JP3660562B2 - Vinyl chloride resin composition for food packaging - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a vinyl chloride resin composition for food packaging. More specifically, the present invention relates to a vinyl chloride resin composition for food packaging that is excellent in coloring resistance, heat resistance, and processability and has little odor.
[0002]
[Technical background]
The vinyl chloride resin stretch film is excellent in transparency, flexibility, gas barrier property, food preservability and packaging suitability, and is used in large quantities as a food packaging film.
In producing this vinyl chloride resin stretch film, epoxidized soybean oil is used in a relatively large amount. For this reason, in the inflation and T-die formulation, there has been a problem with long run properties due to the occurrence of eyelids due to the hardening phenomenon of the epoxidized vegetable oil and the product being burned. Moreover, it became a stretch film with a rough surface, and when using this film, there existed faults, such as lack of slipperiness with a to-be packaged object, and the unwinding resistance of a paper tube winding film was large. Moreover, the transfer of the odor to a foodstuff is seen by the mixing | blending of a large amount of epoxidized soybean oil. When these problems have been solved with conventional additives, it has been very difficult to obtain a vinyl chloride resin stretch film suitable for food packaging that is excellent in initial colorability and transparency and does not cause plate-out and bloom.
Recently, stretch films from which tris (nonylphenyl) phosphite has been removed have been produced, but they tend to be inferior in transparency, antifogging properties and heat resistance.
[0003]
[Problems to be solved by the invention]
As a result of diligent studies to solve these problems, a solution was found as follows.
That is, a film having a lower odor is prepared by using phosphite having a low odor, and addition of the phosphite brings about improvement in heat resistance and improvement in medium-term coloring, so that the amount of epoxidized soybean oil is correspondingly increased. Can be reduced, which further reduces the odor of the film. As a further effect, the amount of inorganic additives as other heat stabilizers can be reduced, so that the transparency of the film is improved. Expecting these effects, the present invention was obtained.
[0004]
[Means for Solving the Problems]
In the present invention, a vinyl chloride resin stretch film having low odor and excellent performance can be obtained by using a specific phosphite in line with the above-mentioned gist. That is, the present invention provides (a) 0.1 to 20 parts by weight of epoxidized vegetable oil, (b) an organic carboxylic acid zinc salt, and (c) an organic carboxylic acid, based on 100 parts by weight of the vinyl chloride resin. It is a vinyl chloride resin composition for food packaging films comprising a calcium salt, (d) an alkyl phosphite compound having 8 to 18 carbon atoms, a β-diketone compound and / or a hydrotalcite compound . Further, an excellent vinyl chloride resin stretch film for food packaging film could be obtained by further adding a plasticizer to this vinyl chloride resin composition.
[0005]
The present invention will be described in more detail but is not limited thereto. The alkyl phosphite compound used in the present invention is a compound represented by the following general formula (1).
[0006]
[Formula 4]
(Where R is an alkyl group having 8 to 18 carbon atoms, and n is 0, 1 or 2)
[0007]
Specific examples of the alkyl phosphite compound include trioctyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, tritridecyl phosphite, tritetradecyl phosphite, tripentadecyl phosphite, Trihexadecyl phosphite, triheptadecyl phosphite, trioctadecyl phosphite, monooctadecyl didecyl phosphite, monododecyl ditridecyl phosphite, monoheptadecyl didodecyl phosphite, didodecyl phosphite, diundecyl phosphite Phyto, didodecyl phosphite, ditridecyl phosphite, ditetradecyl phosphite, dipentadecyl phosphite, dihexadecyl phosphite, diheptadecyl phosphite, di Kutadecyl phosphite, monooctadecyl monododecyl phosphite, monoheptadecyl monohexadecyl phosphite, monododecyl phosphite, monotridecyl phosphite, monotetradecyl phosphite, monohexadecyl phosphite, monooctadecyl phosphite Etc. Phosphite compounds with an alkyl group of 7 or less carbon atoms have a strong odor and are easy to bloom, and those with more than 18 carbon atoms have reduced compatibility with the resin and increased their activity to process molding. Becomes difficult and bloom phenomenon occurs. The addition amount of these alkyl phosphite compounds is 0.01-5.0 weight part with respect to 100 weight part of vinyl chloride resin.
[0008]
The vinyl chloride resin used in the present invention includes a homopolymer resin of vinyl chloride, a copolymer resin mainly composed of vinyl chloride, and a polymer resin blend. Examples of the copolymer resin mainly composed of vinyl chloride include copolymers of vinyl chloride and ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid ester, methacrylic acid ester, maleic acid ester and the like. These vinyl chloride resins may be produced by any production method as long as they are obtained by a well-known polymerization method up to now.
