KR100660362B1 - Polyvinylidene chloride based resin composition and process for producing the same - Google Patents

Abstract

Polyvinylidene chloride-based resin composition having excellent processability, thermal stability, color tone, pigment dispersibility, gas barrier properties, etc., containing an epoxy compound and a glycidyl group-containing (meth) acrylic resin as a thermal stabilizer in the polyvinylidene chloride-based resin . The manufacturing method of this resin composition, the film which consists of this resin composition, and the coloring resin composition containing glycidyl-group containing (meth) acrylic-type resin and a pigment.

Description

Polyvinylidene chloride-based resin composition and its manufacturing method {POLYVINYLIDENE CHLORIDE BASED RESIN COMPOSITION AND PROCESS FOR PRODUCING THE SAME}

The present invention relates to a polyvinylidene chloride-based resin composition, and more particularly to a polyvinylidene chloride-based resin composition excellent in workability, thermal stability, color tone, pigment dispersibility, gas barrier properties and the like. Polyvinylidene chloride-based resin composition of the present invention is suppressed the generation of coarse foreign substances, pigment aggregates, color stains, etc., has a color tone with a sense of quality and excellent sealing, strength, adhesion to food A film can be given.

The present invention also relates to a novel process for producing a polyvinylidene chloride-based resin composition and a film formed by molding a polyvinylidene chloride-based resin composition. The present invention also relates to a coloring resin composition suitable for coloring polyvinylidene chloride-based resins.

Polyvinylidene chloride-based resin (hereinafter abbreviated as "PVDC-based resin") is generally a copolymer of a vinylidene chloride monomer (hereinafter abbreviated as "VDC") and another monomer (comonomer). The homopolymer of VDC has a softening temperature and a decomposition temperature so that melt processing by extrusion molding is difficult. In addition, the homopolymer of VDC has a low compatibility with the plasticizer, making it difficult to improve workability due to plasticization.

Therefore, PVDC resin is a copolymer which internally plasticized by copolymerization of VDC and another monomer, and provided workability. In most cases, plasticizers are added to PVDC resins to improve melt processability. Examples of comonomers include vinyl chloride and acrylate esters.

Extrusion grade PVDC resins molded into films, sheets, fibers and the like are generally produced by suspension polymerization. PVDC resin of an extrusion grade is generally prepared from the powder resin which has an average particle diameter of about 40-600 micrometers. Powder resin of PVDC resin is poor in thermal stability, so it is easily decomposed when melted to produce hydrochloric acid gas. In addition, the powder resin of PVDC resin has a processing temperature and decomposition temperature quite close even if the PVDC resin is a copolymer. Therefore, the powder resin of PVDC resin alone is difficult to melt processing such as extrusion molding alone.

Therefore, in order to satisfy the processability and the required characteristics of the molded product, generally, various additives such as heat stabilizers, plasticizers, lubricants and the like are added to the powder resin of the PVDC resin to prepare a so-called compound (resin composition). The method of extrusion molding this compound is employ | adopted. Films (including sheets) obtained by extruding compound of PVDC resin are excellent in barrier property, heat resistance, heat shrinkage, etc., so they can be used as single layer film or multilayer film as processed food packaging materials such as fish sausage, livestock meat processed products, etc. It is used.                         

Epoxy compounds are widely used as thermal stabilizers of PVDC-based resins. However, when extrusion molding using a compound in which an epoxy compound is added to the powder resin of the PVDC resin, the epoxy compound bleeds over time on the surface of the molded product. As the amount of epoxy compound added increases, such a problem is likely to be present. Moreover, when the addition amount of an epoxy compound is increased in order to improve thermal stability, the gas barrier property of a PVDC resin film will fall.

In the packaging film, when the epoxy compound is bleeded on the surface during storage, the film activity (packaging machine aptitude), sealing property (thermal sealing property, high frequency sealing property, etc.), printing aptitude, etc. may be lowered. Moreover, when the gas barrier property of a packaging film falls, the shelf life of the food which is a to-be-packaged object will fall. Moreover, when the packaging film containing an epoxy compound is applied to packaging, such as fish meat sausage, even if it colors with red pigment etc., the color tone of a film will become dark easily and may adversely affect the commodity value of a to-be-packaged article.

It has been proposed to use glycidyl group-containing (meth) acrylic resins as heat stabilizers for PVDC resins instead of epoxy compounds such as epoxidized vegetable oils. For example, Japanese Patent Application Laid-Open No. 5-148398 discloses a vinylidene chloride copolymer composition containing an epoxy valent glycidyl methacrylate copolymer of at least 0.3 as a heat stabilizer, and a packaging sheet or film using the same. .

Japanese Patent Laid-Open No. 46-42941 proposes a casing for packaging meat mixture products comprising a resin composition containing an unsaturated organic acid glycidyl ester (co) polymer in a vinylidene chloride-vinyl chloride copolymer. Japanese Laid-Open Patent Publication No. 59-89342 proposes a resin composition having improved weather resistance by adding to a halogen resin containing a glycidyl group-containing (meth) acrylate (co) polymer.

Glycidyl group-containing (meth) acrylic resins have a hydrochloric acid trapping function, exhibit thermal stabilization of PVDC-based resins, and have a smaller tendency to bleed than general-purpose epoxy compounds.

However, when the film is molded using a resin composition in which glycidyl group-containing (meth) acrylic resin is blended with PVDC-based resin in an amount necessary for thermal stabilization, the resulting film shows a tendency to slightly decrease transparency. In addition, when glycidyl group-containing (meth) acrylic resin is added to PVDC resin blended with carboxyl group-containing resin for imparting adhesion to meat and the like, glycidyl group-containing (meth) acrylic resin causes crosslinking reaction of PVDC resin. It is easy to reduce the glossiness and transparency of a film. Moreover, when the compounding ratio of glycidyl-group-containing (meth) acrylic-type resin becomes large, molded articles, such as a film, will become hard and it will become a cause of fall of cold-resistant strength. In addition, when the blend conditions are not controlled, aggregates of the glycidyl group-containing (meth) acrylic resin itself tend to be generated.

When a glycidyl group-containing (meth) acrylic resin is blended with the powder resin of the PVDC resin, aggregates of the glycidyl group-containing (meth) acrylic resin itself are liable to occur unless the blending conditions are controlled. In addition, the glycidyl group-containing (meth) acrylic resin is easily softened under blending conditions with the powder resin of the PVDC resin, and thus, the powder resin, pigment particles, and the like are easily aggregated. The agglomerated particles, for example, become a factor of bubble burst during film formation by the inflation method and lower productivity. In addition, the film containing the aggregated particles tends to produce appearance defects due to the production of fish eyes and the like and tends to be poor in sealing properties.

On the other hand, pigments are used to color moldings made of PVDC-based resins. When pigments are added directly to the powder resin of PVDC-based resins and blended, pigment particles aggregate to form stains, streaks, pinholes, etc., in final moldings such as films. Easy to generate. Although a method of preparing a colorant masterbatch in which pigments are dispersed in liquid components such as epoxidized vegetable oils and plasticizers and blending them with powder resins of PVDC resins is known, this masterbatch is difficult to handle and it is difficult to increase the pigment concentration. In addition, there is a problem of contaminating the inside of the mixer.

When a large amount of aggregated particles are removed by sieving in the final process of the blend, most of the glycidyl group-containing (meth) acrylic resin and pigments are removed, which causes problems such as deterioration of the thermal stability of the compound or the inability to obtain a desired coloration. Occurs.

Because of the above problems, glycidyl group-containing (meth) acrylic resins have been proposed as thermal stabilizers of PVDC resins, but in reality, it is difficult to employ them industrially, or repeated studies are required for industrialization. to be.

Disclosure of the Invention

An object of the present invention is to provide a polyvinylidene chloride-based resin composition excellent in workability, thermal stability, color tone, pigment dispersibility, gas barrier properties and the like.                     

Moreover, the objective of this invention is providing the manufacturing method of the polyvinylidene chloride type resin composition excellent in these various characteristics, and the film formed by shape | molding a polyvinylidene chloride type resin composition.

It is also an object of the present invention to provide a coloring resin composition suitable for producing a colored PVDC resin composition.

The present inventors earnestly studied to achieve the above object, and as a result, at least one epoxy selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester, and epoxy resin prepolymer as a heat stabilizer of PVDC resin By using a compound and a glycidyl group-containing (meth) acrylic resin in combination, it has been found that a PVDC resin composition having improved processability, color tone, pigment dispersibility, gas barrier properties and the like can be obtained while maintaining high thermal stability.

