JP4861223B2 - Polyvinylidene chloride resin composition Coloring resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for coloration that is suitable for production of polyvinylidene chloride resin composition. <P>SOLUTION: The resin composition for coloration that is suitable for production of polyvinylidene chloride resin comprises (1) a glycidyl group-containing (meth)acrylic resin (B2) which is a copolymer including 10 to 50 %wt. of glycidyl ester of vinyl polymerizable unsaturated organic acid, 10 to 90 %wt. of (meth)acrylic ester having no glycidyl group, and 0 to 40 %wt. of at least one kind of vinyl monomer that is copolymerizable with the above stated monomer and is selected from the following group consisting of styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride and alkyl vinyl ethers and (2) pigment (C). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to a polyvinylidene chloride-based resin composition wearing color resin composition, and more particularly, workability, thermal stability, color tone, the dispersibility of the pigment, polyvinylidene chloride-based resin composition having excellent such as gas barrier property The present invention relates to a resin composition for coloring a polyvinylidene chloride-based resin composition, which is used for manufacturing a product. The polyvinylidene chloride-based resin composition using the coloring resin composition of the present invention has a high-grade color tone with suppressed generation of coarse foreign matters, pigment agglomerates, color spots, and the like. The film for packaging excellent in property, strength, and adhesion to foods can be provided.

  A polyvinylidene chloride resin (hereinafter abbreviated as “PVDC resin”) is generally a copolymer of a vinylidene chloride monomer (hereinafter abbreviated as “VDC”) and another monomer (comonomer). It is a coalescence. The homopolymer of VDC has a softening temperature and a decomposition temperature close to each other, and is difficult to melt by extrusion. In addition, a homopolymer of VDC has low compatibility with a plasticizer, and it is difficult to improve processability by plasticization.

  Therefore, the PVDC resin is a copolymer imparted with workability by internal plasticization by copolymerization of VDC and other monomers. In many cases, a plasticizer is further added to the PVDC resin to improve melt processability. Typical examples of the comonomer include vinyl chloride and acrylic acid ester.

  Extrusion grade PVDC-based resins formed into films, sheets, fibers, etc. are generally produced by suspension polymerization. The extrusion grade PVDC resin is generally prepared as a powder resin having an average particle size of about 40 to 600 μm. PVDC resin powder resin has poor thermal stability, and when melt processed, it is easily decomposed to generate hydrochloric acid gas. Moreover, the powder resin of a PVDC resin has a processing temperature and a decomposition temperature that are quite close to each other even if the PVDC resin is a copolymer. Therefore, the powder resin of PVDC resin is difficult to be melt processed such as extrusion molding by itself.

  Therefore, in order to satisfy the processability and the required properties of the molded product, generally, various additives such as a heat stabilizer, a plasticizer, and a lubricant are added to and blended with a powder resin of a PVDC resin, so-called compound ( A resin composition is prepared, and this compound is extruded. Films (including sheets) obtained by extruding a PVDC resin compound are excellent in barrier properties, heat resistance, heat shrinkability, etc., so that fish sausage, livestock meat as a single layer film or multilayer film Used as a packaging material for processed foods such as processed products.

  Epoxy compounds are widely used as thermal stabilizers for PVDC resins. However, when extrusion molding is performed using a compound in which an epoxy compound is added to a PVDC resin powder resin, there is a problem that the epoxy compound bleeds over the surface of the molded product over time. As the amount of the epoxy compound added increases, such a problem becomes more obvious. Further, when the amount of the epoxy compound added is increased in order to improve the thermal stability, the gas barrier property of the PVDC resin film is lowered.

  When an epoxy compound bleeds on the surface of a packaging film during storage, film slipperiness (packaging machine suitability), sealability (heat sealability, high frequency sealability, etc.), printability, and the like may deteriorate. Further, when the gas barrier property of the packaging film is lowered, the preservability of the food as the packaged product is lowered. Furthermore, when a packaging film containing an epoxy compound is applied to packaging for fish sausages, etc., even if it is colored with a red pigment, etc., the color tone of the film tends to be dark, which may adversely affect the commercial value of the packaged product. There is.

  It has been proposed to use glycidyl group-containing (meth) acrylic resins as thermal stabilizers for PVDC resins instead of epoxy compounds such as epoxidized vegetable oils. For example, Patent Document 1 (Japanese Patent Laid-Open No. 5-148398) discloses a vinylidene chloride copolymer composition containing a glycidyl methacrylate copolymer having an epoxy value of at least 0.3 as a heat stabilizer, and a package using the same. A sheet or film is disclosed.

