JPH06240082A - Polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a substantially transparent polyvinyl chloride resin which scarcely gives off hydrogen chloride and carbon dioxide when incinerated. CONSTITUTION:This resin composition contains synthetic zeolite X or Y having a means particle diameter of 0.1-1.0mum and a degree of crystallinity of 70% or above. The synthetic zeolite is synthesized in an aqueous water-soluble polymer solution, has the form of a salt of at least one metal selected from among the elements of groups 1, 2 and 12 of the periodic table, and is contained in an amount of 0.5-5wt.%.

Description

Detailed Description of the Invention

[0010]

TECHNICAL FIELD The present invention relates to a polyvinyl chloride resin composition. More specifically, the present invention relates to a substantially transparent polyvinyl chloride resin composition that generates little hydrogen chloride gas and carbon dioxide gas when incinerated.

[0011]

2. Description of the Related Art Polyvinyl chloride resins are widely used because they have excellent physical strength, transparency, flame retardancy, molding processability, and relatively low price. It is plastic. Polyvinyl chloride resin is used in a wide variety of applications because it has excellent molding characteristics in addition to the above-mentioned excellent performance characteristics, and is extremely useful if the generation of hydrogen chloride gas during incineration is reduced. That is. It has been known for a long time that zeolite effectively captures hydrogen chloride generated by thermal decomposition of a chlorine-containing polymer, and it has been proposed to use zeolite as a stabilizer for vinyl chloride resin by utilizing this effect ( Japanese Patent Publication No. 58-18939). In addition, proposals for utilizing various synthetic zeolites for this purpose have also been made (Japanese Patent Publication No. 60-45660).

[0012]

However, in the conventional polyvinyl chloride resins to which synthetic zeolite is added, hydrogen chloride gas generation cannot be reduced unless a large amount is added. It is not suitable for transparent products and products with vivid color tones due to poor transparency.
The present inventors have studied to provide a polyvinyl chloride resin composition that is excellent in transparency and that generates less hydrogen chloride gas and less carbon dioxide gas during incineration.

[0013]

Means for Solving the Problems The polyvinyl chloride resin composition of the present invention contains an X-type or Y-type synthetic zeolite having an average particle size of 0.1 to 1.0 μm and a crystallinity of 70% or more. The above synthetic zeolite is a salt of one or more kinds of metals selected from Groups 1, 2 and 12 of the periodic table of elements, which are synthesized in an aqueous solution of a water-soluble polymer. Is 0.5 to 5% by weight.

The polyvinyl chloride resin composition of the present invention is
It contains an X-type or Y-type synthetic zeolite having an average particle size of 0.1 to 1.0 μm and a crystallinity of 70% or more. The average particle size of the synthetic zeolite used in the present invention is 0.1 to
The thickness is 1.0 μm, preferably 0.1 to 0.7 μm. Further, those having a sharp particle size distribution and no coarse particles are desirable.
As the average particle size of the synthetic zeolite increases, the transparency of the polyvinyl chloride resin containing it decreases. The crystallinity of the synthetic zeolite used in the present invention is 70%.
It is above, and preferably 80% or more. As the crystallinity decreases, the effect of suppressing the hydrogen chloride gas generated during combustion of the polyvinyl chloride resin composition containing the synthetic zeolite decreases. The synthetic zeolite used in this patent is selected from among X-type and Y-type, which results in excellent gas adsorption performance.