The film formed by molding the PVDC-based resin composition of the present invention has a slightly white color tone compared to the case where the epoxy compound is used alone, and can give a high quality to the product when used as a packaging film. The film formed by molding the PVDC-based resin composition of the present invention is suppressed the generation of coarse foreign matter, pigment aggregates, color stains, etc., and is excellent in sealing properties, strength, adhesion to food, and the like.

Epoxy compounds, such as epoxidized vegetable oil, are generally liquid at room temperature. On the other hand, since glycidyl-group-containing (meth) acrylic-type resin is powder, it is hard to bleed and it is excellent in handleability. However, when an epoxy compound and a glycidyl group containing (meth) acrylic resin are used together, the powder of the glycidyl group containing (meth) acrylic resin may be aggregated at the time of blending, and aggregates may be produced. At that time, aggregates of the pigment particles blended due to coloring tend to occur. Therefore, it is preferable to control blend conditions, such as the temperature conditions at the time of blending, and the blending order of each component.

Then, the epoxy compound which is a heat stabilizer, glycidyl-group-containing (meth) acrylic-type resin, and the method of including a pigment in PVDC-type resin were examined. As a result, the manufacturing method of manufacturing the powder resin of the PVDC resin composition containing an epoxy compound at the time of superposition | polymerization, and blending the powder of the resin composition for coloring containing a glycidyl group containing (meth) acrylic-type resin and a pigment to this powder resin. Reached.

Furthermore, after blending various components to temperature resin conditions containing the epoxy compound as needed, the manufacturing method which blends the powder of glycidyl-group-containing (meth) acrylic-type resin in the cooling process was reached.

According to these production methods, a uniform compound can be prepared while effectively suppressing generation of aggregates.

The present invention has been completed based on these findings.

Thus, according to this invention, in the polyvinylidene chloride-type resin composition containing polyvinylidene chloride type resin (A) and a heat stabilizer (B), this heat stabilizer (B) is an epoxidized vegetable oil, an epoxidized animal oil, Polyvinylidene chloride type, characterized in that it contains at least one epoxy compound (B1) selected from the group consisting of an epoxidized fatty acid ester and an epoxy resin prepolymer, and a glycidyl group-containing (meth) acrylic resin (B2). A resin composition is provided.                     

Moreover, according to this invention, glycidyl group containing (meth) which consists of copolymerization of 10-50 weight% of glycidyl esters of the unsaturated organic acid which can be vinyl-polymerized, and 50-90 weight% of at least 1 sorts of vinyl monomers copolymerizable with this (meth A resin composition for coloring containing an acrylic resin (B2) and a pigment (C) is provided.

According to the present invention, a polyvinylidene chloride resin containing at least one epoxy compound (B1) selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester and epoxy resin prepolymer during polymerization. Poly which blends powder of the resin composition for coloring containing glycidyl-group containing (meth) acrylic-type resin (B2) and pigment (C) to the powder resin of (A), and the epoxy compound (B1) added as needed. A method for producing a vinylidene chloride-based resin composition is provided.

Moreover, according to this invention, at least 1 sort (s) chosen from the group which consists of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester, and epoxy resin prepolymer at the time of powder resin or superposition | polymerization of polyvinylidene chloride-type resin (A). Powder, a pigment of a glycidyl group-containing (meth) acrylic resin (B2), and an epoxy compound (B1) or, if necessary, to a powder resin of a polyvinylidene chloride-based resin (A) containing an epoxy compound (B1) There is provided a method for producing a polyvinylidene chloride-based resin composition for blending an epoxy compound (B1) to be added.

Moreover, according to this invention, the film formed by shape | molding the said polyvinylidene chloride type resin composition is provided.

Best Mode for Carrying Out the Invention

1. Polyvinylidene Chloride Resin (A)

Polyvinylidene chloride resin (PVDC resin) used in the present invention is a copolymer of vinylidene chloride (VDC) 60 to 98% by weight (mass%) with 2 to 40% by mass of other monomers (comonomers) copolymerizable with to be.

As comonomer, For example, vinyl chloride; Alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate and the like (alkyl group having 1 to 18 carbon atoms); Methacrylic acid alkyl esters (C1-C18 of an alkyl group), such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; Vinyl cyanide such as acrylonitrile and methacrylonitrile; Aromatic vinyls such as styrene; Vinyl esters of aliphatic carboxylic acids having 1 to 18 carbon atoms such as vinyl acetate; Alkyl vinyl ethers having 1 to 18 carbon atoms; Vinyl-polymerizable unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid; Alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid (including partial esters and having 1 to 18 carbon atoms in the alkyl group); In addition, a diene type monomer, a functional group containing monomer, a polyfunctional monomer, etc. are mentioned.

These comonomers can be used individually or in combination of 2 types or more, respectively. Among these comonomers, vinyl chloride, methyl acrylate, and lauryl acrylate are preferable. If the copolymerization ratio of the comonomer is too small, the internal plasticization is insufficient and the melt processability is lowered. If the copolymerization ratio of the comonomer is too large, the gas barrier property is lowered. The copolymerization ratio of the comonomer is preferably 3 to 35% by weight, more preferably 10 to 25% by weight.

The reduced viscosity [ηsp / C] of the PVDC resin is preferably from 0.035 to 0.070, more preferably from 0.040 to 0.065, particularly preferably from 0.045 to from the viewpoints of workability, packaging machine suitability, cold resistance, etc. in the case of forming into a film. 0.063. If the reduced viscosity of the PVDC-based resin is too low, the workability is lowered, and if it is too high, the coloring tendency is exhibited. Two or more kinds of PVDC-based resins having different reducing viscosities can be used in combination, thereby improving workability. When using 2 or more types of PVDC resin together, it is preferable that the reduced viscosity of a mixed resin exists in the said range.

PVDC-based resins can be blended with other resins as desired. As another resin, for example, an ethylene-vinyl acetate copolymer, a (meth) acrylic acid ester, preferably a (co) polymer of a (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms of an alkyl group [for example, methyl (meth) acrylate- (meth ) Butyl acrylate copolymer, methyl methacrylate-butadiene-styrene copolymer, and the like. These other resins can be blended when preparing a PVDC resin composition, or can be contained in the coloring resin composition blended with the PVDC resin. Other resin is normally used in the ratio of 20 weight part or less with respect to 100 weight part of PVDC system resin.

Among these other resins, the vinyl acetate content is preferably 20 to 40% by weight, more preferably 28 to 35% by weight, and the melt flow rate (MFR) is preferably 1 to 50 g / 10 minutes, more preferably 10 to Preferred is an ethylene-vinyl acetate copolymer (hereinafter abbreviated as "EVA") of 40 g / 10 minutes. By blending EVA, extrusion processability, seal strength, gas barrier properties, and the like can be improved. EVA is particularly suitable as a seal strength modifier for films. When the vinyl acetate content of EVA is too small, transparency and color tone deteriorate, for example, pearl color unsuitable as a food packaging material may be exhibited, or sealing property may fall. When the vinyl acetate content of EVA is too high, the color tone or shape of molded products such as a film tends to decrease.

The blending ratio of EVA is preferably 0.5 to 5 parts by weight, more preferably about 1 to 3 parts by weight based on 100 parts by weight of the PVDC resin. When the blending ratio of EVA is too small, the effect of improving the extrusion processability is small, and when the PVDC resin composition is used as a packaging material, it is difficult to suppress the deterioration of the sealing property during the sterilization of the boil or the retort while sufficiently improving the cold resistance. On the other hand, when the blending ratio of EVA is too large, the seal strength is lowered or the layer peeling state easily occurs in the stretched alignment film.

EVA is usually blended into a PVDC-based resin, but all or part of its blending ratio can be used as a component of a coloring resin composition containing a pigment. EVA is also effective in preventing the micronization and adjusting the particle size in the pulverization step when producing the powder of the colored resin composition (colorant master batch).

When blending other resins, it is preferable to adjust so that the content rate of the vinylidene chloride component in a mixed resin component may be 50 weight% or more from a viewpoint of gas barrier resistance, heat resistance, etc. In addition, the PVDC resin may be mixed with a resin composition which can be recycled, such as molding debris generated during molding processing of the PVDC resin composition.

The PVDC-based resin used in the present invention may be synthesized by any polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization, etc., but in order to form a compound with powder resin, a crushing process is performed with a particle size of about 40 to 600 µm. What is obtained by the suspension polymerization method which is not necessary is preferable. Further, the PVDC resin may contain an antioxidant, a plasticizer, an epoxy compound, or the like during the polymerization.

