JP3132161B2 - Cold resistant sheet made of vinyl chloride resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold-resistant and highly elastic sheet or film made of a vinyl chloride resin.

[0002]

2. Description of the Related Art Vinyl chloride resin sheets have a good balance of physical strength, are excellent in welding workability, and are relatively inexpensive. It is used in water treatment works for waste disposal sites, river embankments, port facilities, etc. Of these, in cold regions,
In particular, a low-temperature-resistant vinyl chloride resin film is desired even in a sheet having excellent cold resistance, a freezer, a refrigerator and the like.

[0003]

Generally, a plasticizer is added to a vinyl chloride resin sheet or film to impart flexibility. As the plasticizer at this time, di-2-ethylhexyl phthalate is widely used because of its well-balanced performance and price. However, in this case, it becomes hard at a low temperature in a cold region or winter, and the handling workability deteriorates.
In addition, the elongation is reduced, making it vulnerable to tearing. In addition, there is a problem that the plasticizer dissipates with time and the flexibility and strength of the sheet decrease.

[0004] Various plasticizers have been studied to improve the disadvantages of the vinyl chloride resin sheet or film. However, the use of conventionally known plasticizers has disadvantages. For example, di-2-phthalic acid
When diisononyl phthalate is used instead of ethylhexyl, the tear strength of the sheet decreases and the plasticizer dissipates. Further, a sheet using diisodecyl phthalate as a plasticizer has insufficient flexibility at low temperatures.

[0005]

Means for Solving the Problems The present inventors diligently studied a method for improving the conventional disadvantages without impairing the balanced performance and economy of a vinyl chloride resin sheet or film. As a result, by blending and using a phthalic acid diester of a specific mixed alcohol and an epoxy resin, a soft temperature is low, and it is found that a cold-resistant sheet made of a vinyl chloride resin having ultra-high cold resistance and high elasticity can be obtained.
The present invention has been completed.

The cold-resistant sheet made of a vinyl chloride resin of the present invention comprises:
95.0% by weight to 99.0% by weight of 2-propylheptanol and 1.0% of 4-methyl-2-propylhexanol
A composition obtained by blending 65 parts by weight to 105 parts by weight of a plasticizer composed of a phthalic acid diester of a mixed alcohol with 100 parts by weight of a vinyl chloride resin in 100 parts by weight of a vinyl chloride resin. It is characterized by the following.

The phthalic acid diester comprises 95.0% by weight to 99.0% by weight of 2-propylheptanol and 4% by weight.
-Methyl-2-propylhexanol obtained by an esterification reaction of mixed decyl alcohol with 1.0 to 5.0% by weight and phthalic acid or phthalic anhydride.

The mixed decyl alcohol is prepared, for example, by oxo synthesis using butene-1 as an olefin to produce a mixture of n-valeraldehyde and 2-methylbutyraldehyde, and by aldol condensation of these aldehydes and subsequent dehydration reaction. Mixtures of 2-propylheptenal and 4-methyl-2-propylhexenal can be prepared and synthesized by hydrogenating these mixtures. If necessary, the mixed decyl alcohol composition may be prepared by distillation. However, the present invention is not limited by these production methods.
For example, 2-propylheptanol and 4-methyl-2-
It is also possible to prepare propylhexanol separately and mix them.

The epoxy resin used in the present invention is a condensation product of epichlorohydrin and bisphenol, for example, bisphenol A type, halogenated bisphenol A type, resorcinol type, bisphenol F type, tetrahydroxyphenylmethane type, polyalcohol Type,
Polyglycol type and the like can be mentioned.

[0010] The vinyl chloride resin used in the present invention is polyvinyl chloride and a vinyl chloride copolymer. The vinyl chloride copolymer is mainly composed of vinyl chloride and other monomers such as ethylene, propylene, vinyl acetate, alkyl vinyl ether, and the like. Copolymers with methacrylic acid esters, acrylic acid esters and the like can be mentioned, but the present invention is not limited to these types of resins.