The content of the synthetic zeolite in the polyvinyl chloride resin composition is preferably 0.5 to 5% by weight, and is 0.5 to 1.5% by weight when transparency is particularly important. . If it is less than 0.5, the generation of hydrogen chloride gas and carbon dioxide gas at the time of incineration is small, and if it exceeds 5% by weight, the transparency is deteriorated. The synthetic zelite used in this patent is selected from the X-type and Y-type, which have excellent gas adsorption performance. This synthetic zeolite consists of AlO4 and SiO4
Are connected by sharing oxygen ions with each other,
An inorganic polymer having a crystalline X-type or Y-type structure having an infinite skeleton can be used. The X-type or Y-type synthetic zeolite has tunnel type pores of 7 to 8 angstrom, and the pores show excellent adsorption performance. The synthetic zeylite used in this patent can be used alone or in combination of two or more kinds. As a concrete example, N
a-X, Na-Y, Ca-X, Ca-Y, Mg-X, M
Examples thereof include g-Y, Zn-X, and Zn-Y types. As an example of the metal of the synthetic zeolite used in the present invention, one of the metals selected from Group 1 (alkali metal), Group 2 (alkaline earth metal), and Group 12 of the periodic table of the elements, or Two or more can be indicated. Further specific examples of metals include Na and K in Group 1 of the periodic table, Ca and Mg in Group 2, and Zn and Cd in Group 12 of the periodic table. N
The salt of a metal other than a is obtained by the ion exchange method of Na salt. In the case of synthetic zeolite, SiO2: Al2
Depending on the ratio of O3 and the conditions of synthesis, A type, X type, Y type
There are many types such as types.

The synthetic zeolite used in the present invention is
It can be obtained by the production method disclosed in JP-A-1-131512, and this method comprises mixing a metal oxide or a metal salt, a metal aluminate salt and colloidal silica in an aqueous solvent containing a water-soluble polymer. This is to synthesize synthetic zeolite. As the water-soluble polymer, gelatin, β-cellulose alginic acid, polyvinyl alcohol and the like are used alone or in combination. Synthetic zeolite produced by this method has performance such as adsorption capacity and ion exchange capacity similar to the conventional synthetic zeolite, but the shape of the synthetic zeolite is rounded and has a conventional cubic shape. The shape is different.

The polyvinyl chloride resin composition of the present invention is
Polyvinyl chloride or vinyl chloride copolymer is mixed with the synthetic zeolite described in this patent, and if necessary, a plasticizer, a stabilizer, an impact toughening agent, a processing aid, a lubricant, an ultraviolet absorber, a colorant, etc. . If transparency is not required, a filler can be added. This composition is formed into a film, a sheet, a plate, a pipe, a joint, various parts and the like by calendering, extrusion molding, injection molding and the like. Further, the film or sheet can be subjected to secondary processing such as vacuum forming or printing. Furthermore, the polyvinyl chloride resin composition of the present invention excels in the property of absorbing infrared rays, and can be suitably used for applications requiring heat retention, such as agricultural films. In addition, by utilizing the hygroscopicity of synthetic zeolite, it is possible to impart antifogging property and humidity control property to products such as agricultural films and wallpapers.

[0018]

EXAMPLES The effects of the present invention will be specifically described by way of examples. The tests of Examples and Comparative Examples followed the following methods. Average particle size and particle size distribution: Measured with a laser diffraction type particle size distribution measuring device (Shimadzu Corporation; SALD-2000 type). The median diameter was defined as the average particle diameter. The particle size distribution is
The minimum value to the maximum value are shown. Crystallinity: Comparative measurement was performed by a relative method using X-ray diffraction, with the crystallinity of the following sample set to 100%. X-type zeolite: 13X (Nika Seiko Co., Ltd.) Y-type zeolite: 2CP-50 (Catalyst Kasei Co., Ltd.) A-type zeolite: 4A (US Union Carbide Co., Ltd.) Haze; Plastic optical property test method (JIS
K 7105). Used as an indicator of transparency. The smaller the number, the better the transparency.