Powder resin of PVDC system resin generally has an average particle diameter of about 40-600 micrometers. In this invention, the powder resin which contained additives, such as an epoxy compound and a plasticizer, at the time of superposition | polymerization can be used. Of course, the powder resin which does not contain additives, such as an epoxy compound and a plasticizer, can be used by this invention.

Powder resins of PVDC resins containing additives such as epoxy compounds and plasticizers at the time of polymerization are added to the polymerization reaction system at least at any time before, during or after polymerization, and then contained in the resulting PVDC resin. It was recovered to resin.

2. Heat stabilizer (B)

In the present invention, at least one epoxy compound (B1) selected from the group consisting of an epoxidized vegetable oil, an epoxidized animal oil, an epoxidized fatty acid ester, and an epoxy resin prepolymer and a glycidyl group-containing (meth) acrylic resin ( B2) is used in combination.

The epoxidized vegetable oil and the epoxidized animal oil used in the present invention are not particularly limited as long as they are conventionally used as heat stabilizers of PVDC-based resins, and a double bond is obtained by epoxidizing a natural animal or vegetable oil having an unsaturated bond with hydrogen peroxide or peracetic acid. What modified | denatured by the oxirane ring can be used. Preferred epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.

Examples of the epoxidized fatty acid esters include epoxides of unsaturated fatty acid esters such as epoxidized octyl stearate. Examples of the epoxy resin prepolymers include bisphenol A glycidyl ether. Among these epoxy compounds, epoxidized vegetable oil is preferred in the field of food packaging.

The epoxy compound is usually 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 1 to 3 parts by weight based on 100 parts by weight of the PVDC resin in combination with a glycidyl group-containing (meth) acrylic resin. Used as a ratio. When the compounding ratio of an epoxy compound is too large, it will become easy to bleed on the surface during the storage of the molding formed from the PVDC resin composition. Moreover, when the compounding ratio of an epoxy compound is too large, the blocking of a molded object will arise easily, the improvement effect of a color tone will fall, or the gas-bearing property of a film will fall. When the compounding ratio of the epoxy compound is too small, the degree of plasticization of the PVDC resin is lowered, the workability tends to be lowered, and the thermal stability also tends to be lowered.

The epoxy compound may be blended with the powder resin of the PVDC resin, or may be added to the monomer mixture in the polymerization step to polymerize, or may be added to the slurry after polymerization, or may be contained in the resin composition by a combination of these methods. Among these, it is preferable to contain an epoxy compound in powder resin at the time of superposition | polymerization, and to add as needed at the time of blending.

As glycidyl-group containing (meth) acrylic-type resin (B2) used by this invention, the copolymer which contains the glycidyl ester of the unsaturated organic acid which can be vinyl-polymerized as a copolymerization component is preferable. Since this copolymer typically contains (meth) acrylic acid ester, such as (meth) acrylic acid glycidyl and (meth) acrylic acid ester which does not contain a glycidyl group, as a copolymerization component, in this invention, glycidyl group containing It is called (meth) acrylic-type resin. Preferred glycidyl group-containing (meth) acrylic resins include glycidyl esters of unsaturated organic acids capable of vinyl polymerization, (meth) acrylic acid esters containing no glycidyl groups, and / or other vinyl monomers copolymerizable with these. Copolymer.

Examples of glycidyl esters of unsaturated organic acids capable of vinyl polymerization include glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), and β-methylglycidyl methacrylate. glycidyl esters of (meth) acrylic acid, such as β-methylglycidyl acrylate; Diglycidyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; Etc. can be mentioned. Glycidyl esters of the unsaturated organic acids capable of vinyl polymerization can be used alone or in combination of two or more thereof. Among them, glycidyl group-containing (meth) acrylic acid esters such as glycidyl methacrylate are preferable.

As (meth) acrylic acid ester which does not contain a glycidyl group, For example, alkyl acrylate esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate (C1-C18 of an alkyl group) ); Methacrylic acid alkyl esters (C1-C18 of an alkyl group), such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; Etc. can be mentioned. Among these, methyl methacrylate, butyl acrylate, etc. are preferable. These (meth) acrylic acid esters can be used individually or in combination of 2 types or more, respectively.

As other vinyl monomer which can be copolymerized, styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride, alkyl vinyl ether, etc. are mentioned. These vinyl monomers can be used individually or in combination of 2 types or more, respectively. Among these, styrene is preferable.

As glycidyl-group-containing (meth) acrylic-type resin, the copolymer of 10-50 weight% of glycidyl esters of the unsaturated organic acid which can be vinyl-polymerized, and 50-90 weight% of at least 1 type of vinyl monomer which can copolymerize with this is preferable. . Among such copolymers, 10 to 50% by weight of glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, 10 to 90% by weight of (meth) acrylic acid ester containing no glycidyl group, and 0 to 40% by weight of other vinyl monomers The copolymer with is more preferable. When the resin composition for coloring (colorant masterbatch) which disperse | distributed the pigment to such a copolymer previously is produced, pigment dispersibility can be improved and it is preferable.

As for content of the glycidyl-group containing monomer in glycidyl-group-containing (meth) acrylic-type resin, typically the glycidyl ester of the unsaturated organic acid which can be vinyl-polymerized, 10-50 weight% is preferable, and when this content is too small, PVDC system resin The compatibility with the resin is reduced, the heat stability of the resin composition is lowered, or changes with the passage of time of the color tone of the packaging film tend to occur. When the content of the glycidyl group-containing monomer component is excessively high, it is easy to cause poor dispersion in the resin composition or to cause appearance defects such as fish eyes in molded articles such as films.

As a specific example of glycidyl-group-containing (meth) acrylic-type resin, glycidyl methacrylate-methyl methacrylate- butyl- acrylate copolymer, glycidyl methacrylate-methyl methacrylate copolymer, and methacrylate Cedyl-methyl methacrylate-styrene copolymer, glycidyl methacrylate-vinyl chloride copolymer, glycidyl methacrylate-ethyl acrylate copolymer, glycidyl methacrylate-butyl acrylate copolymer, methacrylic And acid glycidyl-vinylidene chloride copolymers.

Although the molecular weight of glycidyl-group containing (meth) acrylic-type resin is not specifically limited, Weight average molecular weight (Mw) is 3,000-100,000 normally, Preferably it is about 5,000-50,000. When this weight average molecular weight (Mw) is too big | large, aggregate (fish eye) will generate | occur | produce easily in a film, and when too small, blocking of films will arise easily and packaging machine aptitude deteriorates.

Although the epoxy value of glycidyl-group-containing (meth) acrylic-type resin is not specifically limited, 0.3 or more may be sufficient, Especially when it is less than 0.3, pigment dispersibility, color tone, thermal stability, workability, gas barrier property, etc. are easy to be highly balanced, and it is preferable. This epoxy value becomes like this. Preferably it is 0.25 or less, More preferably, it is 0.2 or less. In most cases, good results can be obtained when the epoxy value is about 0.05 to 0.2. When the epoxy value of glycidyl-group-containing (meth) acrylic-type resin becomes large too much, a fish eye etc. will arise easily and it will become a bad appearance of a molded object. On the contrary, when epoxy value is too small, the effect of thermal stability will fall.

The glycidyl group-containing acrylic resin is usually 0.3 to 5 parts by weight, preferably 0.4 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the PVDC resin in combination with the epoxy compound. When this compounding ratio is too small, thermal stability will fall or a hue improvement effect will fall. When this compounding ratio is too big | large, the gas barrier property and cold resistance of a molded object will fall, and it will become difficult to obtain a clear coloring degree. In most cases, a favorable result can be obtained with this compounding ratio about 0.7-1.5 weight part.

The use ratio of an epoxy compound (B1) and glycidyl-group containing (meth) acrylic-type resin (B2) is 90: 10-40: 60 normally on a basis of weight, Preferably it is 80: 20-50: 50. By using the epoxy compound (B1) and the glycidyl group-containing (meth) acrylic resin (B2) together at such a ratio, the bleeding caused by the epoxy compound is suppressed while maintaining the high thermal stability of the PVDC resin. Properties such as color tone, workability, and gas barrier properties can be improved.

Moreover, the compounding ratio in the sum total of an epoxy compound (B1) and glycidyl group containing (meth) acrylic-type resin (B2) is 0.5-8 weight part normally with respect to 100 weight part of PVDC resin, Preferably it is 1-5 weight Part, More preferably, it is 1.5-4 weight part. When the compounding ratio by the sum of these heat stabilizers is too large, problems such as bleeding or transparency are likely to occur, and when too small, the thermal stability may be lowered or the combined effects of both may not be sufficiently obtained.

