JPH0559242A - Vinyl chloride resin composition improved in processibility - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is excellent in melt extrusion processibility, scorch resistance, long-run properties, transparency, initial resistance to coloration, and plate-out resistance, is easily processible, and is suitable for food wrapping. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. vinyl chloride resin with 10-60 pts.wt. polyester plasticizer, 0.1-10 pts.wt. nonionic surfactant, and 0.05-10 pts.wt. alkyl (meth)acrylate polymer having a number average degree of polymn. of 50 or lower.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition suitable for molding a polyvinyl chloride stretch film for food packaging.

[0002]

2. Description of the Related Art Polyvinyl chloride stretch films have excellent transparency,
Due to its flexibility, gas barrier property, food storability, packaging suitability, etc., it has been used in large quantities in recent years as a film for packaging food such as meat, fresh fish, fruits and vegetables, and prepared foods in food departments such as department stores and supermarkets.

In the production of this polyvinyl chloride stretch film, di (C ₆ -C ₁₀ alkyl) adipates such as dioctyl adipate and diisononyl adipate have been conventionally used in order to impart flexibility and transparency. However, it has been a problem that volatility and extractability are large. Therefore, Japanese Patent Publication No. 28618/1990 proposes to replace a part of the fatty acid dibasic acid ester with a polyester plasticizer.

However, the above polyester-based plasticizer is superior in volatility as compared with an aliphatic dibasic acid ester such as dioctyl adipate, but is inferior in properties such as plasticization efficiency and cold resistance, and particularly vinyl chloride. Since it has poor compatibility with resins, it has a drawback that plate-out is likely to occur during molding.

One or more lubricants have been used to solve these problems and drawbacks and to facilitate processing. Examples of these lubricants include higher fatty acids such as stearic acid, hydroxystearic acid, isostearic acid, and behenic acid, fatty acid amides such as oleic acid amide, methylenebisstearamide, ethylenebisstearamide, and montan wax. Examples thereof include waxes, higher alcohols such as stearyl alcohol, paraffins such as liquid paraffin, and silica fine powder. However, the combination of these conventional lubricants is excellent in initial colorability and transparency, and plate out,
It has been very difficult to obtain a polyvinyl chloride stretch film suitable for food packaging without blooming.
Also, Japanese Patent Publication No. 52-778 and Japanese Patent Publication No. 52-153.
No. 62, etc. proposes to use an oligomer such as acrylic acid or methacrylic acid as a lubricant for vinyl chloride resin, but it is described what effect is obtained by simply adding a polyester plasticizer. However, it has not even been suggested to be applied to vinyl chloride resins used for foods.

[0006]

[Means for Solving the Problems] In view of such a situation,
As a result of diligently studying the development of a vinyl chloride resin suitable for food packaging by improving the above-mentioned drawbacks, vinyl chloride resin 10
0 part by weight, (a) 10 to 60 parts by weight of a polyester plasticizer, (b) 0.1 to 10 parts by weight of a nonionic surfactant, and (c) a number average of acrylic acid or methacrylic acid alkyl ester. Polymer having a degree of polymerization of 50 or less 0.05 to
A vinyl chloride resin composition obtained by adding 10 parts by weight,
Excellent in anti-burn, long-run property, transparency and initial coloring
Moreover, they have found that the present invention is suitable for food packaging that hardly causes plate-out and is easy to process, and completed the present invention.

The vinyl chloride resin composition of the present invention will be described in detail below.

As the polyester plasticizer of component (a) in the vinyl chloride resin composition of the present invention, a polybasic acid component and a polyhydric alcohol component are usually used as a terminal terminating component, if necessary, as a monohydric component. What was manufactured by carrying out condensation using alcohols and / or a monobasic acid is used.

Examples of the polybasic acid component include those containing an aliphatic dibasic acid such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and dodecanedicarboxylic acid as a main component. In addition to these, a small proportion of aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, or aliphatic polybasic acids such as butanetricarboxylic acid, tricarballylic acid, and citric acid. It is also possible to mix and use a basic acid.

Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol and 2-methyl-
1,3-propanediol, 2,2-dimethyl-1,3
-Propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexane Diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2
Examples include those containing an aliphatic glycol such as 4-trimethyl-1,3-pentanediol as a main component, and a small proportion of polyhydric alcohol such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol. Can also be used.

