JPH03143943A - Plasticized vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To enable the production of a molded article which is less sticky and excellent in the printability and adhesion to an ink by compounding a metal salt of an org. acid and an ester with a specific structure into a plasticized vinyl chloride resin compsn. CONSTITUTION:100 pts.wt. vinyl chloride resin is compounded with 0.01-5 pts.wt. metal salt of a 12C or lower org. acid and 0.05-2 pts.wt. ester obtd. by reacting pentaerythritol or a product of condensation by dehydration thereof with a mixture of a polybasic acid and a 12-24C fatty acid. The polybasic acid mainly comprising adipic acid is pref. because of its cost and effect obtd. As the fatty acid, one which is solid at room temp. and gives a solid esterification product is pref., a satd. fatty acid being esp. pref.

Description

Detailed Description of the Invention [Industrial Field of Application 1] The present invention relates to a soft vinyl chloride resin composition suitable for use in the production of molded products that are subjected to secondary processing such as printing and painting. .

[Conventional technology 1] Soft vinyl chloride resins have better adhesion to printing inks and paints than polyolefin resins such as polyethylene and polypropylene, and can be printed without surface treatments such as corona discharge treatment, so they can improve design. It is widely used as molded products such as packaging materials. Therefore, soft vinyl chloride PS resin is used as a composition by blending various additives such as stabilizers and lubricants, mainly considering heat resistance stability and lubricity during molding. etc. are selected mainly with emphasis on moldability.

However, in molded products made using compositions containing these additives, some of the additives erupt onto the surface of the molded product over time after molding, and the additives reduce the adhesion of printing inks, etc. This has become an incentive to inhibit this. In other words, even if good printing is obtained immediately after molding, if printing is performed 2 to 3 months after molding, the adhesion of the printing ink will decrease, and if the printed surface comes into contact with protrusions, the ink will fall off. . Furthermore, there is a problem that the ink is repelled from the molded product during printing, resulting in a significantly poor finish of the molded product and loss of commercial value.

In addition, in order to improve the printability of molded products made of soft vinyl chloride resin, stabilizers with less gushing out, so-called liquid composite stabilizers, are used, but the molded products obtained from the compositions are different from each other. It is sticky and makes it difficult to use.

For example, in the case of film-like high-profile products, the package is usually a roll, and when it is unrolled or processed into secondary processing, the unwinding or secondary processing becomes extremely difficult due to the stickiness. However, this method had the disadvantage of significantly reducing productivity.

[Section J for inventions to solve! E! ] The present inventors conducted extensive studies on a soft vinyl chloride resin composition that has good printability and ink adhesion even after being left and stored for a long period of time, and is capable of producing molded products with less stickiness. By mixing together a hydrocarbon solvent-soluble stabilizer and an ester having a specific structure with a soft vinyl chloride resin, the inventors have found that the desired objective can be achieved and the present invention has been completed.

That is, an object of the present invention is to provide a flexible vinyl chloride resin composition that has excellent printability and ink adhesion and can provide molded products with little stickiness.

[Means for Solving the Problems] Therefore, the gist of the present invention is to provide (A) an organic acid metal soap having 12 or less carbon atoms, (B) penquerythritol or its dehydrated condensation polyol, and a polybasic The present invention is a soft vinyl chloride resin All-in-one compound containing an ester obtained by reacting an acid with a mixture of a fatty acid having 12 to 24 carbon atoms.

To explain the present invention in detail, the vinyl chloride resin used in the flexible vinyl chloride resin composition includes polyvinyl chloride, a copolymer mainly composed of vinyl chloride and copolymerizable copolymers/mers, Other thermoplastic resins may be blended with this.

Como/mers include vinyl acetate, acrylic acid or its esters, methacrylic acid or its esters, maleic acid, crotonic acid, ethylene, propylene, styrene,
Examples include acrylonitrile.

This vinyl chloride resin is usually blended with a plasticizer to become a soft vinyl chloride resin. As a plasticizer, dibutyl 7
7-talic acid ester plasticizers such as 7-talate, dioctyl 7-talate, di-2-ethylhexyl 7-talate, 7-talate of mixed alcohols having 11 to 11 carbon atoms (hereinafter referred to as C1-), dioctyl adipate , dibasic aliphatic carboxylic acid ester plasticizers such as diisononyl adipate and dioctyl sebacate, trimellitic acid ester plasticizers such as trioctyl trimellitate and triisodecyl trinolitate, tricresyl phosphate, triethylphenyl Phosphate ester plasticizers such as phos-7, -trixylenylphos-7, epoxidized soybean oil, epoxidized linseed oil, epoxy plasticizers such as a condensate of bisphenol A and epichlorohydrin, dibasic Examples include polyester plasticizers in which acid and polyhydric alcohol are condensed, and these may be used alone or in combination of two or more. The amount of plasticizer used is preferably in the range of 20 to 80 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount of plasticizer used is less than 20 parts by weight, the molded product will have less stickiness and less squirting, resulting in good printability and ink adhesion, and there is no particular need to use this invention. On the other hand, if the amount is more than 80 parts by weight, the molded product itself becomes too soft and sticky, making it difficult to handle. The amount of the plasticizer to be used is desirably determined appropriately, taking into consideration the degree of polymerization of the vinyl chloride resin, the type of plasticizer, the intended use of the resulting composition, and the like.