3. Other additives

The PVDC resin composition of the present invention may contain various additives such as antioxidants, plasticizers, lubricants, dispersion aids, fillers, ultraviolet absorbers, surfactants, other stabilizers, pH adjusters, and pigments.

As antioxidant, 2, 6- di-tert- butyl- 4-methyl- phenol (BHT), triethylene glycol-bis [3- (3-tert- butyl- 5-methyl-4- hydroxyphenyl) propio Nate (manufactured by Chiba Co., Ltd., Irganox 245), 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and mixtures thereof And phenolic antioxidants such as Irganox 1141); Thioether antioxidants such as thiodipropionic acid and distearylthiodipropionate; Phosphite antioxidants such as trisnonyl phenyl phosphite and distearyl pentaerythritol diphosphite; Etc. can be mentioned. Antioxidant is normally used in the ratio of 0.0001-0.05 weight part with respect to 100 weight part of PVDC resin.

Examples of the plasticizer include dioctyl phthalate, acetyl tributyl citrate, dibutyl sebacate, dioctyl sebacate, acetylated monoglycerides, acetylated diglycerides, acetylated triglycerides, and acetylation containing 2-3 of these. Polyester plasticizers, such as glycerides, adipic acid and 1, 3- butanediol, adipic acid and 1, 4- butanediol, and 2 or more types of these mixtures, are typical.                     

A plasticizer is normally used in the ratio of 0.05-10 weight part with respect to 100 weight part of PVDC resin. The plasticizer can be blended with the powdered resin of the PVDC resin, polymerized by addition to the monomer mixture in the polymerization step, added to the slurry after polymerization, or contained in the resin composition by a combination thereof. Among these, it is preferable to contain a plasticizer in powder resin at the time of superposition | polymerization, and to blend an additional plasticizer as needed at the time of blending.

As the lubricant, suitable for melt processing of PVDC-based resin compositions, waxes such as polyethylene oxide wax, paraffin wax, polyethylene wax, montan ester wax, and calcium montanate; Fatty acid ester, such as glycerin monoester, is mentioned. Moreover, fatty acid mono or bisamide, such as stearic acid amide, is mentioned as what is suitable for the melt processing of a PVDC system resin composition, and the secondary processing of a film. These lubricants are usually used in an appropriate amount of 2 parts by weight or less with respect to 100 parts by weight of PVDC resin.

As a dispersing aid at the time of disperse | distributing a pigment, the said epoxy compound and a plasticizer, lubricating agents, such as paraffin wax, a polyethylene wax, a montan acid ester wax, and a calcium montanate, a glycerin fatty acid ester type, a sorbitan fatty acid ester type, polyoxyethylene Surfactants, such as a sorbitan fatty acid ester type, glycerin, propylene glycol, and an aliphatic hydrocarbon type or an aromatic hydrocarbon type oligomer and polymer are mentioned. Among these, a C2-C8 aliphatic hydrocarbon oligomer is preferable. In particular, a liquid aliphatic hydrocarbon oligomer having a weight average molecular weight of 300 to 5000 is preferably used.                     

The dispersing aid may be used at the time of preparation of the PVDC resin composition, but may be used at the time of preparation of the resin composition for coloring. The dispersing aid improves the dispersibility of the pigment, prevents the pigment from scattering, and lowers the processing temperature, thereby facilitating the preparation of the resin composition for coloring. Dispersion aid is usually used in a ratio of 2 parts by weight or less based on 100 parts by weight of PVDC resin. When the dispersing aid is excessively used, it is easy to deteriorate the grindability of the colorant and to impair the barrier property of the PVDC resin.

Examples of the filler include silicon dioxide and calcium carbonate. Moreover, silicon dioxide and calcium carbonate also act as an uneven | corrugating agent, a film-activating agent (packaging machine aptitude), etc. Silicon dioxide also acts as an inorganic lubricant. Silicon dioxide is effective in preventing EVA agglomeration when blending EVA. A suitable amount of filler is usually 1 part by weight or less, preferably 0.5 parts by weight or less, based on 100 parts by weight of PVDC resin.

As a ultraviolet absorber, 2- (2'-hydroxy-3 ', 5'-di-tert- butylphenyl) -5-chlorobenzotriazole etc. are mentioned, A suitable amount is used as needed.

As surfactant, nonionic surfactant, such as sorbitan fatty acid ester, polyglycerol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, etc. are mentioned, A suitable amount is used as needed. Glycerin fatty acid monoester, sorbitan monobehenylate, sorbitan fatty acid ester, etc. are also useful as a peeling agent of a packaging film.

As another stabilizer, Inorganic bases, such as magnesium hydroxide, magnesium oxide, calcium hydroxyphosphate; Organic weak acid salts such as citric acid and alkali metal citrate salts; Ethylenediamine tetraacetates; Etc. can be suitably used in an appropriate amount.                     

Examples of the pH adjuster include sodium pyrrolate and disodium bipyronate, and an appropriate amount of 0.5 parts by weight or less is used based on 100 parts by weight of the PVDC resin.

Examples of the pigment include organic pigments such as azo, phthalocyanine and quinacridone; Inorganic pigments such as titanium oxide, aluminum, mica and carbon black; Extender pigments such as calcium carbonate and magnesium oxide; Etc. are used. Among these, red pigments, such as pigment red, are common in the field of the packaging film of processed foods, such as a fish sausage and livestock meat processed goods. Pigments can be used individually or in combination of 2 types or more, respectively. An appropriate amount of the pigment is usually 1 part by weight or less based on 100 parts by weight of the PVDC resin. However, in the case of titanium oxide pigment, it may be mixed up to 10 parts by weight.

Some of these additives have various functions such as plasticizers, dispersing aids, lubricants, and the like. In addition, these additives are usually added to and blended with the powder resin of the PVDC resin, but may be mixed with the slurry after the end of the polymerization of the PVDC resin or added to the monomer mixture before the polymerization, as desired.

4. Coloring resin composition (colorant master batch)

In the present invention, when the pigment is contained in the PVDC resin composition, it can be used in the form of a resin composition containing a high concentration of the pigment in advance, that is, a colorant master batch. As a coloring agent masterbatch, the resin composition for coloring containing glycidyl-group containing (meth) acrylic-type resin (B2) and a pigment (C) is preferable.

This coloring resin composition can further contain (meth) acrylic acid ester (co) polymer (F), ethylene-vinyl acetate copolymer (D), etc. which do not contain a glycidyl group as needed.

In addition, a plasticizer, a dispersion aid, or the like can be added to the resin composition for coloring in order to increase the dispersibility of the pigment.

The coloring resin composition is pulverized and used as a powder in order to add to the mixture of the powder resin of polyvinylidene chloride type resin, and various additives, such as an epoxy compound (B1). For grinding, impact mills such as jet mill grinders are used.

As preferable glycidyl-group containing (meth) acrylic-type resin, the copolymer of 10-50 weight% of glycidyl esters of the unsaturated organic acid which can be vinyl-polymerized, and 50-90 weight% of at least 1 type of vinyl monomer which can copolymerize with this is mentioned. Can be. Glycidyl group-containing (meth) acrylic resins include 10 to 50% by weight of glycidyl esters of unsaturated organic acids capable of vinyl polymerization, 10 to 90% by weight of (meth) acrylic acid esters containing no glycidyl groups, and copolymerization thereof. It is more preferable that it is a copolymer of 0-40 weight% of other vinyl monomers which can be possible.

The resin composition for coloring of this invention contains glycidyl-group containing (meth) acrylic-type resin preferably 20 to 90 weight%, More preferably, it is the ratio of 30 to 60 weight%. When the blending ratio of the glycidyl group-containing (meth) acrylic resin is too large, fine powder is likely to occur during the pulverization of the colored resin composition, and when too small, the pulverization tends to decrease.

The pigment is usually contained in a proportion of 10 to 80% by weight, preferably 15 to 60% by weight, more preferably 20 to 40% by weight. If the blending ratio of the pigment is too large, its uniform dispersibility is lowered, and if it is too small, the effect of the colorant master batch becomes small. Increasing the content of the pigment as much as possible within the range capable of maintaining uniform dispersibility of the pigment is particularly preferable in terms of cost since a PVDC resin composition having a desired coloration can be obtained with a small amount of coloring resin composition.