As the end-stopping component, methanol,
Ethanol, propanol, isopropanol, butanol, secondary butanol, isobutanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, isononyl alcohol, isodecanol, isoundecanol, isotridecyl Alcohols, aliphatic monohydric alcohols such as benzyl alcohol and acetic acid, propionic acid, butyric acid, isobutyric acid, octylic acid, 2-ethylhexylic acid, lauric acid, myristic acid, palmitic acid,
Aliphatic monobasic acids such as stearic acid and 12-hydroxystearic acid can be mentioned.

Therefore, as the polyester-based plasticizer used in the present invention, polyester-based plasticizers (No. 1 to No. 5) produced from the respective components shown in Table 1 below can be mentioned.

[0013]

[Table 1]

It is well known to produce a polyester plasticizer using the components shown in Table 1 above, and for example, it can be easily produced by reacting in the presence of a catalyst such as dibutyltin oxide or tetraalkyl titanate. You can

The ratio of the above components varies depending on the type of the components used, the characteristics of the intended polyester plasticizer, the molecular weight, etc., but generally 10 to 80% by weight of the polybasic acid component and 10 of the polyhydric alcohol component. It is preferable that the ratio is -80 wt% and the end-stopping component is 0-50 wt%.

The number average molecular weight of the polyester plasticizer of the component (a) of the present invention is preferably 600 to 5,000, more preferably 800 to 4,000. The acid value of the polyester-based plasticizer is preferably 1 or less, and the hydroxyl value is preferably 30 or less.

The addition amount of the polyester plasticizer as the component (a) of the present invention is 10 to 60 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

As the nonionic surfactant as the component (b) in the vinyl chloride resin composition of the present invention, commercially available nonionic surfactants are used, and these may be used alone or in combination of two or more. It can be used in combination. As the nonionic surfactant, polyoxyethylene various alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and other partial fatty acid esters of polyhydric alcohols, poly Ethylene oxide adduct of partial fatty acid ester of polyhydric alcohol such as oxyethylene sorbitan alkyl esters, ethylene oxide adduct of aliphatic alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of aliphatic amino or fatty acid amide, etc. Is mentioned.

In the vinyl chloride resin composition of the present invention, the addition amount of the nonionic surfactant (b) is 0.1 to 10 parts by weight, preferably 100 parts by weight of the vinyl chloride resin composition. Is 0.2 to 5 parts by weight.

As the alkyl group constituting the polymer of the acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride resin composition of the present invention, methyl, ethyl, propyl, n-butyl, isobutyl, Tert-butyl, pentyl, cyclohexyl, benzyl, n-
Octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, methoxyethyl, ethoxyethyl,
Examples thereof include butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-3-chloropropyl, dimethylaminoethyl, diethylaminoethyl, glycidyl or tetrahydrofurfuryl and other alkyl groups and substituted alkyl groups. In addition, a part of the above-mentioned alkyl group is replaced with Li, Na, K, Mg, Ca, Zn, Al, S
n, a metal salt of a metal such as organic tin may be used.

The polymer of acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride resin composition of the present invention is an oligomer and has a number average degree of polymerization of 50 or less, preferably 3 to 30. belongs to. When the number average degree of polymerization exceeds 50, the transparency of the resin is improved, but on the other hand, the effect of lubricity is lost and mechanical properties are deteriorated, which is not preferable. The polymer of the acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride-based resin composition of the present invention is a vinyl monomer such as ethylene, propylene or butene-1.
-It may contain monomer units such as olefin, styrene, acrylonitrile, vinyl acetate, butadiene, vinyl alcohol, maleic acid, fumaric acid, itaconic acid or esters thereof.

In the vinyl chloride resin composition of the present invention, the added amount of the acrylic acid or methacrylic acid alkyl ester polymer as the component (c) is the vinyl chloride resin 10
It is 0.05 to 10 parts by weight with respect to 0 parts by weight. If the amount added is less than 0.05 parts by weight, almost no effect is observed. Further, even if the amount added exceeds 10 parts by weight, no remarkable improvement in the effect is observed.

The polymer of the acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride resin composition of the present invention may be added alone to the resin during processing, and may be added before the processing. You may use it, mixing with an agent.

The polymer of the acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride resin composition of the present invention is used to adjust the degree of polymerization with an initiator, polymerization in an active solvent, and low ionic polymerization. It can be easily produced by a known method such as low polymerization with an organometallic complex.

For example, as shown in Table 2 below, the polymers (oligomers) of acrylic acid-based or methacrylic acid-based alkyl ester as the component (c) in the vinyl chloride resin composition of the present invention are disclosed in JP-B-52-778. , Japanese Shokoku 53-1
It can be synthesized according to a synthesis example described in Japanese Patent No. 5302.

