JP2990772B2 - Low smoke resin composition and sheet comprising the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition in which the amount of smoke generated during combustion is significantly reduced, and to wallpapers and flooring materials using the composition. .

<Conventional technology and problems> Vinyl chloride resins are widely used in various fields such as various building materials, electric wire covering materials, daily necessities, toys, and interior decorations because of their excellent physical properties, workability, cost, and the like.

Since vinyl chloride resin emits more smoke during combustion than other resins, it has a drawback that it hinders evacuation guidance and fire fighting during a fire.

In general, a method of highly filling and blending an appropriate amount of antimony trioxide or a hydrate of magnesium, aluminum or the like is well known for making a vinyl chloride resin flame-retardant. However, the flame retarding method described above cannot significantly reduce the amount of smoke generated during combustion of the vinyl chloride resin composition.

JP-A-1-297448 discloses a low-smoke fume vinyl chloride resin composition characterized by combining zinc oxide, a polyhydric alcohol compound and antimony trioxide. However, it is desired to develop a technology for further reducing the amount of smoke generated during combustion. In particular, there is a strong demand for wire, wallpaper and flooring applications.

<Problem to be Solved by the Invention> An object of the present invention is to provide a flame-retardant low-smoke-release vinyl chloride resin composition in which the amount of smoke generated during combustion is significantly reduced,
It is to solve the above technical problem.

<Means for Solving the Problems> The present inventors have conducted intensive studies in order to achieve the above-mentioned problems, and by blending a compound having a smoke reducing effect into a vinyl chloride resin composition, the amount of smoke generated during combustion can be reduced. A significantly reduced vinyl chloride resin composition was found. Further, the composition was used as a resin layer or a backing material adhered to a base material, and low-smoke vinyl wallpapers and low-smoke floor materials were developed to complete the present invention.

That is, the low fuming vinyl chloride-based resin composition of the present invention is based on 100 parts by weight of the vinyl chloride-based resin, 1 to 15 parts by weight of zinc oxide and 0.07 of a polyhydric alcohol or a partial ester of a polyhydric alcohol and an organic acid. -7 parts by weight, and 2-200 parts by weight of aluminum hydroxide.

The low fuming wallpaper of the present invention is characterized in that the low fuming vinyl chloride resin composition is adhered to a base material such as paper or cloth.

The low-smoke-producing floor materials of the present invention are characterized by using the low-smoke-generating vinyl chloride resin composition as a backing material.

The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer or a copolymer containing about 50% or more of vinyl chloride. For example, vinyl chloride-vinylidene chloride, vinyl chloride-acrylonitrile, vinyl chloride-vinyl acetate, vinyl chloride-ethylene-vinyl acetate, vinyl chloride-ethylene, vinyl chloride-propylene and the like. The copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. The degree of polymerization and the size of the particle size of the vinyl chloride resin are not particularly limited, and any ordinary commercial product may be used.

The zinc oxide used in the present invention has a particle size of about 0.2 to 20 μm and may be a conventional commercial product. Compounding amount is vinyl chloride resin 10
It is 1 to 15 parts by weight based on 0 parts by weight. If the amount of zinc oxide is less than 1 part by weight, the effect of reducing the amount of smoke generated during combustion is small, and if it is not less than 15 parts by weight, the effect of reducing the amount of generated smoke during combustion is small.

The polyhydric alcohol or the partial ester of the polyhydric alcohol and the organic acid used in the present invention is a polyhydric alcohol containing at least one of pentaerythritol, dipentaerythritol, tripentaerythritol and the like. Or a partial ester of the polyhydric alcohol with a monovalent carboxylic acid such as acetic acid or propionic acid or a divalent carboxylic acid such as adipic acid or glutamic acid, which is a compound having one or more hydroxyl groups in its molecule. Good. In this case, the polyhydric alcohol or the partial ester of the polyhydric alcohol and the organic acid may be each alone or a mixture thereof. The compounding amount is 0.07 per 100 parts by weight of the vinyl chloride resin.
To 7 parts by weight, more preferably a mixture of dipentaerythritol and a partial ester of adipic acid and a polyhydric alcohol having good compatibility with a vinyl chloride resin,
A mixture in which the content of polyhydric alcohol in the mixture is 18 to 80% by weight, for example, AJI-NO-MOTO CO., LTD.
210 is 0.07 to 7 parts by weight. If the blending amount of the polyhydric alcohol compound is 0.07 parts by weight or less, the stability of the vinyl chloride resin composition against heat is extremely poor, and if it is more than 7 parts by weight, the processability of the vinyl chloride resin composition is slightly deteriorated.