The coloring resin composition of this invention can be made to contain a dispersion adjuvant. When it contains a dispersal auxiliary agent, the content rate is 0.05-10 weight% normally, Preferably it is 0.5-5 weight%, More preferably, it is about 1-3 weight%. When the blending ratio of the dispersing aid is too large, the softening temperature of the colored resin composition is lowered and is easily blocked, and when too small, the effect of improving the dispersibility of the pigment is reduced.

The coloring resin composition of this invention can be made to contain a plasticizer. In this case, epoxidized vegetable oils, such as epoxidized soybean oil, can also be used as a plasticizer. However, since the blending ratio of the colored resin composition in the PVDC resin composition is usually small, the ratio of the epoxidized vegetable oil to the entire epoxy compound (B1) of the epoxidized vegetable oil is considerably small.

The epoxidized vegetable oil and other plasticizers are usually contained in a proportion of 0.5 to 10% by weight, preferably 1 to 7% by weight, more preferably 2 to 5% by weight, based on the total amount of the coloring resin composition. If the blending ratio of the plasticizer is too large, the softening temperature of the coloring resin composition is lowered, and it is easy to block. If too small, the degree of plasticizer is insufficient, and uniform blending is difficult when blending with the powder resin of the PVDC resin.

The coloring resin composition of this invention can contain the (co) polymer (F) of the (meth) acrylic acid ester which does not contain a glycidyl group in order to stabilize the extrusion processability. Methyl methacrylate, butyl methacrylate, etc. are mentioned as (meth) acrylic acid ester. Among these, methyl methacrylate-butyl methacrylate copolymer is preferable. The blending ratio of the (meth) acrylic acid ester (co) polymer (F) containing no glycidyl group is preferably 10 to 40% by weight, more preferably 15 to 30% by weight based on the total amount of the resin composition for coloring. . When this compounding ratio is too large, high frequency sealing property will fall, and when too small, extrusion processability may become unstable.

The coloring resin composition of this invention can be made to contain an ethylene-vinyl acetate copolymer (EVA). As mentioned above, the vinyl acetate content in EVA is preferably 20 to 40% by weight, more preferably 28 to 35% by weight. The melt flow rate (MFR) of EVA is preferably 1 to 50 g / 10 minutes, more preferably 20 to 40 g / 10 minutes. It is preferable to contain EVA in a ratio of 50 weight% or less, More preferably, it is 30 weight% or less, Especially preferably, 20 weight% or less in coloring resin composition. When EVA is contained, it is normally contained in the ratio of 1 weight% or more, Preferably it is 5 weight% or more.

When there is too much content of EVA, the melt viscosity of a coloring resin composition will become small, the dispersibility of a pigment will fall, or it will become rubbery at normal temperature, and it will not grind well, or heat resistance will fall and it will become easy to stick and block. When there is too little content of EVA, when the coloring resin composition is grind | pulverized, the particle size of the powder obtained will become too thin.

The coloring resin composition of this invention can be made to contain various additives, such as an organic or inorganic lubricant and antioxidant, as needed in a suitable quantity range.

A coloring resin composition is prepared by mixing each component and heat-kneading the mixture. The resin composition for coloring is normally pulverized and used as powder. Preferably, the kneaded material is melt-extruded into a sheet shape and quenched to obtain a sheet, and then the sheet is pulverized into powder. It is preferable that the particle size of this powder passes through the sieve of # 20 mesh from the viewpoint of dispersibility with the powder resin of PVDC system resin, and it is more preferable to pass through the sieve of # 40 mesh.

The resin composition for coloring of the present invention can be added to conventional thermoplastic resins because of its excellent thermal stability.

5. Manufacturing method of PVDC resin composition

Generally, when preparing a resin composition containing a PVDC resin and various additives, a powdery resin composition (compound) is prepared by blending various additives together with the powder resin of the PVDC resin. By the blend, liquid additives such as epoxidized vegetable oil and plasticizer are absorbed into the powder resin of the PVDC resin, and the additive of the powder is attached to the periphery of the powder resin of the PVDC resin.

Aggregation of an additive component tends to occur at the time of this blend, and in particular, aggregation of pigment particles and glycidyl group-containing (meth) acrylic resin powder is likely to occur. The presence of a large amount of aggregates in the PVDC resin composition impairs workability, extrudability, film formation, stretchability, etc., and also introduces appearance defects due to the formation of fish eyes in moldings such as films. It is preferable to study the addition method of each component in order to improve dispersibility of a pigment and to suppress generation | occurrence | production of the aggregate of a pigment and an additive component.

In the first production method of the present invention, polyvinyl chloride containing at least one epoxy compound (B1) selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester and epoxy resin prepolymer during polymerization. Blend the powder of the resin composition for coloring containing glycidyl-group containing (meth) acrylic-type resin (B2) and pigment (C) in powder resin of a lidene system resin (A), and the epoxy compound (B1) added as needed. It is a manufacturing method of the polyvinylidene chloride type resin composition.

It is preferable that the powder resin of polyvinylidene chloride-type resin (A) was added to the epoxy compound (B1) at the time of superposition | polymerization, and also contained the plasticizer (E) further. In addition, in order to contain an epoxy compound (B1) and / or a plasticizer (E) in the powder resin of PVDC type resin at the time of superposition | polymerization, these are added to the monomer mixture before superposition | polymerization, in superposition | polymerization reaction system during superposition | polymerization, or it is added to the slurry after superposition | polymerization. It is contained in the produced PVDC resin and then recovered in a powdered resin.

When the content of the epoxy compound (B1) and / or the plasticizer (E) in the powder resin is small, the epoxy compound (B) and / or the plasticizer (E) added as necessary in the blending step may be blended. In blending, ethylene-vinyl acetate copolymer (D) and other additives can be blended as desired. As powder of the resin composition for coloring, the above-mentioned thing is used.

According to the 1st manufacturing method of this invention, each component can be blended at normal temperature. Since the main component of the epoxy resin (B1) and the plasticizer is contained in the powder resin of the PVDC resin in advance, it can be blended with the powder of the resin composition for coloring at room temperature, thereby compounding a uniform composition. Can be prepared.

The second production method of the present invention is at least one selected from the group consisting of an epoxidized vegetable oil, an epoxidized animal oil, an epoxidized fatty acid ester, and an epoxy resin prepolymer in powder resin or polymerization of a polyvinylidene chloride-based resin (A). Powder, pigment and epoxy compound (B1) of glycidyl group-containing (meth) acrylic resin (B2), or, if necessary, to the powder resin of polyvinylidene chloride-based resin (A) containing epoxy compound (B1) of species It is a manufacturing method of the polyvinylidene chloride-type resin composition which blends the epoxy compound (B1) added.

It is preferable to contain the epoxy compound (B1) and / or plasticizer (E) in advance at the time of superposition | polymerization in the powder resin of polyvinylidene chloride-type resin (A). At the time of blending, the ethylene-vinyl acetate copolymer (D) and other additives can be blended. When powder resin does not contain an epoxy compound (B1), an epoxy compound (B1) is blended at the time of blending. In addition, even if the powdered resin contains an epoxy compound (B1) and / or a plasticizer (E) at the time of polymerization, when these contents are small, an epoxy compound (B1) and / or a plasticizer (E) is added as necessary at the time of blending. ) Can be blended.

In the second production method of the present invention, glycidyl group-containing (meth) is contained in the powder resin of polyvinylidene chloride-based resin (A) or the powder resin of polyvinylidene chloride-based resin (A) containing epoxy compound (B1). After adding components other than the powder of the acrylic resin (B2) and blending under elevated temperature conditions, blending the powder of the glycidyl group-containing (meth) acrylic resin (B2) during the cooling process suppresses the formation of aggregates and It is preferable in preparing the compound mixed uniformly.

More specifically, liquid additives, such as an epoxy compound (B1) and a plasticizer (E), powder additives, such as a lubricating agent, etc. are added to the powder resin of polyvinylidene chloride-type resin (A), and are blended under temperature rising conditions. As a blend under a temperature rising condition, the method of blending is usually preferable, heating up to the temperature of 65 degreeC or more and 85 degrees C or less.

Powder resin of PVDC resin is added to the mixer to add powder additives such as lubricant, liquid additives such as plasticizer (E), epoxy compound (B1), dispersing aid and the like as necessary, and then the pigment is immediately added. It is preferable to add. These mixtures are blended while raising to temperatures up to 85 ° C (eg, about 80 ° C).

When the mixture is raised to a predetermined temperature, it is usually cooled immediately, and in this cooling process, a powder of glycidyl group-containing (meth) acrylic resin (B2) is added and blended. The addition time of the glycidyl group-containing (meth) acrylic resin (B2) powder is when the temperature of the mixture is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, even more preferably to room temperature. When the blend temperature of glycidyl-group-containing (meth) acrylic-type resin (B2) powder is 80 degreeC or more, the aggregate of a pigment particle will generate | occur | produce easily.

