JPH07179699A - Vinyl chloride resin film - Google Patents

Abstract

PURPOSE:To obtain a resin film having good processability, excellent low- temperature resistance, oil resistance and resistance to soap water extraction, low volatility, and little stickiness. CONSTITUTION:A vinyl chloride resin film containing a plasticizer in an amount of 15-200 pts.wt. based on 100 pts.wt. vinyl chloride resin, wherein a diester of phthalic acid with a mixture of 2-propylheptanol and 4-methyl-2-propylhexanol at a weight ratio of (88:12) to (70:30) is used as the plasticizer and which contains, based on 100 pts.wt. vinyl chloride resin, 15-120 pts.wt. of the plasticizer, 1-10 pts.wt. organophosphoric ester, 0.5-10 pts.wt. epoxy compound and 0.1-10 pts.wt. stabilizing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin film having low volatility, excellent soap water resistance and oil resistance, and low stickiness.

[0002]

2. Description of the Related Art Vinyl chloride resin film is an industrial material,
It is used in many fields such as daily necessities and agricultural covering materials. A typical plasticizer used in these films is di-2-ethylhexyl phthalate (hereinafter referred to as "DO
This DOP is widely used because it has various physical properties such as plasticization efficiency, thermal stability, and cold resistance in a preferable range.

However, in the fields of shower curtains, automobile interior films, flooring materials, furniture, etc., lower volatility,
Also, excellent oil resistance and soap water resistance are required, and in the field of vinyl chloride resin film for agriculture, low volatility and a film for improving work efficiency in order to improve durability. Prevention of stickiness between comrades is required.

Therefore, as a plasticizer, diisononyl phthalate (hereinafter referred to as "DiNP"), diisodecyl phthalate (hereinafter referred to as "DiDP"), or the like is used as a plasticizer, or as a characteristic plasticizer. A diester of 2-propylheptanol and phthalic acid (hereinafter referred to as "DPH
The film using "P") is disclosed in JP-A-5-1947.
No. 61 and Japanese Patent Application Laid-Open No. 5-194810.

[0005]

However, the DiNP and D
Films using iDP have poor cold resistance and oil resistance, and DPHP, which has been proposed as an improved product, has a low gelation rate of the compound due to its low absorbability into vinyl chloride resin, which results in production during processing. There is a risk of deterioration of the properties, and the oil resistance and soap water extraction resistance of the obtained film are insufficient. Therefore, a vinyl chloride resin film having less stickiness, which is more excellent in moldability than DPHP and has oil resistance and soap water extraction resistance equal to or higher than that of a film obtained by using the same has been desired.

[0006]

In view of the state of the art as described above, the inventor of the present invention is to find a vinyl chloride resin film which is excellent in oil resistance, soap water extraction resistance and molding processability. As a result of extensive studies, a vinyl chloride resin film obtained by blending a diester of mixed alcohol and phthalic acid in which 2-propylheptanol and 4-methyl-2-propylhexanol are mixed at a specific composition ratio is obtained. The present invention has been completed by finding that it gives good results.

That is, the gist of the present invention is to provide a vinyl chloride resin film containing 15 to 200 parts by weight of a plasticizer with respect to 100 parts by weight of a vinyl chloride resin as a plasticizer.
A mixture of 2-propylheptanol and 4-methyl-2-propylhexanol (hereinafter referred to as "C10 alcohol"), the weight ratio of 2-propylheptanol and 4-methyl-2-propylhexanol in the mixture. Is from 88/12 to 70/30 and a diester of phthalic acid (hereinafter referred to as "DC10P") is used.

The present invention will be described in detail below. The "film" referred to in the present invention includes so-called films and sheets. As the vinyl chloride resin used in the vinyl chloride resin film of the present invention, in addition to vinyl chloride homopolymers, copolymers with other copolymerizable comonomers containing vinyl chloride as a main component, vinyl chloride can be used. A resin as a main constituent unit can be used. Examples of the copolymerizable comonomer include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester, and methacrylic acid or its ester.

