JPS6210259B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-stable polyvinyl chloride resin-based tile composition, in particular, 100 parts by weight of rosin, structural formula

[Formula] (In the formula, A ₁ and A ₂ are phenol group, alkylphenol group,
Naphthol group, alkylnaphthol group, n
represents a positive integer of 0 to 2) 0.02 to 2 parts by weight of one or more of the compounds represented by 0 to 2, and 0.02 to 3 parts by weight of one or more of tin and tin compounds. , one or more of alkaline earth metal oxides, hydroxides, and acetates;
10 parts by weight is heated to 180°C to 280°C, and the heated product is heated to 0.5 to 25 parts by weight of polyvinyl chloride.
The present invention relates to a polyvinyl chloride resin tile composition characterized in that it is added and kneaded in a proportion corresponding to % by weight. Originally, polyvinyl chloride resin has excellent impact resistance,
It is popular as a raw material for floor tiles because of its moisture resistance, but on the other hand, it has thermal deterioration properties, is susceptible to heat history during tile manufacturing, has poor caking properties with inorganic substances, and is rolled during the roll kneading process. Since there are various drawbacks such as poor roll adhesion, there is a need to improve these. As one remedy for this, alkaline earth metal salts of rosin are now being used. However, the alkaline earth metal salts in this rosin lack thermal stability, and the resin becomes darkly colored during the heat processing process, making it difficult to obtain light-colored products, and at the same time, thermal deterioration of the product cannot be avoided. There are drawbacks. As a result of intensive research to overcome these drawbacks, the present inventors found that 100 parts by weight of rosin, the structural formula

[Formula] (In the formula, A ₁ and A ₂ are phenol group, alkylphenol group, naphthol group,
or an alkylnaphthol group, where n is 0 to 2
(denotes a positive integer)
0.02 to 2 parts by weight of one or more species, 0.02 to 3 parts by weight of one or more of tin and tin compounds, and one of alkaline earth metal oxides, hydroxides, and acetates. A heated product obtained by mixing and heating 2 to 10 parts by weight of seeds or two or more species is added to polyvinyl chloride resin in an amount equivalent to 0.5 to 25% by weight, and the mixture is kneaded and heated. It was discovered that the material is light colored and thermally stable, making it suitable as a resinous material for floor tiles, thus completing the invention. In the present invention, 100 parts by weight of rosin is
Heated to 280℃, structural formula

_One of _the substances represented by the formula or 0.02 to 2 parts by weight of two or more types of tin and one or more types of tin compounds
Add 0.02 to 3 parts by weight and 2 to 10 parts by weight of one or more of alkaline earth metal oxides, hydroxides, and acetates at 180°C to 280°C.
By heating and kneading the heated product obtained by kneading at ℃ for 1 to 10 hours with polyvinyl chloride resin, a polyvinyl chloride resin-based tile composition with the desired excellent performance can be easily obtained. . Examples of the rosin used in the present invention include tall rosin, gum rosin, utoprosin, disproportionate reaction products and aldehyde addition products of these rosins, and dienophile adducts of these rosins such as maleic anhydride, fumaric acid, and alluric acid. Can be mentioned. Structural formula used in the present invention

[Formula] (wherein A ₁ and A ₂ represent a phenol group, an alkylphenol group, a naphthol group, or an alkylnaphthol group, and n represents a positive integer from 0 to 2) include 3 -t-butyl-4-hydroxy-6-methylsulfoxide, 3-t-
butyl-4-hydroxy-6-methylsulfone,
Examples include 4,4'-thiobis-[2-t-butyl-5-methylphenol]. The reason why the amount of these compounds used was limited to 0.02 to 2 parts by weight as mentioned above is that if it is less than 0.02 parts by weight, the thermal stability of the resulting product tile composition will be poor and the degree of coloration will be too high. If the amount is more than 2 parts by weight, the effect of imparting thermal stability will be poor compared to the proportion of the amount added, and at the same time, this will cause uneconomical effects in industrial production. Examples of tin and tin compounds used in the present invention include metallic tin, stannous oxide, stannous chloride, stannic oxide, and stannic chloride. The reason why the amount of these additives is limited to 0.02 to 3 parts by weight is that if it is less than 0.02 parts by weight, the resulting product tile composition will have a poor color and will not have sufficient thermal stability as a floor tile.
This is because if the amount is more than 3 parts by weight, the thermal stability effect will not increase in proportion to the amount added, and it will be uneconomical in terms of industrial production. Structural formula

