JPH04106145A - Vinyl chloride resin film or sheet - Google Patents

Abstract

PURPOSE:To improve nontackniness tear strength, and flexibility by compounding a vinyl chloride resin with di-2-propylheptyl phthalate. CONSTITUTION:100 pts.wt. vinyl chloride resin is compounded with 30-90 pts.wt. di-2-propylheptyl phthalate and, if necessary, a stabilizer (e.g. zinc stearate), an auxiliary stabilizer (e.g. triphenyl phosphite), a lubricant (e. z. stearic acid), an antioxidant (e.g. t-butylhydroxytoluene), a uv absorber [e.g. 2-(5-methyl-2- hydroxyphenyl)benzotriazole], a surfactant (e.g. polyoxyethylenesorbitan monostearate), etc., and formed into a film.

Description

[Detailed description of the invention] [Field of industrial use]

The present invention relates to a flexible vinyl chloride resin film sheet with good so-called non-tack properties, without adhesion between film sheets.

[Conventional technology]

Currently, plastic film sheets are widely used in the fields of industrial materials and daily necessities. There are too many types of plastics to be used, including vinyl chloride resin, polyolefin resins such as polyethylene, polypropylene, polybutadiene, and ethylene-vinyl acetate copolymer, polystyrene, polyester, and polyvinyl alcohol. Among these, vinyl chloride resin exhibits flexibility that cannot be obtained with other plastics by adding a plasticizer, and is used in many fields as a so-called soft vinyl chloride resin. A typical example of this plasticizer is di-2-ethylhexyl phthalate. In addition to being flexible, soft vinyl chloride resin film sheets have a good balance of transparency, heat retention, and physical strength, and are relatively inexpensive, so they are used in a wide variety of industrial materials and daily necessities fields. There is. However, due to the influence of plasticizers and additives contained in soft vinyl chloride resin film sheets, the surface of the film sheet becomes sticky, especially at high temperatures such as in the summer, and the film sheets stick together, making handling difficult. There was a problem in that workability was significantly reduced. In order to improve handling efficiency due to stickiness of this soft vinyl chloride resin film sheet and impart non-tack properties, a blow-out anti-blocking agent is kneaded into the soft vinyl chloride resin film sheet.
Various methods have been proposed, including selecting the type of main plasticizer, adding unevenness to the surface of the film sheet using Shiborol, scattering powder on the surface of the film sheet, and coating the surface of the film sheet with acrylic resin, etc. It's here. C Problems to be Solved by the Present Invention] Each of the above-mentioned methods for improving the stickiness of a soft vinyl chloride resin film sheet and imparting non-tack properties has its drawbacks. That is, mixing in the antiblocking agent causes a decrease in transparency due to bubbling. Regarding the selection of the main type of plasticizer, there is a method of replacing di-2-ethylhexyl phthalate with diisononyl phthalate or isodecyl phthalate, which is effective in improving non-tack properties, but in the case of diisononyl phthalate, tear strength In the case of isodecyl phthalate, flexibility at low temperatures is a problem. Providing unevenness to the film surface causes a decrease in transparency, and scattering powder on the surface of a film sheet is not sustainable, and also causes a decrease in transparency and the generation of mold. In addition, coating the surface of a film sheet with acrylic resin is an effective method, but it inevitably increases the price of the film due to the cost of coating equipment and materials and the complexity of the manufacturing process, creating problems in terms of economic efficiency. be.

[Means to solve the problem]

The present inventors have repeatedly investigated methods for improving stickiness and imparting non-tack properties to soft vinyl chloride resin film sheets without sacrificing their excellent properties and economic efficiency. It has been found that the intended purpose can be achieved by incorporating di-2-propylheptyl. The present invention provides a vinyl chloride resin film sheet characterized by blending di-2-propylheptyl phthalate with vinyl chloride resin. In the present invention, di-2-propylheptyl phthalate is an ester obtained by reacting phthalic acid or phthalic anhydride with 2-propylheptatool. 2-Propylheptatool is produced by, for example, producing n-valeraldehyde by oxo synthesis using butene-1 as the olefin, and producing 2-propylheptabutinal by aldol condensation of n-valeraldehyde and dehydration of the product. , can be synthesized by hydrogenation reaction of butynal to 2-propyl. In the present invention, vinyl chloride resins refer to polyvinyl chloride and vinyl chloride copolymers, and vinyl chloride copolymers are mainly composed of vinyl chloride and other polymers such as ethylene, propylene, vinyl acetate, alkyl vinyl ethers, and acrylic esters. , methacrylic acid ester, etc., but the present invention is not limited to the above types of resins. The vinyl chloride resin film sheet of the present invention is characterized by using di-2-propylheptyl phthalate as a plasticizer in the vinyl chloride resin. It is preferable to blend propylheptyl with 30 to 90 parts by weight of a plasticizer. Further, it is possible to use plasticizers other than di-2-propylheptyl phthalate in combination as long as the effects of the present invention are not impaired. In this case, the plasticizer used in combination is not particularly limited as long as it is generally used for vinyl chloride resin, such as di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-ethylhexyl adipate. , epoxidized soybean oil, tri(alkyl, aryl) phosphates, etc.
More than one species may be used in combination. The vinyl chloride resin film sheet of the present invention contains vinyl chloride resin, di-2-propylbutyl phthalate, and other plasticizers as required, as well as stabilizers, stabilizing aids,
Antioxidants, lubricants, ultraviolet absorbers, surfactants, colorants, etc. can be added. As stabilizers, for example,
Lead salts such as tribasic lead sulfate, metal soap stabilizers such as lead stearate, calcium stearate, barium stearate, zinc stearate, calcium ricinoleate, barium laurate, dibutyltin dilaurate, dibutyltin maleate. Examples include esters, organic tin stabilizers such as dioctyltin mercaptide, and the like. Stabilizing aids include, for example, phosphite esters such as triphenyl phosphite, tri-2-ethylhexyl phosphite, and trinonylphenyl phosphite; antioxidants include, for example, t-butylhydroxy; Examples include toluene and dilaurylthionopropionate. Examples of lubricants include stearic acid, stearamide, and polyethylene wax, and examples of ultraviolet absorbers include 2-(5-methyl-2-hydroquinphenyl)benzotriazole, 2-(3-t- Butyl-5-methyl-2-hydroxyphenyl)-5-chloropenttriazole is mentioned. Examples of the surfactant include polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monopalmitate. Examples of the coloring agent include phthalocyanine blue, titanium oxide, and carbon black. The vinyl chloride resin film sheet of the present invention is formed into a film by blending vinyl chloride resin with a plasticizer of di-2-propylheptyl phthalate as described above. Mixing equipment such as a ribbon blender or Henschel type mixer, kneading equipment such as a Banbury mixer or two rolls, an extruder equipped with a calendar roll or T-die, and even film forming equipment such as a laminator can be used. .