As a polymerization method for obtaining this, a polymerization method generally adopted in the polymerization of vinyl chloride, that is, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method or the like can be used. The C10 alcohol used as a raw material of the plasticizer used for the vinyl chloride resin film of the present invention is
2-propylheptanol / 4-methyl-2-
A propylhexanol weight ratio (hereinafter referred to as "C10 alcohol composition ratio") in the range of 88/12 to 70/30, preferably 85/15 to 75/25 is used.

The plasticizer (DC10P) used in the present invention is
It can be obtained by subjecting a C10 alcohol having the above-mentioned specific composition to phthalic anhydride or phthalic acid by an esterification reaction in the presence of an esterification catalyst by a conventional method. When the composition ratio of C10 alcohol is less than 70/30 in 2-propylheptanol, volatility and cold resistance deteriorate,
In addition, the C10 alcohol composition ratio is 2-
When the amount of propylheptanol is large, the molding processability is deteriorated, and the oil resistance and the soap water extraction resistance tend to be deteriorated.

C10 alcohol composition ratio is 85/15 to 7
When it is in the range of 5/25, it is possible to obtain a vinyl chloride resin film having low volatility, excellent cold resistance and processability, and good properties. The vinyl chloride resin film of the present invention contains a plasticizer in an amount of 15 to 200 parts by weight, preferably 15 to 120 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
It was molded by blending parts by weight, and DC10P is used as the plasticizer. If the compounding amount of the plasticizer is less than 15 parts by weight, the effect of improving the cold resistance is not exhibited, and if it exceeds 200 parts by weight, a bleeding phenomenon (a phenomenon in which the plasticizer exudes to the surface of the molded product) occurs on the film surface. It is easy and often causes stickiness and adhesion of dirt.

The vinyl chloride resin film of the present invention comprises
As the above-mentioned plasticizer, a plasticizer other than DC10P may be used together, if necessary, within a range not impairing the object of the present invention.
However, when a plasticizer is used in combination, it is desirable that DC10P accounts for 50% by weight or more of the total amount of the plasticizer. Further, additives usually added to vinyl chloride resins, such as stabilizers, antioxidants, flame retardants, lubricants, fillers, ultraviolet absorbers, colorants, surfactants, antistatic agents, etc., may be added. .

Examples of the plasticizer that can be used in combination include dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, DOP, DiNP, DiDP, butylbenzyl phthalate, and phthalic acid of a higher alcohol having 11 to 13 carbon atoms. Phthalic acid plasticizers such as diesters, tri-2-ethylhexyl trimellitate, triisononyl trimellitate, trimellitic acid plasticizers such as tri-n-octyl trimellitate, di-2-ethylhexyl adipate, adipic acid Diisodecyl, azelaic acid di-2-
Ethylhexyl, dibutyl sebacate, di-sebacate
Examples thereof include fatty acid ester plasticizers such as 2-ethylhexyl and polyester plasticizers.

The stabilizer to be used is not particularly limited as long as it is a stabilizer for vinyl chloride resin, and examples thereof include tribasic lead sulfate, dibasic lead phthalate and lead orthosilicate-silica gel. Precipitate, dibasic lead stearate, cadmium-barium stabilizer, barium-zinc stabilizer, calcium-zinc stabilizer, tin stabilizer, and inorganic salts such as magnesium, aluminum, silicon And the like.

As the lubricant, higher fatty acids or metal salts thereof, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid esters, fatty acid amides and the like can be used. As the filler, for example, calcium carbonate, clay, talc, fine silica powder, aluminum hydroxide or the like can be used. Examples of the flame retardant include antimony trioxide, barium borate, zinc borate, zinc oxide, halogenated flame retardants such as chlorinated polyethylene and the like.

The vinyl chloride resin film of the present invention contains a vinyl chloride resin, the above DC10P, and, if necessary, the above-mentioned other compounding agents, a ribbon blender or a blender commonly used for processing vinyl chloride resin. General film forming methods such as T-die method, extrusion method such as inflation method, calender molding method, casting method, etc. by mixing and kneading with mixing equipment such as super mixer, kneading equipment such as Banbury mixer and two rolls It can be manufactured by subjecting to.