One of the compounds represented by [Formula] (wherein A ₁ and A ₂ represent a phenol group, an alkylphenol group, a naphthol group, or an alkylnaphthol group, and n represents a positive integer from 0 to 2) or The reason why two or more types and one or more types of tin and tin compounds are used in combination is to reduce the hardness of the resulting tile composition and improve its thermal stability. Examples of alkaline earth metal oxides, hydroxides, and acetates include calcium oxide, zinc oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium acetate, zinc acetate, and magnesium acetate. . The reason for limiting the amount of these compounds added is 2 to 10 parts by weight.
If the amount is less than 10 parts by weight, the softening point will be low, and workability such as roll wrapping properties will not improve, and sufficient thermal stability will not be imparted to the polyvinyl chloride resin system, and if it is more than 10 parts by weight. This is because the above-mentioned heated reaction product according to the present invention thickens, making the manufacturing process difficult to perform, and the effect of imparting thermal stability is not improved depending on the proportion of the amount added. Furthermore, the amount of these heating reaction products added above was limited to 0.5 to 25% by weight based on the polyvinyl chloride resin, because if it is less than 0.5% by weight, the resulting polyvinyl chloride resin will have insufficient thermal stability. This is because the polyvinyl chloride resin obtained by adding 25% by weight is This is because it can maintain sufficient thermal stability and mechanical strength, so it is meaningless to add more than 25% by weight and is uneconomical in terms of industrial production. Wax can also be used as a raw material in the heated product to be kneaded into the polyvinyl chloride resin according to the present invention. By using this combination, various physical properties of the product polyvinyl chloride resin composition were improved, and no deterioration was observed. The polyvinyl chloride resin composition according to the invention has no inferior features compared to conventional rosin made only of alkaline earth metal salts, and has a lower degree of coloring, so product tiles can be produced in various colors. It can be emphasized that it can be made to have the following properties and that it has excellent thermal stability. Example 1 300 g of Chinese gum rosin (acid value 162) was charged into a 500 c.c. five-necked flask equipped with a stirring device, a condenser with Isaac tube, a thermometer, a nitrogen gas blowing tube, and an addition port, and 3-t-butyl was added. - Added 0.9 g of 4-hydroxy-6-methyl sulfoxide, heated to 270°C while passing nitrogen gas, kept for 1 hour, cooled to 230°C, added 0.6 g of stannous oxide, and stirred for 1 hour. I left it alone. Next, a mixture of 24 g of calcium hydroxide and 2 g of calcium acetate was gradually added thereto over a period of 4 hours, and the mixture was then maintained at 240°C to 260°C for 2 hours to obtain a heated product A. Example 2 Into the reaction vessel described in Example 1, 300 g of disproportionated tall rosin (acid value 152) was charged, 1.2 g of 3-t-butyl-4-hydroxy-6-methylsulfone was added, and the mixture was heated at 270°C while passing nitrogen gas. Keep time at 230℃
After cooling, 0.2 g of metal tin was added and the mixture was left stirring for 1 hour. Next, a mixture of 10 g of calcium hydroxide and 2 g of magnesium oxide was gradually added over 3 hours, and then kept at 240-260°C for 2 hours to form heated product B.
I got it. Example 3 300 g of maleic acid-adducted rosin (acid value 208) was charged into the reaction vessel described in Example 1, and 4,4'-thiobis-
[2-t-butyl-5-methylphenol] 1.5g
The mixture was kept at 270°C for 1 hour, and after cooling to 230°C, 1.5g of stannous chloride was added and the temperature was raised to 240°C. A mixture of 10 g of calcium acetate and 11 g of zinc oxide was gradually added over a period of 4 hours, and then kept at 240-260°C for 2 hours to obtain a heated product C. Example 4 100 g of heated product A obtained in Example 1 and 10 g of 140% paraffin wax were mixed at 200°C to obtain heated product D. Comparative Example 1 Thorrosin (acid value) was placed in the reaction vessel described in Example 1.
165) 300g was charged and heated to 240°C under nitrogen gas. 26 g of calcium hydroxide was gradually added over a period of 4 hours, and the temperature was maintained at 240 to 260° C. for 2 hours to obtain heated product E. Comparative Example 2 Gum rosin (acid value
162) Add 0.9 g of 3-t-butyl-4-hydroxy-6-methyl sulfoxide to 300 g, heat to 270°C while passing nitrogen gas, keep for 1 hour, cool to 230°C, and add 24 g of calcium hydroxide. A mixture with 2 g of calcium acetate was gradually added over a period of 4 hours, and the mixture was then maintained at 240 to 260°C for 2 hours to obtain heated product F. Comparative Example 3 Toll rosin (acid value
165) Add 0.6 g of stannous oxide to 300 g, raise the temperature to 230°C while passing nitrogen gas, keep it for 1 hour, and prepare 24 g of calcium hydroxide and 2 g of calcium acetate.
was gradually added over a period of 4 hours, and after 240
The heated product G was obtained by keeping the temperature between 260°C and 260°C for 2 hours. The softening point and hue of the heated products of each of the above Examples and Comparative Examples were measured. At this time, the softening point is JIS
Measurement was performed according to K-2531, and the hue was measured using a Gardner colorimeter. The results are shown in Table 1.