The amount of the phthalic acid diester in the sheet of the present invention depends on the application, but it is used at a low temperature. Therefore, it is preferable to add 65 to 105 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the compounding amount is less than 65 parts by weight, the flexibility of the sheet at low temperature is insufficient, and the characteristics of cold resistance and high elasticity cannot be obtained. If it exceeds 105 parts by weight, the sheet becomes too soft at normal times.

As the plasticizer used in the present invention, in addition to the phthalic acid diester of the mixed alcohol, plasticizers generally used for vinyl chloride resins, for example, di-2-ethylhexyl phthalate, diisononyl phthalate, di-2-adipic acid.
Ethylhexyl, epoxidized soybean oil, phosphate plasticizers and the like may be included, and these may be used in combination. In this case, vinyl chloride resin 100
It is preferable to mix 65 to 105 parts by weight as the total amount of the plasticizer with respect to parts by weight. However, it is preferable that the ratio of the combined use of the plasticizer is within a range that does not impair the effects of the present invention.

The vinyl chloride resin of the present invention includes, in addition to a vinyl chloride resin, a phthalic acid diester of a mixed alcohol, and an epoxy resin, if necessary, a stabilizer, a stabilizing aid, an antioxidant, a lubricant, an ultraviolet absorber, Coloring agents, reinforcing agents, processing aids, fillers and the like can be added.

Examples of the stabilizer include lead salts such as tribasic lead sulfate, metal soap stabilizers such as calcium stearate, barium stearate, zinc stearate, calcium ricinoleate and barium laurate;
Examples thereof include organic tin-based stabilizers such as dibutyltin dilaurate, dibutyltin maleate, and dioctyltin mercaptide.

Examples of the stabilizing aid include phosphites such as triphenyl phosphite, tri-2-ethylhexyl phosphite, and trinonylphenyl phosphite. For example, t-butylhydroxytoluene and dilaurylthiodipropionate can be mentioned.

Examples of the lubricant include stearic acid, stearic acid amide, and polyethylene wax. Examples of the ultraviolet absorber include 2- (5'-methyl-2'-hydroxyphenyl) benzotriazole,
2- (3'-tert-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzo-1,2,4-triazole.

Examples of the coloring agent include inorganic pigments such as phthalocyanine blue, titanium oxide and carbon black;
And organic pigments. Examples of the reinforcing agent include a copolymer of polymethacrylate, butadiene and styrene, acrylonitrile butadiene rubber, and a copolymer of ethylene and vinyl acetate.

Examples of the processing aid include polymethyl methacrylate. Examples of the filler include calcium carbonate. However, these additives
It is not limited to the above types.

The vinyl chloride resin sheet of the present invention is obtained by mixing a vinyl chloride resin with a phthalic acid diester of a mixed alcohol of 2-propylheptanol and 4-methyl-2-propylhexanol as a sheet. It is molded, and as a production means, generally used mixing equipment such as a ribbon blender and a Henschel type mixer, kneading equipment such as a Banbury mixer and two rolls, an extruder equipped with a calendar roll and a T-die, and the like. Film forming equipment such as a laminator can be used.

[0020]

EXAMPLES The excellent properties of the vinyl chloride resin sheet of the present invention will be described more specifically with reference to examples.
In addition, the following evaluation test is performed by the following method. [Tensile strength, elongation] According to JIS K 7113. [Hardness] A spring type hardness tester A type was used in accordance with JIS K6301.

[Tear Strength] A B-type test piece was used for the measurement in accordance with JIS K6301. [Flexible temperature] According to JIS K 6745.

[Heating weight change rate] JIS K 7113
No. 2 test piece in a gear type aging tester at 120 ° C.
Heat for 0 hours and measure the weight change rate. The weight change rate is a percentage obtained by dividing the weight difference between the test pieces before and after the test by the weight before the test. Minus indicates weight loss.

[Hot water weight change rate] JIS K 7113
No. 2 test piece was immersed in warm water of 100 ° C. for 480 hours,
Measure the weight change rate. The weight change rate is a percentage obtained by dividing the weight difference between the test pieces before and after the test by the weight before the test. Minus indicates weight loss. [100% modulus] JI as flexibility at each temperature
According to the tensile test of SK 7113, the elongation is 100
% Was obtained.