Since the PVDC resin composition (compound) thus obtained may contain coarse particles, although it is weak, it is preferable to remove coarse particles using a separator.

When blending EVA separately, it is preferable to blend the resin composition obtained by each said method, and EVA powder. EVA is preferably blended at room temperature. In this case as well, it is preferable to separate the coarse particles by using a sieve after the blending.

Each component can be mixed using a blender such as a wing blender, a ribbon blender, a Henschel mixer, or the like. Moreover, when manufacturing resin composition for coloring, you may knead | mix using two roll machines and three roll machines.

According to the manufacturing method of this invention, generation | occurrence | production of the aggregate of a pigment particle, the aggregate of glycidyl-group-containing (meth) acrylic-type resin, etc. can be suppressed, and the PVDC system composition excellent in workability and various characteristics can be obtained.

"Normal temperature" in this invention means 5-45 degreeC normally, Preferably it is 10-40 degreeC, More preferably, it means the temperature of 15-35 degreeC.

6. Molding of PVDC resin composition

The PVDC resin composition (compound) of the present invention can be melt-extruded and molded into a stretched or unstretched film, sheet or the like. As a method of forming a film, an inflation extrusion method using a circular die is used. An oriented film obtained by stretching, preferably biaxial stretching, is suitably used as a heat resistant film having heat shrinkability and capable of retort. The stretching ratio is preferably 2 to 5 times in the longitudinal direction and 2 to 5 times in the transverse direction.

The film thickness is 5-50 micrometers normally with a single film, Preferably it is 10-30 micrometers. Depending on the application, it is also used as a double film. It is preferable that the thermal contraction rate of a stretched film is about 30 to 60% (120 degreeC glycerine bath, 3 minutes) for both length and width | variety. The main method of use as a food packaging film is, after inflation, overlapped with two sheets, a double film is slitted at both ends of the film, sealed with a packaging machine, and the contents are filled and both ends are gripped to obtain a package. Packaging films are suitable as packaging materials for processed foods such as fish meat sausages and livestock meat processed products.

Films formed from the PVDC resin composition of the present invention randomly selected 10 places of about 100 g (about 1.5 m ² ) at random, and when the pigment dispersion state was observed using a magnifying glass, the number of aggregated masses of 0.4 mm or more was observed. Is 10 or less, the pigment dispersibility is remarkably excellent. This means that the PVDC resin composition of the present invention is excellent in thermal stability because generation of aggregates is suppressed.

The film molded from the PVDC resin composition of the present invention is clearly improved in color tone compared to conventional products obtained by using a general-purpose epoxy compound such as epoxidized soybean oil or epoxidized linseed oil alone as a heat stabilizer. Shows a slightly bright luxury. Therefore, processed foods such as fish meat sausages and livestock meat processed products packaged with this film have a sense of quality and can contribute to the improvement of product value.

The film molded from the PVDC-based resin composition of the present invention has excellent adhesion to meat and the like. However, when the surface treatment such as corona discharge treatment is performed, the effect of improving the adhesion to the film is further improved. It can be increased to reduce the occurrence of drips such as juicy in the meat.

When an epoxy compound such as epoxidized soybean oil or epoxidized linseed oil is contained in the PVDC resin, the gas barrier property of the film generally shows a tendency to decrease. However, the PVDC resin composition of the present invention has excellent thermal stability due to the action of dispersed epoxy compound and glycidyl group-containing (meth) acrylic resin during molding, but after molding, Because of its good compatibility with epoxy compounds, finely dispersed glycidyl group-containing (meth) acrylic resins absorb liquid epoxy compounds, and as a result, adhesion to gas barriers and meats is maintained while maintaining thermal stability. Is improved. Therefore, the film molded from the PVDC resin composition of the present invention has excellent gas barrier properties.

Blending EVA contributes to the improvement of extrusion processability and seal strength, and also to the improvement of gas barrier properties by absorbing epoxy compound together with glycidyl group-containing (meth) acrylic resin after molding. Since the epoxy compound contributes to the thermal stability during melt processing such as extrusion molding, the epoxy compound does not adversely affect the thermal stability of moldings such as a film even when absorbed by glycidyl group-containing (meth) acrylic resin or EVA after molding.

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated more concretely, this invention is not limited to these. The evaluation method used by this invention is as follows.

(1) reduced viscosity

The PVDC resin was extracted and treated with a Soxhlet extractor using methanol as a solvent, and then dried, as a sample. The solvent was cyclohexane, the resin concentration was 4 g / l, and the measurement temperature was 30 ° C. using an Uberod viscometer. The reduced viscosity was determined under the conditions.

(2) Evaluation of extrusion stability (thermal stability, workability)

 The PVDC resin composition (compound) was melt-extruded using an extruder (motor 15KW) having a screw diameter of 90 mm. The variation range of the motor load of the extruder was recorded. In addition, the extrusion situation was observed. The following criteria evaluated.

○: ± 3A or less (processability is stable),

(Triangle | delta): ± 5A or less (The stability of workability is poor, but can be manufactured), or a lot of adhesion (decomposition) of resin generate | occur | produces in the die exit part from which the molten resin is extruded from an extruder,

X: It exceeds +/- 5 A (manufacturing difficulty).

(3) Compound yield

When the PVDC resin composition and the coloring resin composition were used in a blend, they were separated using a sieve of # 10 mesh and a sieve of # 50 mesh. The weight of the thing which did not pass through the sieve after sieving was measured and evaluated based on the following criteria.

○: the amount remaining on the mesh is less than 0.2% by weight of the input amount,                     

X: The quantity remaining on a mesh is 0.2 weight% or more of an input amount.

(4) color tone

The retort sterilized package was observed in 10 healthy adults to determine whether the color tone or shape was improved compared to the conventional product. Evaluation criteria are as follows. It judged that the evaluation of seven or more persons agreed.

(Circle): A hue and a pattern are better than a conventional product, and there is a sense of quality,

△: white and slightly opaque,

X: Blue-green, slightly blackish.

(5) Coarse particle count in film

The dispersion state in the film was observed with a magnifying glass, and random 100 g ranges (about 1.5 m ² ) were randomly observed at ten places, and the number of aggregates of 0.4 mm or more was investigated and evaluated as the evaluation criteria.

○: 10 or less,

△: more than 10 pieces

(6) Evaluation of High Frequency Sealability [Packaging Machine Aptitude, Film Activity]

The original 1m width was cut | disconnected narrowly to width 70mm, and the original wound up was created. Using an automatic charging ligating device (Kure 500 KAP500 type, Kureha Kagaku Kogyo Co., Ltd.) with a film supply unit, a high frequency seal unit, an automatic charging unit, and a ligation unit, a current value of 70 mA, an electrode surface pressure of 400 g and a charging speed of 100 The raw meat for pork sausage was filled at 200 mm / minute and the product length (between all clips) of the package was set. High frequency sealing was evaluated based on the following criteria.

(Circle): The film activity at the time of umbilical cord is good, there is no squiggle, there is no film peeling of the forming plate, the folding width is uniform, and stable high frequency sealing is possible, and the product length of the package is ± 2.5 of the set value. It is finished within mm.

X: The film activity at the time of umbilization is poor, there is an unevenness, the film peeling of the forming plate, the folding width is uneven, and stable high frequency sealing is impossible, and the product length of the package is finished at ± 2.5 mm or more of the set value. It is becoming.

(7) Breakage rate of package (from seal part during retort sterilization)

The 100 packages obtained above were heated and autoclaved for 20 minutes at a gauge pressure of 2.0 kg / cm 2 and a temperature of 120 ° C. in a heating can, and the pressure was cooled to 25 ° C. while maintaining the pressure, and then opened and taken out of the heating can. It was. The number of pieces shredded from the seal portion of the package was examined to determine the percentage shredded.

Example 1

1. Preparation of coloring resin composition

As shown in Table 1, 41 weight% of glycidyl-group-containing (meth) acrylic-type resin [methacrylate glycidyl-methyl methacrylate- styrene- butyl acrylate (30/31/31/8 weight%)], meta 23% by weight methyl methacrylate-butyl methacrylate copolymer, 25% by weight pigment red mixture (pigment), 5% by weight of silicon dioxide (inorganic lubricant; average particle diameter 5.2㎛), 3% by weight epoxidized soybean oil, aliphatic hydrocarbon oligomer 2 weight% (Mw = 2,100) and 1 weight% of calcium montanate were stirred at room temperature (23 ° C) for 5 minutes by a Henschel mixer to obtain a resin composition for coloring. The composition is shown in Table 1.