A plasticizer (50% by weight or more of which is DC10P) is added to 100 parts by weight of the vinyl chloride resin.
15 to 120 parts by weight, further containing 1 to 10 parts by weight of an organic phosphate, 0.5 to 10 parts by weight of an epoxy compound, and 0.1 to 10 parts by weight of a stabilizer, a vinyl chloride resin film. Can be molded quickly and has less stickiness, less volatilization of plasticizer, and excellent weather resistance.
Moreover, since it has good cold resistance, it is particularly suitable for use in agricultural vinyl chloride resin films.

The amount of the plasticizer used here is preferably 15 to 120 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. If it is less than 15 parts by weight, the effect of improving cold resistance is not exhibited. If it exceeds 120 parts by weight, the stickiness preventing effect tends to be insufficient. Examples of the organic phosphate used include tributyl phosphate, tri-2-ethylhexyl phosphate, 2-ethylhexyl diphenyl phosphate,
Examples thereof include tricresyl phosphate, and the amount of the organic phosphate ester is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, and if less than 1 part by weight, the effect of improving weather resistance is insufficient. Even if the amount is more than 10 parts by weight, the effect is not increased in proportion to the amount added, and the organic phosphate ester oozes out on the film surface, which is not preferable.

As the epoxy compound, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-
An epoxy-based plasticizer such as 2-ethylhexyl or a liquid epoxy resin may, for example, be incorporated in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If it is less than 0.5 part by weight, the effect of improving weather resistance and thermal stability is insufficient, and if it exceeds 10 parts by weight, the film surface tends to be sticky.

The above-mentioned various stabilizers can be used as the stabilizer, and the amount thereof is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Addition amount is 0.
If it is less than 1 part by weight, the thermal stability is insufficient, while if it is used in excess of 10 parts by weight, the stabilizing effect does not increase so much.
Not economically favorable.

This vinyl chloride resin film can also be used with DC10P as described above, as long as the object of the present invention is not impaired.
Other plasticizers may be used in combination, and in addition to the above-mentioned essential components, additives usually used in vinyl chloride resin films, for example, flame retardants, lubricants, antioxidants, ultraviolet absorbers, fillers. A colorant, a release agent or the like may be used. Further, when using this film as a vinyl chloride resin film for agriculture, the components that are usually blended with the vinyl chloride resin film for agriculture, for example, an antifogging agent, an antifog agent,
Heat retaining agent, antioxidant, ultraviolet absorber, light stabilizer, lubricant,
Dyes, pigments and the like can be added.

Examples of the plasticizer that can be used in combination include the plasticizers for vinyl chloride resins as described above. However, as described above, DC10P is preferably 50% by weight or more of the total amount of the plasticizer. Further, as the lubricant and the filler, those exemplified above can be applied as they are.

This vinyl chloride resin film can also be manufactured using the above-mentioned manufacturing equipment. The vinyl chloride resin film of the present invention is suitable for an agricultural film as described above, and by taking advantage of low volatility loss and good cold resistance, it is used for outdoor applications obtained by laminating this film with a woven or non-woven fabric. It is also suitable for canvas and the like.

[0024]

EXAMPLES The embodiments of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples and comparative examples, "part" and "%" mean "part by weight" and "% by weight", respectively.

<Preparation of Ester> Example 1 148 g (1 mol) of phthalic anhydride and 347.6 g (2.20) of 2-propylheptanol as C10 alcohol.
0 mol) and 4-methyl-2-propylhexanol 4
7.4 g (0.300 mol) (C10 alcohol composition ratio:
88/12) and 0.30 g (0.2% / phthalic anhydride) of tetraisopropyl titanate as an esterification catalyst, a thermometer, a nitrogen introduction tube, a stirrer, a Dean-Stark type water divider (hereinafter, simply “water divider”). , And a reflux condenser were attached to a flask having an internal volume of 2 liters, and the mixture was heated while stirring under a nitrogen stream, and the reaction liquid temperature was raised to 210 ° C. to start the reaction. Subsequently, the produced water was continuously removed from the system by a water separator, and the reaction was continued until the acid value of the reaction solution became 1 mgKOH / g or less. After completion of the reaction, unreacted C10 alcohol was recovered by depressurizing the system, and then neutralized by a conventional method.
After washing with water and dehydration under reduced pressure, 433 g of a phthalic acid diester of C10 alcohol was obtained.