Example 1 [Mixed alcohol] Commercially available n-valeraldehyde 68 was placed in a two-liter four-necked flask equipped with a magnetic stirrer, a Dimroth condenser, a thermocouple thermometer and a dropping device.
8.3 g and 14.2 g of 2-methylbutyraldehyde were charged and stirred. Prepare a 1.0 wt% aqueous NaOH solution,
This was dropped into the flask at 25 ° C. After 60 minutes, the dropwise addition was completed, and the temperature in the system at this time was 58 ° C. Thereafter, heating was started and, after reaching 85 ° C., stirring was continued for 4 hours. Next, after cooling to room temperature, stirring was stopped and oil-water separation was performed to obtain 584.8 g (water content: 0.54% by weight) of an oil layer (aldol condensate).

Oil layer of aldol condensate in a 1 liter stainless steel autoclave equipped with a magnetic stirrer, hydrogen pressure regulator and thermocouple under nitrogen atmosphere.
2 g and 26.5 g of Raney nickel as a catalyst were charged. After replacing the inside of the system with hydrogen three times, the hydrogen pressure was increased to 50 kg /
It was set to cm ² and stirred at 500 rpm. At the same time,
When the electric furnace was heated and the temperature was raised, the temperature in the system was 95%.
Hydrogen absorption started at around ° C., and continued for 3.5 hours thereafter (the highest temperature reached during this period was 160 ° C.). Stirring was continued at 130 to 145 ° C. for another 2 hours after the hydrogen absorption ceased, and then heating was stopped. After standing overnight, the catalyst was filtered off using a membrane filter to obtain 540.2 g of an oil layer. This oil layer was distilled under reduced pressure using a 25-stage Oldershaw distillation apparatus. At the beginning of distillation, the operation was performed at a reduced pressure of 30 to 60 mmHg, and then the reduced pressure was reduced to 10 mmHg.
Was changed to 30 mmHg, and a distillate having an overhead temperature of 105 ° C / 16 mmHg to 106 ° C / 17 mmHg was obtained. This was analyzed by capillary gas chromatography, and as a result, 96.0% by weight of 2-propylheptanol (2PHO) and
4-methyl-2-propylhexanol (MPHO)
It was found to be a mixed decyl alcohol containing 3.9% by weight.

[Phthalic acid diester] In a 2 liter flask, 413.2 g of phthalic anhydride and 1086.5 g of mixed decyl alcohol were charged as raw materials under a nitrogen atmosphere. The solution is heated while stirring, and the temperature of the reaction solution is 60 ° C.
Then, 7.0 g of a 25% by weight decanol solution of tetraisopropoxytitanium as a catalyst was added, and the temperature was further raised to 220 ° C. Produced water was removed from the system using an oil-water separator attached to the reactor, and unreacted alcohol was returned to the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C. When the acid value became 0.3 or less (after about 5 hours), heating was stopped, and normal neutralization, washing with water, After subjecting to vacuum distillation and post-treatment operations, the target substance, didecyl phthalate (DXP-1) 1160
g was obtained. At this time, the acid value was 0.021, the residual alcohol content was 100 ppm or less, and the water content was 0.07% by weight.

[Cold-resistant sheet made of vinyl chloride resin] Polyvinyl chloride having an average polymerization degree of 1300 (manufactured by Chisso Corporation: PVC)
70 parts by weight of didecyl phthalate (DXP-1), 2 parts by weight of epoxy resin (bisphenol A type, n = 2 to 3), 2 parts by weight of barium-zinc liquid stabilizer, stearin A sheet was prepared by mixing 0.5 part by weight of an acid stabilizer. Furthermore, this is 18
After preheating at 5 ° C. for 2 minutes, pressurizing at 150 kg / cm ² for 3 minutes to make a 1 mm thick sheet,
The elongation, hardness, tear strength, softening temperature, rate of change in weight by heating, rate of change in weight of warm water, and 100% modulus were measured.

