket becomes difficult. In the vinyl chloride resin composition of the present invention, in addition to the above-mentioned blending components, known components such as a flame retardant, a stabilizer, a filler, a lubricant, an antioxidant, a UV inhibitor, a foaming agent, and a coloring agent are required. Various additives such as agents can be added in an amount within the range where the physical properties of the composition are not deteriorated.

Examples of the flame retardant include antimony trioxide, zinc borate, barium metaborate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, dawsonite, calcium aluminate, red phosphorus, zinc stannate and zinc hydroxystannate. , Molybdate, and the like. In particular, by using zinc borate in combination with silicon oxide, there is an action of solidifying the carbide after carbonization of the composition, and the effect of maintaining airtightness is excellent. Thus, the amount of the flame retardant added is 250 parts by weight or less based on 100 parts by weight of the vinyl chloride resin,
It is preferably 150 parts by weight or less, and more preferably 20 to 80 parts by weight. Examples of the filler include carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica and white carbon.
The proper amount of the compound has the effect of facilitating the kneading and molding of the composition. Aluminum hydroxide and magnesium hydroxide also act as a flame retardant as described above. An appropriate amount of the filler added is 250 parts by weight or less, preferably 150 parts by weight or less, based on 100 parts by weight of the vinyl chloride resin. The total amount of the refractory agent and the filler to be added should be kept in the range of 250 parts by weight or less relative to 100 parts by weight of the vinyl chloride resin, and if the addition amount exceeds 250 parts by weight, the gasket The tensile strength and cold resistance of are decreased.

In order to produce the vinyl chloride resin composition of the present invention, the vinyl chloride resin, the plasticizer and silicon oxide and, if necessary, the above-mentioned various additives are added in a temperature range in which the vinyl chloride resin does not deteriorate. It is prepared by uniformly mixing or kneading. The device used to mix the above-mentioned blending components, for example, a Henschel mixer, a ribbon blender, a mixer such as a planetary mixer, and the like, to knead the mixture, for example, an extruder, a roll,
A device such as a Banbury mixer or a kneader capable of kneading under shear while heating is used. As a kneading method, it is also possible to adopt a method in which a resin component and various additives are charged in the former stage and an plasticizer is injected in the latter stage by using an extruder having multiple addition ports.

The thus obtained vinyl chloride resin composition of the present invention is molded by various molding methods such as extrusion molding method, injection molding method, rotational molding method, press molding method and calender roll method. Products such as gaskets, insulation boards,
It is processed into partition walls, floor materials, and wire coating. And, it was confirmed that the composition or gasket of the present invention did not ignite and had little deformation even when a heating test was carried out in a heating furnace specified by JIS A1321 (Ministry of Construction Notification No. 1828). Therefore, it can be used as a fire-resistant gasket, and its utility value is extremely high, for example, as various gaskets for construction specified in JIS A5756.

[0014]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof. Examples 1 to 6 and Comparative Examples 1 to 165 were prepared from vinyl chloride resin compositions having the compositions shown in Table-1.
After kneading with a mill roll having a surface temperature of ° C, it is made into a sheet, and this sheet is press-formed at a temperature of 180 ° C,
A gasket having a thickness of 5 mm was prepared. A test piece having a diameter of 40 mm was punched out from this gasket and subjected to a flame retardancy test. The flame retardancy test was conducted by heating the test piece at a temperature of 500 ° C. for 30 minutes using a heating furnace specified by Ministry of Construction Notification No. 1828, and evaluating the state of the test piece during and after heating. , As shown in Table-1.

[0015]

[Table 1]

[0016]

EFFECTS OF THE INVENTION The vinyl chloride resin composition of the present invention does not ignite the composition itself even when it is exposed to high temperatures because the plasticizer volatilizes little. The molded product obtained from the composition is not carbonized and solidified while maintaining its shape, and does not collapse as ash. For example, when used as a gasket, airtightness is not impaired. Further, by using zinc borate together, the solidification property after carbonization is further improved, and the disintegration can be prevented. Therefore, the composition of the present invention has an excellent performance of flame resistance and is
The utility value as a raw material of the building gasket specified in 5756 is extremely high.

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Claims (6)

[Claims] 1. A vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin, 50 to 200 parts by weight of a plasticizer containing 20% by weight or more of a flame retardant plasticizer, and 5 to 100 parts by weight of silicon oxide as main components. Stuff. 2. The vinyl chloride resin composition according to claim 1, wherein the flame-retardant plasticizer is at least one selected from phosphoric acid ester plasticizers, chlorinated paraffins and chlorinated fatty acid esters. 3. The vinyl chloride resin composition according to claim 1, wherein the silicon oxide has an average particle diameter of 50 μm or less. 4. The vinyl chloride resin composition according to any one of claims 1 to 3, which contains zinc borate. 5. A vinyl chloride resin composition for a fire resistant gasket, which comprises the vinyl chloride resin composition according to any one of claims 1 to 4. 6. A fire resistant gasket formed by molding the vinyl chloride resin composition according to claim 1.