The stabilizer which is an essential component of the present invention is an organic acid metal soap, and it is preferable that the organic acid has 12 or less carbon atoms. Furthermore, the structure of the organic acid is not particularly limited. Such stabilizers include, for example, barium octoate, barium nonyl phenate, non-quoctoate, Schiff-2F-7-enate, non-phthalate butyl metatoluate, calcium octoate, magnesium octoate, dibutyl tin maleate. ate and dioctyltin laurate, and these may be used alone or in combination of two or more.

In addition, due to the adhesion of the printing ink, stabilizers may be used in organic solvents, such as aliphatic or aromatic hydrocarbon solvents such as petroleum ether, benzine, ligroin, mineral spirit, kerosene, toluene, and xylene. Those that dissolve are selected. Here, dissolution refers to exhibiting solubility of 10 or more at 20°C in an organic solvent with a boiling point of 250°C or less.

The amount of the stabilizer added is desirably in the range of 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin. The stabilizer may be dissolved in the above-mentioned solvent and added to the vinyl chloride resin.

The composition of the present invention contains, together with stabilizers, IJ7enyl7osphite, octylnophenyl7osphite, trinonyl72277osphite, noisodecyl7enyl7osphite, nophenyl7osphite, and nophenyl7osphite. It is desirable to add a chelator such as an acid. Among metal soaps, a combination of barium field or zinc salt and the above-mentioned 7t sphite is particularly preferred from the viewpoint of thermal stability and cost.

(B) Nijinchiru, which is one component of the composition of the present invention, contains pentaerythritol or its dehydrated condensed polyol, a polybasic acid, and a carbon atom number of 12 to 24, preferably 14 to 2.
It is obtained by reacting two types of mixed acids of No. 4 fatty acids.

Pentaerythritol or its dehydration condensation polyols has a structure represented by the following general formula.

[In the formula, n represents an integer of 0 or 1 or more] - Among the m elements expressed in the form, it is best to use an ester mainly composed of dipentaerythritol, where n is 1, because it improves the adhesion of printing ink. desirable in that respect. Dipentaerythritol 1 is obtained by dehydration condensation of pentaerythritol, and some of the product with n = 2.3 is produced as a by-product during the production process, but it may be used without separating the by-products during ester production.

Examples of polybasic acids include succinic acid, glutaric acid, anopic acid, cepatic acid, heptalacid, isophthalic acid, terephthalic acid, trimellitic acid, citraconic acid, methaconic acid, propane-1,2,3-tricarboxylic acid, and citric acid. , tartaric acid, etc., and at least one of these is used. Considering the effect and cost of the produced ester on the composition of the present invention, it is preferable to use an ester mainly composed of anopic acid.

Examples of the fatty acid include myristic acid, valmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, citric acid, and wasinolic acid, and at least one of these can be used. Among these, those that are solid at room temperature and whose ester reaction product is solid are preferred, and saturated fatty acids are particularly preferred. If the number of carbon atoms in the fatty acid is less than 12, the effect of preventing the resulting ester from becoming sticky will be small, and if it is more than 24, the cost will be high, making it impractical.

The proportions of polybasic acids, fatty acids, and pentaerythritol or their dehydrated condensation polyols are
It may be determined within a range such that unreacted hydroxyl groups of polyhydric alcohols (hereinafter referred to as polyhydric alcohols) remain, for example, at a rate of 65% or less, preferably 5 to 50%. If the number of equivalents is P, it is preferable to use X moles of polyhydric alcohol represented by the following formula per mole of polybasic acid.

1+1−≦×≦1.1P − The residual rate of hydroxyl groups in the final ester is adjusted to fall within the above range by adjusting the amount of fatty acid added.

If the polyhydric alcohol
If the amount is more than 1 P mole, esters consisting only of polyhydric alcohol and fatty acid will be produced in large quantities, and when added to vinyl chloride P or resin, printability will be reduced.

In addition, the esterification reaction can be carried out by a commonly known method.
k V Narani - ■ Mountain ＾ Fan☆ Le Continuation Lp eθ7 Kei - If it is, the adhesion of printing ink will be poor or will tend to decrease, and conversely, if it exceeds 65%, the stickiness will tend to worsen. , exceeds the permissible range.

Therefore, the added amount of the generated (B) ester is preferably in the range of ~2 parts by weight; if it is less than 0.05 parts by weight, the effect of preventing stickiness will be small, and if it exceeds 2 parts by weight. and the effect of improving printability becomes smaller.

The soft vinyl chloride P of the present invention and the resin composition include, for example, a vinyl chloride resin, a plasticizer, a stabilizer, an ester obtained as described above, and optionally a chelator-1 antioxidant, a colorant, a filler, etc. It is usually produced by uniformly mixing additives that can be mixed with vinyl chloride resin using a known mixer or kneader. Note that it is preferable that the stabilizer is added after being dissolved in an organic solvent, since the stabilizer is uniformly dispersed in the composition.