The obtained ester is good as a colorless and transparent oily appearance, and has a hue of 25 APHA and an acid value of 0.01 mgKOH /
g, the ester value is 251 mgKOH / g, and the retention times in the gas chromatographic analysis (hereinafter referred to as "GLC") of the saponified decomposition product are 2-propylheptanol and 4 respectively.
Consistent with -methyl-2-propylhexanol.

Example 2 2-propylheptanol 3 as C10 alcohol
35.8 g (2.125 mol) and 4-methyl-2-propylhexanol 59.3 g (0.375 mol) (C10
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the alcohol composition ratio: 85/15) was used to obtain 435 g of a phthalic acid diester of C10 alcohol. The obtained ester was a colorless and transparent oily appearance and had a good hue of 25AP.
HA, acid value 0.01mgKOH / g, ester value 251mgKOH / g
g, and the retention time of the saponified degradation product by GLC is 2 each.
Consistent with -propylheptanol and 4-methyl-2-propylhexanol.

Example 3 2-propylheptanol 2 as C10 alcohol
96.3 g (1.875 mol) and 4-methyl-2-propylhexanol 98.8 g (0.625 mol) (C10
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the alcohol composition ratio: 75/25) was used to obtain 431 g of a phthalic acid diester of C10 alcohol. The obtained ester was a colorless transparent oily appearance, and had a hue of 30AP.
HA, acid value 0.01mgKOH / g, ester value 251mgKOH / g
g, and the retention time of the saponified degradation product by GLC is 2 each.
Consistent with -propylheptanol and 4-methyl-2-propylhexanol.

Example 4 2-propylheptanol 2 as C10 alcohol
76.5 g (1.750 mol) and 4-methyl-2-propylhexanol 118.5 g (0.750 mol) (C1
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the composition ratio of 0 alcohol: 70/30) was used to obtain 434 g of phthalic acid diester of C10 alcohol. The obtained ester was a colorless and transparent oily appearance, and had a hue of 30.
APHA, acid value 0.01mgKOH / g, ester value 251mgKO
At H / g, the GLC retention times of the saponification products were consistent with 2-propylheptanol and 4-methyl-2-propylhexanol, respectively.

Comparative Example 1 2-propylheptanol 3 as C10 alcohol
Reaction and post-treatment were carried out in the same manner as in Example 1 except that 95.0 g (2.500 mol) (C10 alcohol composition ratio: 100/0) was used to obtain 430 g of phthalic acid diester of 2-propylheptanol. It was The resulting ester is
Appearance is clear and colorless oily, good with a hue of 25 APHA, acid value of 0.01 mgKOH / g, ester value of 250 mgKOH / g,
The retention time of the saponified product by GLC was in agreement with that of 2-propylheptanol.

Comparative Example 2 2-propylheptanol 3 as C10 alcohol
75.3 g (2.375 mol) and 4-methyl-2-propylhexanol 19.8 g (0.125 mol) (C10
The reaction and post-treatment were carried out in the same manner as in Example 1 except that the alcohol composition ratio: 95/5) was used to obtain 429 g of a phthalic acid diester of C10 alcohol. The obtained ester was good in appearance as a yellowish transparent oily substance and had a hue of 35
APHA, acid value 0.01mgKOH / g, ester value 251mgKO
At H / g, the GLC retention times of the saponification products were consistent with 2-propylheptanol and 4-methyl-2-propylhexanol, respectively.