Coloring resin composition Furtherance 2 parts by weight wt.% Breakdown Glycidyl group-containing (meth) acrylic resin Glycidyl methacrylate-methyl methacrylate-styrene-butyl acrylate = 30/31/31/8 (wt.%), Epoxy value = 0.19 41 0.82 Methyl methacrylate-butyl methacrylate copolymer 23 0.46 Pigment Red (mixture) 25 0.50 Silicon dioxide 5 0.10 Epoxidized Soybean Oil 3 0.06 Aliphatic hydrocarbon oligomer 2 0.04 Calcium carbonate One 0.02

(Footnote) In Example 1, since this coloring resin composition was blended in the ratio of 2.0 weight part with respect to 100 weight part of PVDC-type resin, it shows in order to refer to the description of each component in this 2.0 weight part.

The obtained coloring resin composition was heat-kneaded for 10 minutes with the biaxial heating roller (phi = 200mm) set to the surface 150 degreeC. After kneading, the kneaded product was quenched to obtain a sheet. This sheet was pulverized using a jet mill grinder (impact pulverizer) and the pulverized product was passed through a screen of # 40 mesh to obtain powder of a resin composition for coloring.

2. Preparation of PVDC resin composition

As PVDC resin, PVDC (1) [vinylidene chloride (VD) / vinyl chloride (VC) = 88/12 (wt%), reduced viscosity = 0.063] and PVDC (2) [VD / VC = 83/17 (weight %), Reduced viscosity = 0.052]. At the time of polymerization of each powder resin, 2.4 parts by weight of epoxidized linseed oil (O-180) and 3.5 parts by weight of dibutyl sebacate were contained in 100 parts by weight of the PVDC resin.

The powder of the coloring resin composition prepared above and the various additives were added to the powder resin of the said 2 types of PVDC system resin, and the PVDC system resin composition which has a composition shown in Table 2 was prepared. About each component, what was contained at the time of powder resin manufacture (at the time of polymerization), and what was contained at the time of blend were shown separately. Moreover, about the epoxy compound and the plasticizer, the total amount was shown including what is contained in the coloring resin composition.

First, PVDC resin composition (compound) was prepared by mixing the powder resin of PVDC resin, coloring resin composition, EVA, and various additives using a blade blender. Mixing time was 15 minutes. The mixing temperature was room temperature (23 ° C.) (room temperature blend). The PVDC resin composition was separated by a sieve of # 10 mesh to remove coarse particles.

3. Creation of film

The PVDC resin composition was melt-extruded in a ring shape using a 90-mm-diameter extruder (vacuum pressure = approximately -680 mmHg mercury column) with a vacuum hopper, and then quenched in a cooling bath at 7 ° C., followed by 20 A stretched film was made by passing a hot water bath at 0 ° C. and inflation by inflation with air between two pinch rollers having different rotational surface speeds and stretching orientation about 2.5 times in the longitudinal direction and about 4.2 times in the transverse direction. The evaluation results are shown in Table 2.

Comparative Example 1

At the time of polymerization of each powder resin, 3.4 parts by weight of epoxidized linseed oil (O-180) and 3.5 parts by weight of dibutyl sebacate were contained with respect to 100 parts by weight of the PVDC resin. Operation was carried out in the same manner as in Example 1, except that these powder resins were used and no coloring resin composition and glycidyl group-containing (meth) acrylic resin were used. The results are shown in Table 2.

Example 2

At the time of polymerization of the powder resin of PVDC (1), 0.3 parts by weight of epoxidized linseed oil (O-180) and 4.0 parts by weight of dibutyl sebacate were contained in 100 parts by weight of the PVDC resin. In each component shown in Table 2, components other than glycidyl-group containing (meth) acrylic-type resin are powder resin of PVDC (1), powder additive, a liquid additive (tributyl acetate, epoxidized linseed oil), and a pigment order. It heated up to about 80 degreeC, putting into a blade blender and mixing as it was (warming blend). After temperature rising, it cooled immediately, and when the temperature fell to about 65 degreeC, the powder of glycidyl-group-containing (meth) acrylic-type resin was thrown in and mixed (blend after temperature rising). After cooling, the resin composition (compound) was obtained by separating into a # 50 mesh sieve. A stretched film was created and evaluated in the same manner as in Example 1 except that this resin composition was used. The results are shown in Table 2.

Comparative Example 2

At the time of superposition | polymerization of the powder resin of PVDC (1), 4.0 weight part of dibutyl sebacates were contained with respect to 100 weight part of PVDC-type resin so that it might become these ratio. It operated similarly to Example 2 using this powder resin and adding the glycidyl group containing (meth) acrylic-type resin at the time of blending together with another powder additive collectively. The results are shown in Table 2.

Comparative Example 3

At the time of polymerization of each powder resin, 2.46 parts by weight of epoxidized linseed oil (O-180) and 3.5 parts by weight of dibutyl sebacate were contained in 100 parts by weight of the PVDC resin. About 80 using these powder resins and putting components other than glycidyl-group-containing (meth) acrylic-type resin and EVA among powder components, a powder additive, and a pigment blender in order in order to mix them, about 80 The temperature was raised to ° C (temperature blend). After temperature rising, it cooled immediately, and when the temperature fell to about 65 degreeC, the powder of glycidyl-group-containing (meth) acrylic-type resin was thrown in and mixed (blend after temperature rising). Thereafter, EVA was blended at room temperature (room temperature blend). The stretched film was produced like Example 1 using the obtained resin composition. The results are shown in Table 2.                     

(footnote)

* 1: The numerical value in () shows the weight part of each component contained in 2.0 weight part of coloring resin compositions.

In Example 1, the epoxy compound and the plasticizer were added at the time of polymerization and not at the time of blending. If there is no liquid additive in the blend, the liquid additive does not need to be temperature-blended in order to be absorbed into the powder resin of the PVDC resin, and can be blended at room temperature, and the blend time is shortened. Moreover, the powder of the resin composition for coloring can be blended at normal temperature, and generation | occurrence | production of an aggregate is suppressed. On the other hand, in Comparative Example 1, since the blend was performed at room temperature without using the resin composition for coloring, the number of coarse particles in the film, high frequency sealing property, and breaking ratio of the package were poor.

In Example 2, the powder of the epoxy compound and the glycidyl group-containing (meth) acrylic resin are used in combination, and the powder of the glycidyl group-containing (meth) acrylic resin is blended in the cooling step, whereby no aggregates are generated and the color tone is also improved. On the contrary, in Comparative Example 2, the compound yield, the coarse particle number in the film, the high frequency sealing property, and the breaking rate of the package were poor depending on the timing of the glycidyl group-containing (meth) acrylic resin, and the glycidyl group-containing (meth The use of acrylic resin alone makes the film color unsatisfactory, resulting in poor extrusion stability.

In Example 3, the same temperature rising blend as in Example 2 was used instead of the room temperature blend, but it can be seen that a resin composition and a film having desired characteristics were obtained.

Example 4

0.4 parts by weight of epoxidized linseed oil (O-180) and 3.5 parts by weight of dibutyl sebacate (DBS) based on 100 parts by weight of the PVDC resin in the polymerization of the respective powder resins of PVDC (1) and PVDC (2). It was contained so that it might become. Among each component shown in Table 3, components other than glycidyl-group containing (meth) acrylic-type resin (GMA) and ethylene-vinyl acetate copolymer (EVA) are powder resin of PVDC (1) and PVDC (2), powder additive , Liquid additives (epoxidized linseed oil) and pigments were added to the blade blender in order of temperature and heated up to about 80 ° C. while being mixed (heated blend). After temperature rising, it cooled immediately, and when the temperature fell to about 65 degreeC, the powder of glycidyl-group-containing (meth) acrylic-type resin was thrown in and mixed (blend after temperature rising). Thereafter, EVA was blended at room temperature. After cooling, the resin composition (compound) was obtained by separating into a # 50 mesh sieve. A stretched film was created and evaluated in the same manner as in Example 1 except that this resin composition was used. The results are shown in Table 3.

Comparative Example 3

In Example 4, the compounding amount of the epoxidized linseed oil at the time of the temperature rising blend was changed from 2.2 parts by weight to 3.0 parts by weight, and further, the glycidyl group-containing (meth) acrylic resin (GMA) was not blended after the temperature rising. In the same manner, a stretched film was prepared. The results are shown in Table 3.