[0009]
Examples of the epoxidized vegetable oil used in the present invention include epoxidized soybean oil, epoxidized linseed oil, and epoxidized castor oil. The addition amount of these epoxidized vegetable oils is 0.1-20 weight part with respect to 100 weight part of vinyl chloride resin.
[0010]
The organic carboxylic acid of the organic carboxylic acid zinc and calcium salt used in the present invention is caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid , Pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, heneicosanoic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, oleic acid, elaidic acid, erucic acid, brassic acid, seracoleic acid, linoleic acid, linolenic acid Acid, ricinoleic acid, 12-hydroxyoctadecanoic acid, tallow fatty acid, coconut oil fatty acid, pearl fatty acid, tung oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, etc., cinnamic acid, benzoic acid, p-tertiary- Butyl benzoic acid, dimethyl benzoic acid, ethyl Benzoic acid, dimethylhydroxybenzoic acid, toluic acid, acetoxybenzoic acid, propylbenzoic acid, 3,5-di-tertiary-butyl-4-hydroxybenzoic acid, salicylic acid, p-tertiary-octylsalicylic acid, etc. Monovalent carboxylic acids, as well as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, adiline acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, phthalic acid And divalent carboxylic acids such as isophthalic acid, terephthalic acid and oxyphthalic acid, and monoester compounds of these divalent carboxylic acids with alcohols.
The addition amount of the organic carboxylic acid zinc salt or calcium salt is 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0011]
Examples of the β-diketone compound used in the present invention include 4-cyclopentene-1,3-dione, 4-methylcyclohexane-1,3-dione, 2-phenylcyclohexane-1,3-dione, and 2,2-dimethylcyclohexane. -1,3,5-trione, 2-benzylcyclohexane-1,3-dione, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, 1,4-bis (2,6 -Dioxocyclohexyl) -2-butene, bis (4-butylbenzoyl) methane, benzoyl-acetylmethane, 4-methoxybenzoyl-hexanoylmethane, benzoyl-acetyl-octylmethane, tribenzoylmethane, dehydroacetic acid, dehydropropionylacetic acid , 2- (2-Cyclohexene- -Yl) cyclohexane-1,3-dione, caproyl acetylmethane, benzoyl diacetylmethane, cyclohexylcarbonyl acetylmethane, cyclohexylcarbonyl benzoylmethane, benzoyltetralone, acetyltetralone, bis (cyclohexylcarbonyl) methane, dibenzoyl Methane, acetylacetone, butanoylacetone, stearoylacetone, lauroylacetone, benzoyl-phenylacetylmethane, benzoylformylmethane, benzoyl-palmitoylmethane, hexadecanoyl-formylmethane, isovaleryl-cyclohexylcarbonylmethane, cyclohexylcarbonyl-acetyl-ethylmethane, etc. Can be mentioned.
The added amount of these β-diketone compounds is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
[0012]
The hydrotalcite compound used in the present invention is a compound represented by the following formula (2). The addition amount of these compounds is 0.01-10 weight part with respect to 100 weight part of vinyl chloride resin.
[0013]
[Chemical formula 2]
[Mg _a Zn _b ] _1-x Al _x (OH) ₂ A _{x / 2} · mH ₂ O (2)
[Here, A is a CO ₃ or SO ₄ anion, and a, b, and x are positive numbers that satisfy the following conditions. a + b = 1, 0 ≦ b <a, 0 <x ≦ 0.5. m is a number satisfying 0 ≦ m <2. ]
[0014]
As plasticizers used in the present invention, phthalate ester plasticizers (dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, didecyl Phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, etc.), ester plasticizer or polyester plasticizer of carboxylic acid other than phthalic acid (di-n-butyl adipate, di-n) -Octyl adipate, diisononyl adipate, diisodecyl adipate, polypropylene adipate, polybutylene adipate, diisobutyl azelate, di-2-ethylhexyl azelate, dibutyl Bacate, di-2-ethylhexyl sebacate, polypropylene sebacate, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, di-2-ethylhexyl fumarate, tributyl citrate, dibutyl malate, dioctyl malate, Methyl acetyl ricinolate, polypropylene sebacate, etc.).
The addition amount of these plasticizers is 0-50 weight part with respect to 100 weight part of vinyl chloride resin.