Comparative Example 3 2-propylheptanol 1 as C10 alcohol
97.5 g (1.250 mol) and 4-methyl-2-propylhexanol 197.5 g (1.250 mol) (C1
The reaction and post-treatment were carried out in the same manner as in Example 1 except that 0: alcohol composition ratio: 50/50) was used to obtain 431 g of a phthalic acid diester of C10 alcohol. The obtained ester was a colorless and transparent oily appearance, and had a hue of 30.
APHA, acid value 0.01mgKOH / g, ester value 250mgKO
At H / g, the GLC retention times of the saponification products were consistent with 2-propylheptanol and 4-methyl-2-propylhexanol, respectively.

Comparative Example 4 Reaction was carried out in the same manner as in Example 1 except that 395.0 g (2.500 mol) of 4-methyl-2-propylhexanol (C10 alcohol composition ratio: 0/100) was used as the C10 alcohol. -Post-treatment was performed to obtain 436 g of phthalic acid diester of 4-methyl-2-propylhexanol. The obtained ester was a colorless transparent oil and had a good appearance. The hue was 30APHA, the acid value was 0.01 mgKOH / g, the ester value was 251 mgKOH / g, and the retention time of the saponification product by GLC was 4-methyl. Consistent with 2-propylhexanol.

<Evaluation Method of Plasticizer Composition>

[Table 1] (1) Appearance The transparency and the presence of impurities are visually inspected. (2) Hue Based on JIS K6751. (3) Acid value Based on JIS K6751. (4) Ester value Based on JIS K6751.

<Physical Property Evaluation Method> (1) Processability Evaluation The phthalic acid diesters of Examples and Comparative Examples were mixed in the following composition, and Brabender Plastograph (Brabender) was used.
(Plastic coder PLV151 type, mechanical torque detection method manufactured by K.K.), cell temperature 160 ° C, rotation speed 80rp
The mixture was kneaded at m 2, and the time required to reach the maximum torque value (expressed as "gelling time") was measured. It was determined that the shorter the gelation time, the better the workability.
The evaluation results are shown in Table-1.

[0036]

[Table 2] Vinyl chloride resin 100 parts (Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (registered trademark) 37L, average degree of polymerization 1050) Phthalic acid diester 50 Cd-Ba stabilizer 1

(2) Physical Properties of Sheet (Transparent Blending Test) Using the phthalic acid diesters of Examples and Comparative Examples as a plasticizer, a vinyl chloride resin composition was prepared with the following formulation.

[0038]

[Table 3] Vinyl chloride resin 100 parts (manufactured by Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (registered trademark) 37H, average degree of polymerization 1300) Phthalic acid diester 67 Barium-zinc-based liquid stabilizer 3

The above blends were premixed in a beaker, thoroughly mixed on a two-mill roll whose temperature was adjusted to 170 ° C. by a conventional method (5 minutes), and then pressed to a predetermined thickness. (Temperature: 175 ° C, preheat: 1.96
MPa (20kg / cm ² ) for 2 minutes, Press: 19.6MPa (200kg /
cm ² ) for 5 minutes). The physical properties of the obtained sheet were measured by the following methods, and the performance was evaluated. The results are also shown in Table-1.

[0040]

[Table 4] Tensile test According to JIS K6723. Hardness Based on JIS K6301. Volatilization Loss ASTM D1203-52
Compliant with T. Oil resistance (kerosene extraction amount) A sample having a diameter of 5 cm is weighed, immersed in petroleum (kerosene) at 23 ° C. for 24 hours, and then taken out. The taken-out sample is dried in an air circulation oven at 80 ° C. for 4 hours to remove absorbed petroleum, and then cooled to room temperature in a desiccator. The sample after cooling is re-weighed to determine the amount of loss of plasticizer extracted by petroleum (% by weight). Soap water extractability In the above oil resistance (kerosene extraction amount), 1% soap water was used in place of petroleum (kerosene), and the same test was performed as in the evaluation of the kerosene extraction amount except that it was immersed for 4 days at a temperature of 50 ° C. It was Cold resistance (low temperature flexible temperature) ASTM D1043-51
Compliant with.