[Comparative Example 4]

The stretched film was produced like Example 4 except not having used the epoxidized linseed oil at the time of superposition | polymerization and temperature-blending blending in Example 4. The results are shown in Table 3.

Example 5

A stretched film was prepared in the same manner as in Example 4 except that EVA was not blended in Example 4. The results are shown in Table 3.

Example 6

0.4 parts by weight of epoxidized linseed oil (O-180) and 3.5 parts by weight of dibutyl sebacate (DBS) based on 100 parts by weight of the PVDC resin in the polymerization of the powder resins of PVDC (1) and PVDC (2). It was contained so that it might become. The powdery resin of PVDC (1) and PVDC (2) and 2.2 weight part of epoxidized linseed oil were heated up to about 80 degreeC, mixing and mixing into a wing blender (warming blend). After the temperature was raised, 0.1 parts by weight of the film lubricant (silicon dioxide), 2.0 parts by weight of the colored resin composition, and 2.5 parts by weight of EVA were mixed at the time of cooling to room temperature (23 ° C.) (room temperature blend). Thereafter, a resin composition (compound) was obtained by separation with a sieve of # 50 mesh. A stretched film was created and evaluated in the same manner as in Example 1 except that this resin composition was used. The results are shown in Table 3.

Example 7

In Example 6, powder powder, 2.2 parts by weight of epoxidized linseed oil, 0.1 part by weight of a film lubricant (silicon dioxide), 2.0 parts by weight of a colored resin composition, and 2.5 parts by weight of EVA were mixed at room temperature (at room temperature blend). A stretched film was created and evaluated in the same manner as in Example 6. The results are shown in Table 3.

[Comparative Example 5]

Example 7 except that 2.2 parts by weight of the epoxidized linseed oil 3.0 parts by weight, 0.1 parts by weight of the film lubricant (silicon dioxide) 0.2 parts by weight, 2.0 parts by weight of the coloring resin composition to 0.5 parts by weight of the pigment, and In the same manner, a stretched film was prepared and evaluated. The results are shown in Table 3.                     

(footnote)

* 1: The numerical value in () shows the weight part of each component contained in 2.0 weight part of coloring resin compositions.

 ADVANTAGE OF THE INVENTION According to this invention, the polyvinylidene chloride-type resin composition excellent in workability, heat stability, color tone, pigment dispersibility, gas barrier property, etc. is provided. Moreover, according to this invention, the manufacturing method of the vinylidene chloride-type resin composition excellent in these various characteristics, and the film formed by shape | molding this polyvinylidene chloride-type resin composition are provided.

Further, according to the present invention, there is provided a coloring resin composition suitable for producing a colored PVDC resin composition. The film obtained by using the PVDC resin composition of the present invention is excellent in color tone and shape and is suitable for packaging materials for processed foods such as fish meat sausage, processed meat and meat products.

Claims (28)

In a polyvinylidene chloride-based resin composition containing polyvinylidene chloride-based resin (A) and a heat stabilizer (B), the heat stabilizer (B) is (1) at least one epoxy compound (B1) selected from the group consisting of epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters, and epoxy resin prepolymers, and (2) glycidyl group-containing (meth) acrylic resin (B2) Polyvinylidene chloride-based resin composition comprising a. The amount of polyvinylidene chloride-based resin (A) according to claim 1, containing 0.1 to 5 parts by weight of the epoxy compound (B1) and 0.3 to 5 parts by weight of the glycidyl group-containing (meth) acrylic resin (B2). Resin composition. The glycidyl group-containing (meth) acrylic resin (B2) according to claim 1, wherein the glycidyl group-containing (meth) acrylic resin (B2) is 10 to 50% by weight of glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, and at least one vinyl monomer 50 to 90 capable of copolymerization with the glycidyl group-containing (meth) acrylic resin (B2). Resin composition which is a copolymer with weight%. The glycidyl group-containing (meth) acrylic resin (B2) is 10 to 50% by weight of glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, and (meth) acrylic acid ester 10 to no glycidyl group. A resin composition, which is a copolymer of 90% by weight and 0 to 40% by weight of other vinyl monomers copolymerizable therewith. The resin composition according to claim 1, wherein the glycidyl group-containing (meth) acrylic resin (B2) has an epoxy value of less than 0.3. The resin composition according to claim 1, further comprising a pigment (C). The powder resin of polyvinylidene chloride-type resin (A) of Claim 6 which contained the epoxy compound (B1) at the time of superposition | polymerization, (Ii) a powder of a resin composition for coloring containing a glycidyl group-containing (meth) acrylic resin (B2) and a pigment (C), and (Iii) Epoxy compounds added as necessary (B1) Resin composition which is a blend containing. The powder resin of (6) polyvinylidene chloride-based resin (A), (Ii) powder of glycidyl group-containing (meth) acrylic resin (B2), (Iii) pigments, (Iii) Epoxy Compounds (B1) Resin composition which is a blend containing. The powder resin of polyvinylidene chloride-type resin (A) of Claim 6 which contained the epoxy compound (B1) at the time of superposition | polymerization, (Ii) powder of glycidyl group-containing (meth) acrylic resin (B2), (Iii) pigments, (Iii) Epoxy compounds added as necessary (B1) Resin composition which is a blend containing. The resin composition according to claim 1, further comprising an ethylene-vinyl acetate copolymer (D). The resin composition according to claim 1, further comprising a plasticizer (E). (1) A glycidyl group-containing (meth) acrylic resin comprising a copolymer of 10 to 50% by weight of glycidyl ester of an unsaturated organic acid capable of vinyl polymerization and 50 to 90% by weight of at least one vinyl monomer capable of copolymerizing with it. (B2) and, (2) Pigment (C) Coloring resin composition containing the. The glycidyl group-containing (meth) acrylic resin (B2) according to claim 12, wherein the glycidyl group contains 10 to 50% by weight of a glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, and a (meth) acrylic acid ester 10 containing no glycidyl group. The resin composition for coloring which is a copolymer of 0 to 40 weight% of -90 weight% and the other vinyl monomer which can be copolymerized with this. The resin composition for coloring of Claim 12 which further contains the (meth) acrylic acid ester (co) polymer (F) which does not contain a glycidyl group. 13. The coloring resin composition according to claim 12, further comprising an ethylene-vinyl acetate copolymer (D). (1) Polyvinylidene chloride resin containing at least one epoxy compound (B1) selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester and epoxy resin prepolymer during polymerization (A ) Powdered resin, (2) powder of a resin composition for coloring containing a glycidyl group-containing (meth) acrylic resin (B2) and a pigment (C), and (3) Epoxy compound added as needed (B1) Method for producing a polyvinylidene chloride-based resin composition blended. The manufacturing method of Claim 16 in which the powder resin of polyvinylidene chloride-type resin (A) contains a plasticizer (E) further at the time of superposition | polymerization. The production method according to claim 16, wherein the ethylene-vinyl acetate copolymer (D) is further blended. The method of claim 16, wherein each component is blended at room temperature. (1) at least one epoxy compound selected from the group consisting of epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters, and epoxy resin prepolymers in powder resin or polymerization of polyvinylidene chloride-based resin (A) ( Powder resin of polyvinylidene chloride-based resin (A) containing B1), (2) powder of glycidyl group-containing (meth) acrylic resin (B2), (3) pigments, and (4) Epoxy compound (B1) or epoxy compound (B1) added as needed Method for producing a polyvinylidene chloride-based resin composition blended. The process according to claim 20, wherein the plasticizer (E) is further blended. The manufacturing method of Claim 20 in which the powder resin of polyvinylidene chloride-type resin (A) contains a plasticizer (E) at the time of superposition | polymerization. 23. The process according to claim 22, wherein further plasticizer (E) is further blended as necessary. The glycidyl group-containing (meth) according to claim 20, wherein (I) the powder resin of the polyvinylidene chloride-based resin (A) or the powder resin of the polyvinylidene chloride-based resin (A) containing the epoxy compound (B1). After adding components other than the powder of acrylic resin (B2) and blending under temperature rising conditions, (II) A process for blending powder of glycidyl group-containing (meth) acrylic resin (B2) during cooling. The production method according to claim 20, wherein the ethylene-vinyl acetate copolymer (D) is further blended. The method according to claim 24, wherein the powder of the glycidyl group-containing (meth) acrylic resin (B2) is blended in the cooling process, cooled to room temperature, and then further blended with the ethylene-vinyl acetate copolymer. The film formed by shape | molding the polyvinylidene chloride-type resin composition of any one of Claims 1-11. 28. The film of claim 27 which is a biaxially oriented film.