  Patent Document 2 (Japanese Examined Patent Publication No. 46-42941) discloses a casing for packaging a meat paste product comprising a resin composition containing an unsaturated organic acid glycidyl ester (co) polymer in a vinylidene chloride-vinyl chloride copolymer. Has been proposed. Patent Document 3 (Japanese Patent Application Laid-Open No. 59-89342) proposes a resin composition with improved weather resistance obtained by adding a glycidyl group-containing (meth) acrylate (co) polymer to a halogen-containing resin. Yes.

  The glycidyl group-containing (meth) acrylic resin has a hydrochloric acid scavenging function, exhibits a thermal stabilization effect on the PVDC resin, and has an advantage of less tendency to bleed than a general-purpose epoxy compound. .

  However, when a film is formed using a resin composition obtained by blending a PVDC-based resin with a glycidyl group-containing (meth) acrylic resin in an amount necessary for thermal stabilization, the obtained film tends to have a slightly lower transparency. Indicates. In addition, when a glycidyl group-containing (meth) acrylic resin is added to a PVDC resin blended with a carboxyl group-containing resin for adhesion to meat or the like, the glycidyl group-containing (meth) acrylic resin is converted into a PVDC resin. It causes a cross-linking reaction and tends to reduce the gloss and transparency of the film. Furthermore, when the blending ratio of the glycidyl group-containing (meth) acrylic resin increases, a molded article such as a film becomes hard, which causes a decrease in cold resistance. Moreover, if the blending conditions are not controlled, aggregates of the glycidyl group-containing (meth) acrylic resin itself are likely to be generated.

  Furthermore, when a glycidyl group-containing (meth) acrylic resin is blended with a PVDC resin powder resin, an agglomerate of the glycidyl group-containing (meth) acrylic resin itself is likely to occur unless the blending conditions are controlled. In addition to this, the glycidyl group-containing (meth) acrylic resin is easily softened under a blending condition of the PVDC resin with the powder resin, thereby easily aggregating the powder resin, pigment particles, and the like. Aggregated particles, for example, cause bubble bursting during film formation by an inflation method and reduce productivity. In addition, a film containing agglomerated particles tends to cause poor appearance due to the formation of fish eyes and the like, and the sealing property tends to be poor.

  On the other hand, when coloring a molded product made of PVDC resin, a pigment is used. However, when a pigment is directly added to a powder resin of PVDC resin and blended, the pigment particles aggregate to form a final molded product such as a film. Easily causes color spots, streaks, pinholes, etc. There is known a method of preparing a colorant masterbatch in which a pigment is dispersed in a liquid component such as an epoxidized vegetable oil or a plasticizer, and blending this with a powder resin of a PVDC resin. However, it is difficult to increase the pigment concentration, and further, there is a problem that the inside of the mixer is contaminated.

  In the final blending process, if a large amount of agglomerated particles are removed by sieving, most of the glycidyl group-containing (meth) acrylic resin and pigment will be removed, so that the thermal stability of the compound may be lowered or desired. This causes inconveniences such as inability to obtain the degree of coloring.

Because of the above-mentioned problems, glycidyl group-containing (meth) acrylic resins are proposed as thermal stabilizers for PVDC resins, but are actually difficult to employ industrially, At present, further studies are needed for industrialization.
JP-A-5-148398 Japanese Examined Patent Publication No. 46-42941 JP 59-89342 A

An object of the present invention is to provide processability, thermal stability, color tone, the dispersibility of the pigment, excellent polyvinylidene chloride-based resin composition wearing color resin composition such as gas barrier properties.

  As a result of intensive studies to achieve the above object, the present inventors have selected from the group consisting of epoxidized vegetable oils, epoxidized animal oils, epoxidized fatty acid esters, and epoxy resin prepolymers as thermal stabilizers for PVDC resins. In combination with at least one epoxy compound and a glycidyl group-containing (meth) acrylic resin, processability, color tone, pigment dispersibility, and gas barrier properties are improved while maintaining high thermal stability. It was found that the obtained PVDC resin composition was obtained.

  A film formed by molding such a PVDC-based resin composition has a slightly white color as compared with the case where an epoxy compound is used alone, and gives a high-class feeling to a product when used as a packaging film. be able to. A film formed by molding such a PVDC resin composition is suppressed in the generation of coarse foreign matters, pigment agglomerates, and color spots, and is excellent in sealing properties, strength, adhesion to foods, and the like.