【Effect of the invention】

Since the vinyl chloride resin film sheet of the present invention is characterized by blending butyl into di-2-propyl phthalate, it not only improves the non-tack properties of conventional soft vinyl chloride resin film sheets, but also has tear strength. I was satisfied with the flexibility and flexibility at the same time. As a result, stickiness and the resulting decrease in handling efficiency were improved, and furthermore, dust adhesion and contamination caused by stickiness were prevented.

【Example】

The excellent properties of the flexible vinyl chloride resin film sheet of the present invention will be specifically illustrated by Examples and Comparative Examples. In addition, phthalic acid di-2 used in the formulation of Examples and Comparative Examples
- Propyl heptatool is obtained by hydrogenating 2-propyl heptatool obtained by aldol condensation and dehydration reaction of commercially available valeraldehyde, and esterifying this with commercially available phthalic anhydride. Synthesized by reaction. In addition, the evaluation test method in the following examples is as follows. [Tensile strength, elongation] According to JIS K 7113. [Hardness] According to JIS K 6301, a spring type hardness tester type A was used. [Tear strength] According to JIS K 6301, a B-type test piece was used for measurement. [Softness temperature] According to JIS K E3745. [Sticky peeling load] Cut to 50 x 120 m, thickness 0.07511111
Layer two test films of 50x5 on one side.
0aa+ from above and below a smooth 50x50mm glass plate (
Sandwich with thickness 1 ■). Further, a load of Ikg was placed on the upper glass plate, and this was placed in a constant temperature and humidity chamber at a temperature of 70° C. and a humidity of 80% and left for 2 hours. After 2 hours, it was taken out of the constant temperature and humidity chamber, the load and glass plate were immediately removed, and it was left in a room at 23° C. and 50% humidity for 24 hours. Then, attach the ends of the two stacked film samples, on which no load was placed, to the upper and lower grips of the tensile testing machine, respectively, and measure the force required to separate the two stacked films. did. Measurements were performed on three sets of film samples, and the average of the values was taken as the measured value. The smaller the measured value is, the less stickiness there is, the better the peeling between films, and the better the so-called non-tack properties. Example 1 Polyvinyl chloride with an average degree of polymerization of 1000 (Kyodo PVC Sales ■
; 5L), 50 parts by weight of di-2-propylheptyl phthalate (DPHP), and 100 parts by weight of calcium
Add 2 parts by weight of zinc-based composite stabilizer and heat at 175°C.
Knead for 5 minutes with a test roll of 1. A 3mm sheet was made. Furthermore, after preheating this at 185°C for 2 minutes, it was pressurized at a pressure of 150 kg/cl for 3 minutes to a thickness of 1
A sheet with a thickness of mm was prepared, and its tensile strength, elongation, hardness, tear strength, and softening temperature were measured. Further, the same formulation was used and kneaded under the same test roll conditions to prepare a film with a thickness of 0.075 mm, and the stickiness peeling load was measured. The measurement results are shown in Table-1. Example 2 Di-2-propylheptyl phthalate (DPH) from Example 1
P) The same test as in Example 1 was conducted except that 50 parts by weight was changed to 70 parts by weight. The measurement results are shown in Table-1. Comparative Example 1 Di-2-propylheptyl phthalate (DPH) of Example 1
P) 50 parts by weight of di-2-ethylhexyl phthalate (
The test was carried out in the same manner as in Example 1 except that the amount was changed to 50 parts by weight (DOP) manufactured by Chisso ■. The measurement results are shown in the table.
As shown in 1. Comparative Example 2 Di-2-propylheptyl phthalate (DPH) of Example 1
P) 50 mffi parts were changed to 50 parts by weight of diisononyl phthalate (manufactured by Block Chemical Industry Itl: DINP),
In other respects, the same test as in Example 1 was conducted. The measurement results are shown in Table-1. Comparative Example 3 Di-2-propylheptyl phthalate (DPH) of Example 1
The same test as in Example 1 was conducted except that 50 parts by weight of P) was changed to 50 parts by weight of diisodecyl phthalate (manufactured by Block Chemical Industry H1: DIDP). The measurement results are shown in the table.
As shown in 1.

Claims (1)

[Claims] 1) A vinyl chloride resin film sheet characterized by blending di-2-propylheptyl phthalate with vinyl chloride resin.