[Effect 1] Even if the soft vinyl chloride resin composition of the present invention uses a stabilizer that is easily spewed out from the composition, the stabilizer dissolves in the solvent of the ink or paint used for printing, so it can be easily used in the ink or paint. It has good adhesion and also contains an ester of pentaerythritol or its dehydrated condensed polyol and a mixed carboxylic acid of polybasic acid and fatty acid, which prevents stickiness on the surface of the molded product and allows it to be rolled for a long time. Even if the film is left unused, it has good rewinding and printing properties, excellent secondary processability, and productivity is greatly improved.

Therefore, the composition of the present invention is suitable for use in the production of printing materials such as packaging films that are produced in large quantities and stored.

[Example 1] Next, the composition of the present invention will be explained in detail in Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

The printability and stickiness of the composition of the present invention were evaluated as follows.

Evaluation of printability> Gravure ink for soft vinyl chloride resin <VCH-3, red, manufactured by Toyo Ink Co., Ltd., was diluted twice with methyl ethyl ketone, and coated with a bar coater using the method described below. It was applied to the remaining film at room temperature and dried. After drying, a cellophane tape was attached to the tape, and the tape was then peeled off to evaluate the printability on the following five scales. In addition,
The film was stored at 40° C. for one month after production.

5. No peeling at all.

Approximately 41/4 peels off.

Approximately 31/2 peels off.

Approximately 23/4 peels off.

1 Peel off the entire surface.

Evaluation of stickiness> Two films with a width of 3cm and a length of 10cm are stacked together,
After crimping with a rubber roller with a load of 5 kg, it was heated at 40°C for 1 hour. Cool at a temperature of 20°C for 1 hour, and perform a 180°C peel test using a universal tensile tester.

Stabilizer B: Determine the average peeling force from the chart at a length of 40 mm.

Examples 1 to 13, Comparative Examples 1 to 4 The stabilizers and esters used in the following examples were prepared as follows.

Stabilizer A: Barium nonyl 7-enate, non-phthalate butyl metatoluate and tris-7-nylphenyl 7-mole-7-ite were dissolved in mineral spirits. The components ILr& are 38.5%, 21%, respectively.
6.5% and 34%, and the stabilizer component is 27.5%. 6 Mineral spirits (23%) and toluene (20%), barium octoate (16%), non-quoctoate ( 7%) and tri-7enyl 7-osphite (34%).The content in parentheses indicates the content of each component.Synthesis method of stabilizer or ester> Dipentaerythritol 254g (1 mol) was dissolved with adipine fi73g (0%). , 5 mol) and stearic acid 1136 g
(4 mol) was added and heated, and the dehydration reaction was carried out with stirring at an internal temperature of 200 and 230°C. After reacting for 15 hours, the mixture was cooled to 120°C, passed through ψ filtration, and cooled to room temperature. The obtained ester was a white solid with a melting point of 40 to 80°C and a residual rate of hydroxyl groups of 16%.

In addition, various esters were synthesized in the same manner as described above by changing the feed ratio of fatty acids or the type of fatty acids, and are summarized in Table 1.

Note that dipentaerythritol is a commercially available product (melting point 205
;, ~224°C, to hydroxyl group 38, 40%) 1. j: used r:,'::,'1 Table hydroxyl group residual rate: Chlorinated beer resin (average degree of polymerization 1100) 1. O0
Part by weight No. 2-ethylhexyl 7 clay) 33//Epoxidized soybean oil 2 Stabilizer A or B (as a solution) 2 Various esters
The formulation with the fa amount shown in the pJ2 table was mixed in a lath beaker and kneaded for 5 minutes at a roll surface temperature of 165°C using two rolls with a diameter of 8 inches, and then the film thickness was adjusted to 0.1 theory. Adjust the roll spacing to 11 and set it to 0.
, a 1 mm thick film was formed. The printability and stickiness of the film were evaluated and shown in Table 2.

For comparison, films were molded and evaluated in the same manner as in the above Examples, with respect to films in which no ester was added and films in which a powder stabilizer was used in combination and no ester was added. Those without added stabilizers were thermally decomposed and could not be rolled.

Table 2 stabilizer kinds two synthesis No.

Added amount of Stell (parts by weight) Printability (g/3cm>Actual;:) ~ ~ ~ ~ 0.04 0.1 0.3 0.7 1.5 0.3 805 5 0 0 Book Ba-8t: Zn=St: Barium Stearate Nonxterate 0.3 parts by weight 0.3 parts by weight As is clear from the results in Table 2, the composition of the present invention has excellent printability and stickiness. It can be seen that both have been improved.

Claims (1)

[Claims] (1) Obtained by reacting (A) an organic acid metal soap having 12 or less carbon atoms and (B) pentaerythritol or its dehydration condensation polyol with a mixture of a polybasic acid and a fatty acid having 12 to 24 carbon atoms. A soft vinyl chloride resin composition containing an ester.