[0015]
Since the surface of the synthetic resin is itself hydrophobic, depending on conditions such as temperature and humidity, moisture that has been adsorbed or agglomerated may form fine water droplets that cover the surface and cause fogging. For this reason, various inconveniences occur. In order to remove these defects, an antifogging agent is blended when processing and molding a vinyl chloride resin product. As specific examples of these antifogging agents, cationic surfactants, anionic surfactants, nonionic surfactants and the like can be appropriately used depending on the purpose. Nonionic surfactants are preferable because they improve the slipperiness and the unwinding property of the film.
[0016]
Specific examples thereof include glycerol monopalmitate, glycerol monostearate, glycerol monooleate, glycerol monolinato, glycerol mono12-hydroxystearate, glycerol monocaprylate, glycerol monolaurate and the like as glycerol fatty acid ester system. Glycerin mono-dipalinate, glycerin mono-distearate, glycerin di-tristearate, glycerin mono-diolate, glycerin di-trioleate, glycerin mono-dilinoleate, glycerin mono-dibehenate, glycerin mono-dilysinolate, glycerin mono-di-12- Mono-diglycerides such as hydroxystearate, glycerol mono-diolate stearate, glycerol mono-dioxalate Glycerin tri-2-ethylhexoate, glycerin tricaprylate, triglycerides such as glycerin trifatty acid (C7-11) ester, glycerin diacetomonolaurate, glycerin diacetomonostearate, glycerin diacetomonooleate, glycerin diacetomonolinoleate, Glycerin diacetomono 12-hydroxystearate, glycerin diacetomonomyristate, glycerin diacetomonopalmitate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin monoacetomonomyristate, glycerin monoacetomonopalinate, glycerin monopalinate Acetomonoricinoleate, glycerol monoacetomono 12-hydroxystearate, glycerol monoacetomonobehenate Acetylated glycerides such as glycerol monoacetomonooleate, glycerol monoacetomonolaurate, glycerol monoacetodiolate, glycerol monoacetodiricinolate, glycerol monoacetodicaprylate, glycerol monoacetodilaurate, glycerol monoacetodistearate, Succinic acid saturated fatty acid monoglyceride, citric acid saturated fatty acid monoglyceride, citric acid unsaturated fatty acid monoglyceride, diacetyltartaric acid saturated fatty acid monoglyceride, diacetyltartaric acid unsaturated fatty acid monoglyceride, lactic acid saturated fatty acid monoglyceride and other organic acid monoglycerides, sorbitan fatty acid esters and their oxidation Ethylene adducts include sorbitan laurate, sorbitan palmitate, sorbitan stearate, Rubitan tristearate, sorbitan oleate, sorbitan trioleate, sorbitan behenate, sorbitan tribehenate, sorbitan dilaurate, sorbitan distearate, sorbitan dipalinate, sorbitan monoerucinate, sorbitan monoricinoleate, sorbitan palm fatty acid ester , Sorbitan palm fatty acid ester, sorbitan beef fatty acid ester, etc., polyoxyethylene (6) sorbitan monolaurate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20 ) Sorbitan monostearate, polyoxyethylene 20) sorbitan tristearate, polyoxyethylene (20) sorbitan trioleate, polyoxye Len (30) sorbitan monomyristate, polyoxyethylene (20) sorbitan tetraoleate, polyoxyethylene (40) sorbitan dipearl fatty acid ester, polyoxyethylene (60) sorbitan tetraoleate, polyoxyethylene (60) sorbitan tricoco Diglycerin laurate, diglyceryl stearate, diglycerin oleate, diglycerin caprylate, diglycerin behenate, diglycerin myristate, diglycerin palm fatty acid ester, diglycerin palm Fatty acid esters, diglycerin fatty acid esters such as diglycerin beef fatty acid ester, tetraglyceryl stearate, tetraglycerin oleate, hexaglycerin lauret , Decaglycerol laurate, decaglycerol oleate, polyglycerol fatty acid esters such as polyglycerin polyricinoleate and the like.
The addition amount of these anti-fogging agents is 0.5-5 weight part with respect to 100 weight part of vinyl chloride resin.
[0017]
In addition, lubricants, antioxidants, antistatic agents, fillers, reinforcing agents, mold release agents, foaming agents, cross-linking agents, antifungal agents, processing aids, plate-out prevention agents, pigments, viscosity reduction as necessary An agent or the like can be included in the food packaging vinyl chloride resin of the present invention.
[0018]
【Example】
Next, the effects of the present invention will be described in detail with reference to examples. The evaluation values of thermal stability and colorability in the examples are as follows. Strong: 5; Excellent: 4, Medium: 3, Weak / Inferior: 2, Inferior: 1.