[Table] Also, using the heated products according to the present invention and comparative examples,
After kneading the composition shown in Table 2 with a mixing roll at 150°C to 160°C, a sheet was formed to a film thickness of 2 mm, and pressed at 150°C, 50 kg/cm ² for 3 minutes. The thermal stability test of the specimen was measured in a gear oven at 170°C, and the weather resistance was measured with a weatherometer.

[Table] The results are shown in Table 3. The deterioration time in Table 3 indicates the time required for the test piece to become colored.

[Table] From the results in Table 3, it can be seen that the heated product of the present invention is excellent in thermal stability and weather resistance. In addition, the thermal stability and weather resistance of A and E were tested using the formulations shown in Table 4 while varying the blending ratio. The results are shown in Table 5.

[Table] After kneading the above compound with a mixing roll at 150 to 160°C, a sheet was formed to a film thickness of 2 mm, and pressed at 150°C, 50 kg/cm ² for 3 minutes. The thermal stability test of the specimen was measured in a gear oven at 170°C, and the weather resistance was measured with a weatherometer.

[Table] From the results in Table 5, it can be seen that the thermal stability and weather resistance improve as the amount of the heated product increases, and the heated product of the present invention is superior to that used as a comparative example. Recognize. Further, in the case of the present invention, the roll windability was good, and there were no problems with the water absorption rate and strength of the obtained polyvinyl chloride resin sheet.

Claims (1)

[Claims] 1 100 parts by weight of rosin, structural formula [Formula] (wherein A ₁ and A ₂ represent a phenol group, an alkylphenol group, a naphthol group, or an alkylnaphthol group, and n is 0 to 0.02 to 2 parts by weight of one or more of the compounds represented by (representing a positive integer of 2), 0.02 to 3 parts by weight of one or more of tin and tin compounds, and alkaline earth. A heated product obtained by adding 2 to 10 parts by weight of one or more of metal oxides, hydroxides, and acetates, mixing, and heating at 180°C to 280°C, 0.5 for PVC resin
Added at a rate of 25% by weight, 150℃ to 160℃
A polyvinyl chloride resin tile composition obtained by heating and kneading the composition.