Aluminum hydroxide used in the present invention has a particle size of 0.5 to 3
Any commercially available product having a thickness of about 0 μm may be used. Further, a surface-treated product using a titanate coupling agent or the like may be used. The compounding amount is 2 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 2 parts by weight, the effect of reducing the amount of smoke generated during combustion of the vinyl chloride resin composition is small, and if it is more than 200 parts by weight, there is a concern that the physical properties of the vinyl chloride resin decrease, and preferably from 20 to 180 parts by weight. is there.

The vinyl chloride resin composition of the present invention may optionally contain a plasticizer, for example, dioctyl phthalate, phthalate esters such as diisodecyl phthalate, dioctyl adipate, fatty acid esters such as dioctyl sebacate, adipic polyester, phthalate Polyesters such as acid polyesters, phosphates such as tricresyl phosphate and octyl diphenyl phosphate, epoxidized soybean oil, chlorinated fatty acid esters, and chlorinated paraffins may be used alone or in combination with two or more kinds.

In addition, stabilizers, flame retardants, antioxidants, lubricants, inorganic fillers,
Various additives such as a coloring agent, a foaming agent and a fungicide may be blended.

The vinyl wallpaper of the present invention has a structure in which a resin layer made of the low-smoke-generating vinyl chloride resin composition is bonded to a base material such as flame-retardant paper or cloth as a backing material. At this time, the foaming state of the resin layer, the pattern on its surface, the coloring, and the like are not limited at all.

The flooring material of the present invention may be, for example, the one shown in FIGS.
The low-smoke-generating vinyl chloride-based resin composition is used for the backing material portion, and a structure in which a nonwoven fabric or the like is laminated on the backing material to impart strength may be used. The thickness of the backing material is about 1 to 4 mm, a 0.1 to 0.3 mm printing layer and a 0.2 to 0.6 mm transparent resin layer thereon,
A protective layer such as 0.3 mm UV curable resin may be laminated,
Alternatively, the backing material is a pile cloth, for example, 750 to 850 g / cm
^The structure which decorated the surface with the nylon pile of ² may be sufficient.

<Function> The vinyl chloride resin composition of the present invention significantly reduces the amount of smoke generated during combustion without deteriorating physical properties such as thermal stability.

With respect to the wallpaper and flooring material of the present invention, since the low-smoke-generating vinyl chloride resin composition is used, the amount of smoke generated from the wallpaper and flooring material is significantly reduced.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. These examples do not limit the invention.

<Examples 1 to 5> The blends of Formulation Nos. 1 to 5 in Table 1 were rotated at 6 ° C open roll (manufactured by Toyo Seiki Co., Ltd.) at 160 ° C. for 10 minutes at 11 rpm of the front roll and 13.5 rpm of the roll. Roll kneading was performed to produce a sheet having a thickness of about 1 mm.

Next, after preheating this sheet with a press machine at 160 ° C for 5 minutes,
It was pressurized to 100 kg / cm ² for 5 minutes and formed into 0.5 mm and 3 mm thick sheets, respectively.

A sheet with a thickness of 0.5 mm is cut into a square with a side of 76 mm,
The test piece was used for measuring the amount of smoke emitted. The test piece is heated with a fixed radiant heat (2.5 W / cm ² ) on the surface of the test piece by a combustion furnace installed in a combustion box of a smoke tester, and NBS smoke is measured optically to measure the amount of generated smoke. The smoke emission amount Ds was determined by the non-framing method of a sex tester (manufactured by Toyo Seiki Co., Ltd.) according to the following equation.

The symbols in the formula are as follows: Ds: Specific visual density V: Burning chamber volume A: Specimen surface area L: Optical path length F ₀ : Incident light quantity F: Propagating light quantity Sheets with a thickness of 3 mm conform to JIS K 7201 The oxygen index was measured.

The sheet before press molding was cut into about 4 × 5 cm and heated in a gear oven (manufactured by Toyo Seiki Co., Ltd.) adjusted to 180 ° C. At this time, the time until the color changed to black-brown was measured to judge the quality of the thermal stability.

 Table 1 shows the obtained test results.

<Comparative Examples 6 to 15> The same operation as in Examples 1 to 5 was performed on the compounds of Formulation Nos. 6 to 15 in Table 1, and the obtained test results are shown in Table 1.

As a result, any of the vinyl chloride resin compositions in which zinc oxide, aluminum hydroxide and the prene riser ST-210 were combined reduces the amount of smoke generated. Heat stability was good. But the Pren riser ST
The amount of smoke generated from the vinyl chloride resin composition using zinc oxide and aluminum hydroxide in combination without adding -210 can be reduced to some extent, but the thermal stability is extremely poor and lacks practicality. The vinyl chloride resin composition containing aluminum hydroxide showed a tendency toward flame retardancy and low smoke emission as compared with heavy calcium carbonate and magnesium hydroxide.