[0026]

[Table 2]

The vinyl chloride resin used in the present invention includes vinyl chloride homopolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene vinyl acetate copolymers, vinyl chloride-ethylene copolymers, and chlorides. Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylic ester copolymer, Vinyl chloride-
Styrene-maleic anhydride terpolymer, vinyl chloride-
Styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer,
Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-
Vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-maleimide copolymer, etc. A, and α of such resins as polyethylene, polypropylene, polybutene, and poly-3-methylbutene
-Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, polyurethane, styrene and other monomers (for example, maleic anhydride, butadiene) , Acrylonitrile, etc.), an acrylonitrile-styrene-butadiene copolymer, an acrylic acid aster-styrene-butadiene copolymer, a blended product with a methacrylic acid ester-styrene-butadiene copolymer, and the like. .. These vinyl chloride resins may be obtained by any of the conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization. L in the composition of the present invention
By using an organic acid salt of a metal such as i, Na, K, Mg, Ca, Zn, Al or Sn, the stabilizing effect is remarkably improved.

As the organic acid residue constituting the organic acid salt of the above metal, residues derived from carboxylic acid, phenols, acid phosphates, acid phosphites and the like are useful.

Examples of the carboxylic acid include acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid Acid, 12-hydroxystearic acid, behenic acid, montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid,
Mercaptopropionic acid, octyl mercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid , Ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid and other monocarboxylic acids, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, phthalic acid,
Divalent carboxylic acids such as isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanoic acid, pyromellitic acid And tri- or tetravalent carboxylic acid di- or triester compounds.

The above-mentioned phenols include phenol,
Cresol, xylenol, methylpropylphenol, methyl tertiary octylphenol, ethylphenol, isopropylphenol, tertiary butylphenol,
n-butylphenol, diisobutylphenol, isoamylphenol, diamylphenol, isohexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol, tertiary nonylphenol, decylphenol, dodecylphenol, octadecylphenol, Examples thereof include cyclohexylphenol and phenylphenol.

Examples of the acid phosphate include mono / distearyl acid phosphate, mono / diphenyl acid phosphate, mono / dinonyl phenyl acid phosphate and the like.

Examples of the acid phosphite include phenyl acid phosphite, nonyl phenyl acid phosphite, octyl acid phosphite and stearyl acid phosphite.

The amount of the metal salt of the organic acid added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Further, an alkyl tin stabilizer may be used in combination with the composition of the present invention.

Examples of the above-mentioned alkyl tin stabilizers include mercaptide, malate, and laurate of mono / dimethyl tin, mono / dibutyl tin, mono / dioctyl tin alone or in a mixture.

The amount of the alkyl tin stabilizer added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

In order to obtain a suitable vinyl chloride resin composition, the composition of the present invention is further prepared by adding trisnonylphenylphosphite, tris (dinonylphenyl) phosphite, C ₁₂ -C ₁₅ alkyl bisphenol A.・ Polyphosphite, tris (2,4-di-tert-butylphenyl)
It is preferable to add an organic phosphite compound such as phosphite, distearyl pentaerythritol diphosphite, and bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite.

The amount of the above organic phosphite compound added is
0.1 to 5 parts by weight is preferable with respect to 100 parts by weight of the vinyl chloride resin.

Depending on the purpose, the vinyl chloride resin composition of the present invention may be adipate diester such as dioctyl adipate, dinonyl adipate, sebacate ester, azelaic acid ester, acetyl citrate ester, or epoxidized soybean oil, epoxy. Epoxidized vegetable oils such as linseed oil, epoxidized castor oil, epoxidized tung oil, etc.,
Plasticizers usually used for vinyl chloride resins can be used in combination.

A metal perchlorate may be used in combination with the vinyl chloride resin composition of the present invention. These may be anhydrides or hydrates, or may be dissolved in a solvent such as alcohol. Alternatively, a hydrotalcite compound or the like may be treated with perchloric acid.

Inorganic compounds such as metal oxides, metal hydroxides, hydrotalcite compounds, zinc-modified hydrotalcites, dehydrated products thereof, and zeolites can be added to the vinyl chloride resin composition of the present invention. ..

Further, the vinyl chloride resin composition of the present invention may be added to a β-diketone compound such as dehydroacetic acid, benzoylacetylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, lauroylbenzoylmethane or dibenzoylmethane, or a β-diketone compound thereof. It is preferred to add a metal salt.