(3) Stickiness Using the phthalic acid diesters of Examples and Comparative Examples as plasticizers, vinyl chloride resin compositions were prepared with the following formulation.

[0042]

[Table 5] Vinyl chloride resin 100 parts (manufactured by Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (trademark) 37H, average degree of polymerization 1300) Phthalic acid diester 45 Organic phosphate ester (tricresyl phosphate) 5 Epoxy resin 2 Barium-zinc liquid stabilizer 2 Barium-zinc powder stabilizer 1 Sorbitan monopalmitate 1.5 Benzophenone ultraviolet absorber 0.2

The above mixture was stirred and mixed for 10 minutes by using a super mixer, then kneaded on a two-mill roll whose temperature was adjusted to 165 ° C., and further, the width was 100 cm and the thickness was 0.075 mm by an L-type calender device. A transparent soft vinyl chloride resin film was prepared. The stickiness of this film was evaluated by the following method. The results are also shown in Table-1.

Evaluation of Stickiness A sample of 50 cm square was cut out from the obtained film, folded in four, and a load of 30 kg was applied from above and left at 40 ° C. for 24 hours. After that, the load was removed and the sticky condition of the film surfaces was observed when the film was spread.
The evaluation results are shown below.

[0045]

[Table 6] ○: Almost no stickiness △: Some stickiness ×: Significant stickiness

[0046]

[Table 7]

<Evaluation of Results> From the above Examples and Comparative Examples, the following points are recognized in the vinyl chloride resin film of the present invention. Processability: C10 alcohol composition ratio is higher in 2-propylheptanol than in those outside the preferred range of the present invention (Comparative Examples 1 and 2), and gelation is faster and good processability is exhibited. Oil resistance: C in oil resistance (kerosene extraction amount)
10 Comparative Examples 1 and 2 in which the alcohol composition ratio is outside the range of the present invention
The amount of extraction is smaller than that of (100/0, 95/5).

Cold resistance: Comparative Examples 3 and 4 (50/50, 0/10) in which the composition ratio of C10 alcohol was out of the range of the present invention.
Cold resistance is better than 0). Soap water extractability: The extract amount by soap water is smaller than that of the composition having a large C10 alcohol composition ratio of 2-propylheptanol (Comparative Examples 1 and 2). Volatilization loss: C10 alcohol composition ratio is 4-methyl-
Comparative Examples 3 and 4, which contain a large amount of 2-propylhexanol, have a large volatilization loss and inferior durability. Stickiness: Good without any problem.

From these results, it is recognized that the vinyl chloride resin film of the present invention has little stickiness and is excellent in volatility resistance, oil resistance, cold resistance, soap water extraction resistance, and processability. Such characteristics are particularly suitable for agricultural films and canvas.

[0050]

The vinyl chloride resin film of the present invention is
It has favorable properties such as excellent workability, good cold resistance, oil resistance, soap water extraction resistance, low volatility and low stickiness, and can be suitably used for various applications. In particular, it is suitable for agricultural vinyl chloride resin films and canvas.

Claims (3)

[Claims] 1. A vinyl chloride resin film containing 15 to 200 parts by weight of a plasticizer with respect to 100 parts by weight of a vinyl chloride resin, and 2-propylheptanol and 4-methyl-2-propylhexanol as plasticizers. A mixture of 2-propylheptanol and 4 in the mixture.
The weight ratio with methyl-2-propylhexanol is 8
A vinyl chloride resin film characterized by using a diester of phthalic acid with a resin of 8/12 to 70/30. 2. With respect to 100 parts by weight of vinyl chloride resin,
15 to 120 parts by weight of plasticizer and 1 of organic phosphate ester
-10 parts by weight, 0.5 to 10 parts by weight of epoxy compound,
The vinyl chloride resin film according to claim 1, further comprising 0.1 to 10 parts by weight of a stabilizer. 3. A vinyl chloride resin film for agriculture comprising the vinyl chloride resin film according to claim 2.