  Epoxy compounds such as epoxidized vegetable oil are generally liquid at room temperature. On the other hand, since the glycidyl group-containing (meth) acrylic resin is a powder, it is difficult to bleed and has excellent handleability. However, when an epoxy compound and a glycidyl group-containing (meth) acrylic resin are used in combination, the powder of the glycidyl group-containing (meth) acrylic resin may be aggregated to generate an aggregate during blending. In that case, the aggregate of the pigment particle mix | blended for coloring tends to generate | occur | produce. Therefore, it is desirable to control the blending conditions such as the temperature conditions during blending and the blending order of each component.

  Therefore, an investigation was made on a method for incorporating a PVDC resin into an epoxy compound as a heat stabilizer, a glycidyl group-containing (meth) acrylic resin, and a pigment. As a result, a powder resin of a PVDC resin composition containing an epoxy compound at the time of polymerization was produced, and a coloring resin composition containing a glycidyl group-containing (meth) acrylic resin and a pigment in the powder resin. A production method for blending powders was conceived.

In addition, the present inventors have conceived a manufacturing method in which various components are blended under a temperature rising condition in a powder resin containing an epoxy compound as required, and then a glycidyl group-containing (meth) acrylic resin powder is blended in the cooling process. . According to these production methods, a uniform compound can be prepared while effectively suppressing the generation of aggregates.
The present invention has been completed based on these findings.

Thus, according to the present invention, (1) 10 to 50% by weight of vinyl-polymerizable unsaturated organic acid glycidyl ester, 10 to 90% by weight of (meth) acrylic acid ester containing no glycidyl group, and copolymerized therewith Glycidyl group-containing (meth) acryl which is a copolymer of 0 to 40% by weight of at least one vinyl monomer selected from the group consisting of styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride and alkyl vinyl ether Is not copolymerized in the presence of a tackifier resin selected from rosin acid ester, terpene resin, coumarone resin, styrene resin, xylene resin, petroleum resin, or tammer during copolymerization Glycidyl group-containing (meth) acrylic resin (B2) 3 which is a glycidyl group-containing (meth) acrylic resin 0-60% by weight ,
(2) 10 to 40% by weight of (meth) acrylic acid ester (co) polymer (F) containing no glycidyl group, and
(3) Pigment (C) 15-60% by weight
Containing copolymer is a polyvinylidene chloride-based resin composition wearing color resin composition of 60 to 98% by weight of vinylidene chloride and a copolymerizable other monomer 2-40% by weight which can be provided .

  The method for producing a polyvinylidene chloride-based resin composition using the coloring resin composition of the present invention is at least one selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester, and epoxy resin prepolymer during polymerization. Resin composition for coloring containing glycidyl group-containing (meth) acrylic resin (B2) and pigment (C) in polyvinylidene chloride resin (A) powder resin containing various epoxy compounds (B1) A method of blending a powder of a product and, if necessary, an additional epoxy compound (B1) is preferred.

According to the present invention, PVDC resin composition wearing color resin composition colored is provided. By using this coloring resin composition, a PVDC resin composition excellent in processability, thermal stability, color tone, pigment dispersibility, gas barrier property and the like is provided. Furthermore, since the film obtained by using this PVDC resin composition is excellent in color tone and texture and has a high-class feeling, it is suitable as a packaging material for processed foods such as fish sausages and processed meat products.

1. Polyvinylidene chloride resin (A) used in the manufacture of polyvinylidene chloride resin composition
The polyvinylidene chloride resin (PVDC resin) used in the production of the polyvinylidene chloride resin composition is another monomer (copolymer) copolymerizable with 60 to 98% by weight (mass%) of vinylidene chloride (VDC). Monomer) is a copolymer of 2 to 40% by mass.

  Examples of the comonomer include vinyl chloride; alkyl acrylate esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and the like. -18); methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methacrylic acid alkyl esters such as stearyl methacrylate (alkyl group having 1 to 18 carbon atoms); cyan such as acrylonitrile and methacrylonitrile Aromatic vinyl such as styrene; vinyl ester of aliphatic carboxylic acid having 1 to 18 carbon atoms such as vinyl acetate; alkyl vinyl ether having 1 to 18 carbon atoms; acrylic acid, methacrylic acid, maleic acid, fumaric acid, itacon Acid Polymerizable unsaturated carboxylic acids; alkyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid (including partial esters, having 1 to 18 carbon atoms in the alkyl group); Body, functional group-containing monomer, polyfunctional monomer and the like.