[0019]
Comparative Example 1
The following formulation is kneaded at 180 ° C. for 5 minutes by a two-roll mill to form a sheet having a thickness of 1 mm, this sheet is cut into about 5 cm 2, and about 2 cm from the bottom of a 50 ml bottle. put, to warm the bottle to 60 ℃, it was compared the smell at the time of it. Odor evaluation values are as follows. Odorless: 5, weak odor: 4, moderate odor: 3, strong odor: 2, very strong odor: 1.
Further, this sheet was cut to make a fine piece, and this was put into a gear oven at 180 ° C. to evaluate the thermal stability of the sheet over time. Further, six pieces of this sheet were stacked and pressed at 180 ° C. for 5 minutes to prepare a press sheet having a thickness of 5 mm, and the colorability was evaluated.
[Combination]
Vinyl chloride resin (degree of polymerization: 1300) 100 parts by weight Diisononyl adipate 30
Epoxidized soybean oil Table 1 Calcium benzoate Table 1 Calcium ricinoleate Table 1 Zinc oleate Table 1 Zinc octylate Table 1 Alkyl phosphite compounds Table 1
[Table 1]
[0021]
Example 1
The following composition was kneaded at 180 ° C. for 5 minutes by a two-roll mill to prepare a sheet having a thickness of 1 mm. The sheet was cut into small pieces, which were placed in a gear oven at 180 ° C., and the thermal stability of the sheet was evaluated over time. In addition, several small pieces of this sheet were stacked, and a press sheet having a thickness of 5 mm was prepared by applying pressure at 180 ° C. for 5 minutes to evaluate the colorability.
[Combination]
Vinyl chloride resin (degree of polymerization: 1300) 100 parts by weight Diisononyl adipate 30
Epoxidized soybean oil 10
Calcium benzoate 0.05
Calcium ricinoleate 0.1
Zinc octylate 0.1
Alkyl phosphite compounds Table 2 β-diketone compounds Table 2 Hydrotalcite compounds Table 2
[Table 2]
[0023]
Example 2
The following blend was kneaded at 180 ° C. for 5 minutes by a two-roll mill to prepare a sheet having a thickness of 1 mm. The sheet was cut into small pieces, which were placed in a gear oven at 180 ° C., and the thermal stability of the sheet was evaluated over time. In addition, several pieces of this sheet were stacked and pressed at 180 ° C. for 10 minutes to prepare a press sheet having a thickness of 5 mm, and the colorability was evaluated.
[Combination]
Vinyl chloride resin (degree of polymerization: 800) 100 parts by weight Epoxidized soybean oil Table 3 Calcium benzoate salt Table 3 Calcium stearate salt Table 3 Zinc stearate salt Table 3 Zinc octylate salt Table 3 Alkyl phosphite compound Table 3 β-diketone compounds Table 3 Hydrotalcite compounds Table 3
[Table 3]
[0027]
【The invention's effect】
By using epoxidized vegetable oil, organic carboxylic acid zinc salt, organic carboxylic acid calcium salt and alkyl phosphite compound having 8 to 18 carbon atoms in combination with vinyl chloride resin, the odor of epoxidized vegetable oil is improved, A vinyl chloride resin composition for food packaging films having excellent stability and colorability could be obtained.

Claims (4)

(A) 0.1 to 20 parts by weight of epoxidized vegetable oil with respect to 100 parts by weight of vinyl chloride resin, (b) organic carboxylic acid zinc salt, (c) organic carboxylic acid calcium salt, (d) A vinyl chloride resin composition for food packaging films, comprising an alkyl phosphite compound represented by the following general formula (1) and a β-diketone compound .
(Where R is an alkyl group having 8 to 18 carbon atoms, and n is 0, 1 or 2) (A) 0.1 to 20 parts by weight of epoxidized vegetable oil with respect to 100 parts by weight of vinyl chloride resin, (b) organic carboxylic acid zinc salt, (c) organic carboxylic acid calcium salt, (d) A vinyl chloride resin composition for food packaging films, comprising an alkyl phosphite compound and a hydrotalcite compound represented by the following general formula (1).
(Where R is an alkyl group having 8 to 18 carbon atoms, and n is 0, 1 or 2) (A) 0.1 to 20 parts by weight of epoxidized vegetable oil with respect to 100 parts by weight of vinyl chloride resin, (b) organic carboxylic acid zinc salt, (c) organic carboxylic acid calcium salt, (d) A vinyl chloride resin composition for food packaging films, comprising an alkyl phosphite compound represented by the following general formula (1), a β-diketone compound and a hydrotalcite compound .
(Where R is an alkyl group having 8 to 18 carbon atoms, and n is 0, 1 or 2)   The vinyl chloride resin composition for food packaging film according to any one of claims 1 to 3, further comprising a plasticizer.