Combustion gas generation rate: Calculated from the gas generation amount measured by the plastic combustion gas analysis method (JISK 7217). When the synthetic zeolite described in this patent is not mixed (Comparative Example 1), the generated amount is a, and when the mixed amount is b,

Examples 1 to 15 10 parts by weight of MBS resin-based impact toughening agent, 2 parts by weight of epoxidized soybean oil, and octyl per 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 700 (Kyoto PVC Co., Ltd .; SE) 2.2 parts by weight of a tin stabilizer, 0.3 parts by weight of a wax lubricant, and 0.2 parts by weight of stearic acid were added. To this, as shown in Examples 1 to 15 in Table 1, synthetic zeolite (Special Kika Kogyo Co., Ltd .; Seabright) was added and mixed with a Henschel mixer, which was then rolled with an 8-inch two-roll mill. The mixture was kneaded at 195 ° C. for 3 minutes to obtain a sheet having a thickness of 0.3 mm.
Table 1 shows the transparency of the sheet and the amount of gas generated during combustion. The synthetic zeolites of the examples were synthesized in an aqueous solvent using gelatin as a water-soluble polymer.

Comparative Example 1 Those excluding the synthetic zeolites of Examples 1 to 10 were mixed with a Henschel mixer, and then mixed with an 8-inch two-roll mill for 19 hours.
Kneading at 5 ° C. for 3 minutes to obtain a sheet having a thickness of 0.3 mm. The optical properties of the sheet and the amount of gas generated during combustion are shown in Table 2. Comparative Examples 2 to 7 10 parts by weight of MBS resin-based impact toughening agent, 2 parts by weight of epoxidized soybean oil, and octyltin-based stability with respect to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 700 (Kyoto PVC Co., Ltd .; SE). 2.2 parts by weight of the agent, 0.3 parts by weight of the wax lubricant, and 0.2 parts by weight of stearic acid are compounded. As shown in Comparative Examples 2 to 7 in Table 2, synthetic zeolite (Mizusawa Chemical Industry Co., Ltd .; TAF) was added thereto and mixed with a Henschel mixer, and the mixture was mixed with an 8-inch two-roll mill at 195 ° C.
Kneading for 3 minutes to obtain a sheet having a thickness of 0.3 mm. The optical properties of this sheet and the amount of gas generated during combustion are shown in Table 2.

Comparative Examples 8-9 10 parts by weight of MBS resin-based impact enhancer, 2 parts by weight of epoxidized soybean oil, and octyl with respect to 100 parts by weight of polyvinyl chloride having an average degree of polymerization of 700 (Kyoto PVC Co., Ltd .; SE) 2.2 parts by weight of a tin stabilizer, 0.3 parts by weight of a wax lubricant, and 0.2 parts by weight of stearic acid were added. As shown in Comparative Examples 8 to 9 in Table 2, synthetic zeolite (Union Carbide Co., USA; 4A) was added thereto and mixed with a Henschel mixer, and the mixture was mixed with an 8-inch two-roll mill to 19
Knead at 5 ° C for 3 minutes to form a sheet, and add 19
After heating at 5 ℃ for 2 minutes, at the same temperature for 3 minutes 200Kg / c
The sheet was pressed at a pressure of m ² to obtain a sheet having a thickness of 0.3 mm.
Table 2 shows the haze of this sheet and the amount of gas generated during combustion.

[0023]

The effect of the present invention is that the transparency of the polyvinyl chloride resin is not substantially reduced, the generation of hydrogen chloride gas during incineration is reduced, and further the generation of carbon dioxide gas is suppressed. Is Rukoto. In addition, the importance of recycling is emphasized from the viewpoint of effective use of resources, and for example, when a used polyvinyl chloride resin product is decomposed and recovered as an oil, the polyvinyl chloride resin composition of the present invention is There is an advantage that it can be easily recovered as oil by the catalytic action of zeolite.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

Claims (2)

[Claims] 1. A polyvinyl chloride resin composition containing an X-type or Y-type synthetic zeolite having an average particle diameter of 0.1 to 1.0 μm and a crystallinity of 70% or more. 2. The synthetic zeolite according to claim 1, which is synthesized in an aqueous solution of a water-soluble polymer, and which is a group 1 or 2 element of the periodic table of elements.
It is a salt of one or more metals selected from Group 12 and Group 12, and has a synthetic zeolite content of 0.5 to 5
Polyvinyl chloride resin composition which is wt%