Example 2 [Mixed alcohol] Commercially available n-valeraldehyde 69 was placed in a two-liter four-necked flask equipped with a magnetic stirrer, a Dimroth condenser, a thermocouple thermometer and a dropping device.
5.3 g and 7.0 g of 2-methylbutyraldehyde were charged and stirred. A 1.0% by weight aqueous NaOH solution was prepared and added dropwise to the flask at 25 ° C. After 60 minutes, the dropwise addition was completed, and the temperature in the system at this time was 58 ° C. Thereafter, heating was started and, after reaching 85 ° C., stirring was continued for 4 hours. Next, after cooling to room temperature, stirring was stopped, and oil-water separation was performed to obtain 585.7 g (water content: 0.56% by weight) of an oil layer (aldol condensate).

Oil layer of aldol condensate in a 1 liter stainless steel autoclave equipped with a magnetic stirrer, hydrogen regulator and thermocouple under nitrogen atmosphere.
1 g and 26.5 g of Raney nickel as a catalyst were charged. After replacing the inside of the system with hydrogen three times, the hydrogen pressure was increased to 50 kg /
It was set to cm ² and stirred at 500 rpm. At the same time,
When the electric furnace was heated and the temperature was raised, the temperature in the system was 95%.
Hydrogen absorption started at around ° C., and continued for 3.5 hours thereafter (the highest temperature reached during this period was 160 ° C.). Stirring was continued at 130 to 145 ° C. for another 2 hours after the hydrogen absorption ceased, and then heating was stopped. After standing overnight, the catalyst was filtered off using a membrane filter to obtain 540.2 g of an oil layer. This oil layer was distilled under reduced pressure using a 25-stage Oldershaw distillation apparatus. At the beginning of distillation, the operation was performed at a reduced pressure of 30 to 60 mmHg, and then the reduced pressure was reduced to 10 mmHg.
Was changed to 30 mmHg, and a distillate having an overhead temperature of 105 ° C / 16 mmHg to 106 ° C / 17 mmHg was obtained. This was analyzed by capillary gas chromatography, and as a result, 97.9% by weight of 2-propylheptanol (2PHO) and
4-methyl-2-propylhexanol (MPHO)
It was found to be a mixed decyl alcohol containing 2.0% by weight.

[Phthalic acid diester] As a raw material, 413.4 g of phthalic anhydride and 1086.5 g of mixed decyl alcohol were charged in a 2 liter flask under a nitrogen atmosphere. The solution is heated while stirring, and the temperature of the reaction solution is 60 ° C.
Then, 7.0 g of a 25% by weight decanol solution of tetraisopropoxytitanium as a catalyst was added, and the temperature was further raised to 220 ° C. Produced water was removed from the system using an oil-water separator attached to the reactor, and unreacted alcohol was returned to the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C. When the acid value became 0.3 or less (after about 5 hours), heating was stopped, and normal neutralization, washing with water, After subjecting to vacuum distillation and post-treatment operations, the target substance, didecyl phthalate (DXP-2) 1161
g was obtained. At this time, the acid value was 0.020, the residual alcohol content was 100 ppm or less, and the water content was 0.06% by weight.

[Cold-resistant sheet made of vinyl chloride resin] DXP-
1 was changed to DXP-2, and the other steps were performed in the same manner as in Example 1.

Example 3 [Cold-resistant sheet made of vinyl chloride resin] The same procedure as in Example 2 was carried out except that 70 parts by weight of DXP-2 was changed to 80 parts by weight.

Example 4 [Cold-resistant sheet made of vinyl chloride resin] The same operation as in Example 2 was performed except that 70 parts by weight of DXP-2 was changed to 100 parts by weight.

Comparative Example 1 [Vinyl chloride resin sheet] The same operation as in Example 2 was carried out except that no epoxy resin was used.