<Examples 16 to 17> The blends of Formulation Nos. 16 to 17 in Table 2 were mixed and stirred for 30 minutes with an Ishikawa-type stirring and crushing machine (manufactured by Ishikawa Plant Co., Ltd.) to obtain a flame-retardant paper (Chuetsu pulp ( The weight of wallpaper is 350 on CF-70YN)
It was coated so as to be ~400g / m ^2. Next, after heating in a gear oven controlled at 150 ° C. for 10 minutes, it was further heated in a gear oven controlled at 220 ° C. for 30 seconds to produce a vinyl wallpaper prototype. NB after cutting this wallpaper into a square with a side of 76mm
S The smoke emission amount Ds is calculated by the non-framing method of the smoke emission tester.
Was measured.

<Comparative Examples 18 to 21> The blending Nos. 18 to 21 in Table 2 were operated in the same manner as in Examples 16 to 18 to measure the amount of smoke Ds. Table 2 shows the obtained results.

As a result, the vinyl wallpaper applied with the vinyl chloride resin composition in which the zinc oxide, the pren riser ST-210 and the aluminum hydroxide were combined was low in smoking. The wallpaper coated with the vinyl chloride resin composition containing zinc oxide and aluminum hydroxide was able to reduce smoke to some extent, but black spots were generated during the heating step, suggesting poor thermal stability.

<Examples 22 to 23> The formulations of Formulation Nos. 22 and 23 in Table 3A were roll-kneaded at 170 ° C. for 10 minutes using the 6-inch open roll described above to produce a sheet having a thickness of about 1 mm. Next, after preheating the sheet at 170 ° C. for 5 minutes with a press machine, the sheet was pressed to 100 kg / cm ² for 5 minutes, and then pressed at 0.
It was molded into a 5 mm thick sheet.

On the other hand, the compositions of Nos. 22 and 23 of the B composition in Table 3 were roll-kneaded at 160 ° C. for 10 minutes using the 6-inch open roll described above, and the thickness was about 1 mm Was prepared. Next, the three sheets were stacked, preheated by a press at 160 ° C. for 5 minutes, and then pressed to 100 kg / cm ² for 5 minutes to form a 2.5 mm thick sheet. Adhesive (Takibond 200 Takiron Co., Ltd.)
), And a floor material was prototyped.

The prototype floor material was cut into a square having a side of 76 mm, and the amount of smoke Ds was measured by a non-framing method using an NBS smoke emission tester.

<Comparative Examples 24-27> The compositions of Formulation Nos. 24-27 in Table 3 were operated in the same manner as in Examples 22 and 23, and the amount of smoke Ds was measured. Table 3 shows the obtained results.

As a result, the floor material using the vinyl chloride resin composition in which zinc oxide, the planizer ST-210 and the aluminum hydroxide were combined and used as a backing material produced low smoke.

<Effects of the Invention> As described above, an appropriate amount of zinc oxide, a polyhydric alcohol compound, and an alcohol hydroxide are added to a vinyl chloride resin. The combined use of ruminium significantly reduces the amount of smoke generated during combustion without deteriorating physical properties such as thermal stability of the vinyl chloride resin composition.

By applying the low-smoke-generating vinyl chloride resin composition, specifically, the smoke emission of vinyl wallpaper and flooring materials can be reduced. Furthermore, the low-smoke-generating vinyl chloride resin composition can be widely used in other fields such as various building materials, electric wire covering materials, daily necessities, toys, and interior decorations. Therefore, in the event of a fire, evacuation guidance and fire extinguishing activities are easier than in the past.

[Brief description of the drawings]

Figure 1 is a cross-sectional view of a flooring material, 1 is a backing material, 2 is a nonwoven fabric, etc.
Reference numeral 3 denotes a printing layer, 4 denotes a transparent resin layer, and 5 denotes a surface protection layer. Figure 2 is a sectional view of a tile carpet, 1 is a backing material, 2
Is a non-woven fabric and 6 is a pile fabric.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06N 7/00 D06N 7/00 D21H 27/20 D21H 27/20 A 27/30 27/30 C (58) Fields surveyed (Int. .Cl. ⁶ , DB name) C08L 27/06 C08K 3/22 C08K 5/053 C08K 5/103

Claims (3)

(57) [Claims] (1) 100 parts by weight of a vinyl chloride resin, 1 to 15 parts by weight of zinc oxide, 0.07 to 7 parts by weight of a polyhydric alcohol or a partial ester of a polyhydric alcohol and an organic acid, and aluminum hydroxide. A low fuming vinyl chloride resin composition comprising 2 to 200 parts by weight. 2. Wallpapers having a resin layer and a base material, wherein the resin layer is a low-smoke vinyl chloride resin composition according to claim 1. 3. A flooring material having a surface layer and a backing material, wherein the backing material is the low fuming vinyl chloride resin composition according to claim 1.