Further, in order to facilitate the processing, one or more of the above-mentioned conventionally known lubricants or processability improvers can be added.

Further, if necessary, other thermoplastic resin, epoxy resin, rubber, cross-linking agent, filler, foaming agent, plate-out preventing agent, surface treating agent, flame retardant, fluorescent agent, mildew-proofing agent, A bactericidal agent, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer and the like can be added.

[0045]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 The following formulations were subjected to a kneading test at 170 ° C. with a two-roll mill to measure roll stains and peelability. Further, the same composition was compression-molded under the conditions of 160 ° C. and 150 kg / cm 5 for 5 minutes to prepare a press sheet having a thickness of 3 mm, and the initial colorability and transparency were observed. The results are shown in Table 3 below.

The roll stain is evaluated on a scale of 10 and is 1
Indicates no abnormality, the stain becomes more severe as the number increases below, 5 indicates that a thin film having a bluish color is formed on the whole, and 10 indicates that a thick film having a glare is formed. Further, the peelability is evaluated on a scale of 6, and it is shown that the larger the number, the worse the peelability.

[Composition] Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Polyester plasticizer No. 4 40 Epoxidized soybean oil 8 Calcium oleate 0.1 Zinc ricinoleate 0.1 Zinc octylate 0.1 Sorbitan monolaurate 2.0 Trisnonylphenyl phosphite 0.5 Alkyl ester polymer (oligomer) (Table) 3) 0.3

[0049]

[Table 3]

Example 2 The following composition was subjected to a kneading test at 170 ° C. with the present roll mill to measure roll stains and peelability. The results are shown in Table 4 below.

[Composition] Polyvinyl chloride resin (TK-1300) 100 parts by weight diisononyl adipate 15 epoxidized soybean oil 15 calcium benzoate 0.15 zinc octylate 0.2 diglycerol monooleate 1.5 tris Di-mixed nonylphene 1.5 nyl) phosphite 2-ethylhexyl acrylate 0.15-pseudocumene telomer polyester plasticizer (Table 4) 20

[0052]

[Table 4]

Example 3 The following formulation was tested for initial colorability and transparency, as well as for Example 1, and also for heat resistance. Further, a press sheet having a thickness of 2 mm was prepared and tested for anti-fogging property with time at low temperature and high temperature.

The antifogging property was evaluated by placing a press sheet on a beaker filled with water at 60 ° C., evaluating the degree of cloudiness after 10 seconds on a 10-point scale, and then pressing on a beaker filled with water at room temperature. The sheet is placed and placed in a refrigerator at 5 ° C., and the degree of haze after 30 seconds is evaluated. Further, another press sheet was put in a constant temperature room at room temperature and 5 ° C., and the same evaluation was performed one month later. As for the evaluation standard of the antifogging property, 1 means that there is no fog at all,
10 represents a state in which the opposite side of the sheet is barely visible.

[Composition] Polyvinyl chloride resin (Geon 103EP) 100 parts by weight Polyester plasticizer No. 225 Epoxidized linseed oil 10 Epoxidized soybean oil 5 Calcium benzoate 0.5 Zinc oleate 1.0 Trisnonylphenyl phosphite 0.4 LS-5 ^{* 1} 0.2 Surfactant (Table 5) 1. 0 * 1 Asahi Denka Kogyo Co., Ltd. acrylic acid oligomer lubricant

[0056]

[Table 5]

As is clear from the results of each of the above-mentioned examples, a polyester plasticizer, a nonionic surfactant, and a polymer of acrylic acid-based and methacrylic acid-based alkyl ester (oligomer) are added to vinyl chloride resin. )
By blending, it is possible to obtain a vinyl chloride resin composition which is excellent in transparency, flexibility, gas barrier property, food storability, and packaging suitability and is suitable for molding a polyvinyl chloride stretch film for food packaging.

[0058]

EFFECT OF THE INVENTION The vinyl chloride resin composition of the present invention has particularly excellent suitability for melt extrusion processing, is excellent in burn prevention, long-run property, transparency, initial coloring property, and hardly causes plate-out. It is suitable for food packaging that is easy to process.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08L 33:06) 7242-4J

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 10 to 60 parts by weight of polyester plasticizer, (b)
0.1 to 10 parts by weight of nonionic surfactant and (c)
A vinyl chloride resin composition having improved processability, which is obtained by adding 0.05 to 10 parts by weight of a polymer of an acrylic acid-based or methacrylic acid-based alkyl ester having a number average polymerization degree of 50 or less.