Comparative Example 2 [Mixed alcohol] Commercially available n-valeraldehyde 668.0 was placed in a 2-liter flask equipped with a magnetic stirrer, a Dimroth condenser, a thermocouple thermometer and a dropping device.
g, 2-methylbutyraldehyde and 35.5 g were stirred. A 1.0% by weight aqueous NaOH solution was prepared and added dropwise to the flask at 25 ° C. After 60 minutes, the dropwise addition was completed, and the temperature in the system at this time was 57 ° C. Thereafter, heating was started and, after reaching 85 ° C., stirring was continued for 4 hours. Next, after cooling to room temperature, stirring was stopped and oil-water separation was performed to obtain 584.2 g (water content: 0.54% by weight) of an oil layer (aldol condensate).

An oil layer of an aldol condensate was placed in a 1-liter stainless steel autoclave equipped with a magnetic stirrer, hydrogen pressure regulator and thermocouple under a nitrogen atmosphere.
9 g and 26.7 g of Raney nickel as a catalyst were charged. After replacing the inside of the system with hydrogen three times, the hydrogen pressure was increased to 50 kg /
It was set to cm ² and stirred at 500 rpm. At the same time,
When the electric furnace was heated and the temperature was raised, the temperature in the system was 95%.
Hydrogen absorption started at around ° C., and continued for 3.5 hours thereafter (the highest temperature reached during this period was 160 ° C.). Stirring was continued at 130 to 145 ° C. for another 2 hours after the hydrogen absorption ceased, and then heating was stopped. After standing overnight, the catalyst was filtered off using a membrane filter to obtain 540.2 g of an oil layer. This oil layer was distilled under reduced pressure using a 25-stage Oldershaw distillation apparatus. At the beginning of distillation, the operation was performed at a reduced pressure of 30 to 60 mmHg, and then the reduced pressure was reduced to 10 mmHg.
From 30 ° C / 15 mmHg to 106 ° C / 17 mmHg. This was analyzed by capillary gas chromatography, and as a result, 89.9% by weight of 2-propylheptanol (2PHO) and
4-methyl-2-propylhexanol (MPHO)
It was found to be a mixed decyl alcohol containing 9.9% by weight.

[Phthalic acid diester] In a 2 liter flask, 413.0 g of phthalic anhydride and 1086.3 g of mixed decyl alcohol were charged as raw materials under a nitrogen atmosphere. The solution is heated while stirring, and the temperature of the reaction solution is 60 ° C.
Then, 6.9 g of a 25% by weight decanol solution of tetraisopropoxytitanium as a catalyst was added, and the temperature was further raised to 220 ° C. Produced water was removed from the system using an oil-water separator attached to the reactor, and unreacted alcohol was returned to the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C. When the acid value became 0.3 or less (after about 5 hours), heating was stopped, and normal neutralization, washing with water, After subjecting to vacuum distillation and post-treatment operations, the target substance, didecyl phthalate (DXP-3) 1158
g was obtained. At this time, the acid value was 0.022, the residual alcohol content was 100 ppm or less, and the water content was 0.05% by weight.

[Vinyl chloride resin sheet] The procedure was the same as in Example 1 except that DXP-1 was replaced with DXP-3.

Comparative Example 3 [Mixed alcohol] Commercially available n-valeraldehyde 70 was placed in a 2-liter four-necked flask equipped with a magnetic stirrer, a Dimroth condenser, a thermocouple thermometer and a dropping device.
0.5 g was charged and stirred. A 1.0% by weight aqueous NaOH solution was prepared and added dropwise to the flask at 25 ° C.
After 60 minutes, the dropping was completed, and the temperature in the system at this time was 62 ° C. Thereafter, heating was started and, after reaching 85 ° C., stirring was continued for 4 hours. Next, after cooling to room temperature, stirring was stopped, and oil-water separation was performed to obtain 585.4 g (water content: 0.58% by weight) of an oil layer (aldol condensate).

In a 1-liter stainless steel autoclave equipped with a magnetic stirrer, a hydrogen pressure regulator and a thermocouple thermometer, an oil layer 53 of an aldol condensate was placed under a nitrogen atmosphere.
4.5 g and 26.5 g of Raney nickel as a catalyst were charged. After purging the system three times with hydrogen, the hydrogen pressure was increased to 50
It was set to kg / cm ² and stirred at 500 rpm. At the same time, when the electric furnace was heated and the temperature was raised, hydrogen absorption started at a temperature around 95 ° C. in the system, and hydrogen absorption continued for 3.5 hours thereafter (the maximum temperature during that time was 160 ° C.) ). 130 hours after hydrogen absorption stopped
After the stirring was continued at 145 ° C., the heating was stopped. After standing overnight, the catalyst was filtered off using a membrane filter to obtain 540.4 g of an oil layer. This oil layer was distilled under reduced pressure using a 25-stage Oldershaw distillation apparatus. At the beginning of the distillation, the operation was performed at a reduced pressure of 30 to 60 mmHg, and then the reduced pressure was reduced to 1 mm.
Change the temperature from 0 to 30mmHg and the top temperature is 112 ℃ / 20mmHg
To obtain a distillate of 113 ° C./20 mmHg. This was analyzed by capillary gas chromatography.
99.8% by weight of propylheptanol (2PHO) and 4-methyl-2-propylhexanol (MPH
O) It was found to be decyl alcohol containing 0.1% by weight.

[Phthalic acid diester] As a raw material, 413.2 g of phthalic anhydride and 1086.5 g of mixed decyl alcohol were charged into a 2 liter flask under a nitrogen atmosphere. The solution is heated with stirring to bring the reaction solution temperature to 60.
When the temperature reached 0 ° C., 7.0 g of a 25% by weight decanol solution of tetraisopropoxytitanium as a catalyst was added.
The temperature was further raised to 220 ° C. Produced water was removed from the system using an oil-water separator attached to the reactor, and unreacted alcohol was returned to the system. Sampling was performed every hour after the temperature of the reaction solution reached 220 ° C. When the acid value became 0.3 or less (after about 5 hours), heating was stopped, and normal neutralization, washing with water, After subjecting to vacuum distillation and post-treatment operations, the objective substance, didecyl phthalate (DXP-4) 116
0 g was obtained. At this time, the acid value was 0.021, the residual alcohol content was 100 ppm or less, and the water content was 0.04% by weight.

[Vinyl chloride resin sheet] The procedure was the same as that of Example 1 except that DXP-1 was replaced with DXP-4.

Comparative Example 4 [Vinyl chloride resin sheet] DXP-1 was replaced with a commercially available DOP
(Manufactured by Chisso Corporation), and the other procedures were the same as in Example 1.

Comparative Example 5 [Vinyl chloride resin sheet] The same test as in Example 1 was conducted except that DXP-1 was changed to diisononyl phthalate (DINP manufactured by Sekisui Chemical Co., Ltd.).

Comparative Example 6 [Vinyl chloride resin sheet] DXP-1 was changed to diisodecyl phthalate (DIDP manufactured by Sekisui Chemical Co., Ltd.), and the other conditions were the same as in Example 1.

Table 1 shows the results of these examples and comparative examples.

[Table 1]

[Table 2]

[0047]

As can be seen from the measurement result of the softening temperature, the vinyl chloride resin sheet or film of the present invention maintains the softness even at a low temperature and is not too hard.
Good handling workability. In addition, it is resistant to tearing.
In addition, as evaluated by the rate of change of weight by heating and the rate of change of weight of warm water, the dissipation of the plasticizer due to long-term heat or water is small, and the flexibility and strength of the vinyl chloride resin sheet or film due to the dissipation of the plasticizer are reduced. The drop is less than conventional sheets.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 27:06 (58) Investigated field (Int.Cl. ⁷ , DB name) C08J 5/18 C08K 5/12 C08L 27/06

Claims (1)

(57) [Claims] 1. A phthalic acid diester of a mixed alcohol of 95.0% to 99.0% by weight of 2-propylheptanol and 1.0% to 5.0% by weight of 4-methyl-2-propylhexanol. 65 parts by weight of a plasticizer consisting of
A sheet made of a vinyl chloride resin, characterized by using a composition in which 05 parts by weight and 1 to 5 parts by weight of an epoxy resin are mixed with 100 parts by weight of a vinyl chloride resin.