  These comonomers can be used alone or in combination of two or more. Among these comonomers, vinyl chloride, methyl acrylate, and lauryl acrylate are preferable. When the copolymerization ratio of the comonomer is too small, the internal plasticization becomes 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 0.040, from the viewpoints of processability when molded into a film, suitability for packaging machinery, cold resistance, and the like. 0.065, particularly preferably 0.045 to 0.063. If the reduced viscosity of the PVDC-based resin is too low, the processability is deteriorated, and if it is too high, a coloring tendency is exhibited. Two or more kinds of PVDC resins having different reduced viscosities can be used in combination, thereby improving workability. When two or more kinds of PVDC resins are used in combination, the reduced viscosity of the mixed resin is preferably within the above range.

  The PVDC-based resin can be blended with other resins as desired. Examples of other resins include ethylene-vinyl acetate copolymer, (meth) acrylic acid ester, preferably (co) polymer of alkyl group (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms [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 the PVDC-based resin composition or can be contained in the coloring resin composition blended with the PVDC-based resin. The other resin is usually used at a ratio of 20 parts by weight or less with respect to 100 parts by weight of the PVDC 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%. An ethylene-vinyl acetate copolymer (hereinafter abbreviated as “EVA”) of ˜40 g / 10 min is preferred. By blending EVA, extrudability, seal strength, gas barrier properties, and the like can be improved. In particular, EVA is suitable as a film seal strength improver. When the vinyl acetate content of EVA is too small, transparency and color tone are deteriorated, for example, a pearl color inappropriate for a food packaging body may be exhibited, or the sealing property may be lowered. When the vinyl acetate content of EVA is too large, the color tone and texture of molded articles such as films tend 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 with respect to 100 parts by weight of the PVDC resin. If the blending ratio of EVA is too small, the effect of improving the extrudability is small, and when the PVDC-based resin composition is used as a packaging material, the seal during sterilization of boil and retort while sufficiently improving the cold resistance It becomes difficult to suppress the decrease in sex. On the other hand, when the blending ratio of EVA is too large, the sealing strength is lowered, or a layer peeling state is likely to occur in the stretched oriented film.

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

  When blending other resins, it is preferable to adjust the content ratio of the vinylidene chloride component in the mixed resin component to be 50% by weight or more from the viewpoint of gas barrier properties and heat resistance. In addition, the PVDC resin can be mixed with a recyclable resin composition such as molding waste generated during the molding process of the PVDC resin composition.

  The PVDC resin may be synthesized by any polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization, etc., but in order to form a compound as a powder resin, it has a particle size of about 40 to 600 μm, What was obtained by the suspension polymerization method which does not require a grinding | pulverization process is preferable. In addition, the PVDC resin can contain an antioxidant, a plasticizer, an epoxy compound, and the like during the polymerization.

  The PVDC resin powder resin generally has an average particle size of about 40 to 600 μm. In the present invention, a powder resin containing an additive such as an epoxy compound or a plasticizer can be used during polymerization. Of course, even a powder resin not containing an additive such as an epoxy compound or a plasticizer can be used.

  A powder resin of a PVDC resin containing an additive such as an epoxy compound or a plasticizer at the time of polymerization is added to the polymerization reaction system at least at any time before, during or after the polymerization. Then, after being contained in the produced PVDC resin, it is recovered as a powder resin.

2. Thermal stabilizer (B) used in the production of polyvinylidene chloride resin composition
In the production of a polyvinylidene chloride resin composition, as a heat stabilizer, 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; In addition, a glycidyl group-containing (meth) acrylic resin (B2) is used in combination.

  Epoxidized vegetable oils and epoxidized animal oils are not particularly limited as long as they are conventionally used as heat stabilizers for PVDC resins, and natural animal and vegetable oils having unsaturated bonds can be used for hydrogen peroxide, peracetic acid, etc. By epoxidizing with a oxirane ring, a double bond modified to an oxirane ring can be used. Preferred epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.

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

  The epoxy compound is usually 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 100 parts by weight of the PVDC resin in combination with the glycidyl group-containing (meth) acrylic resin. Is used in a proportion of 1 to 3 parts by weight. When the compounding ratio of the epoxy compound is too large, it tends to bleed to the surface during storage of a molded product formed from the PVDC resin composition. Moreover, when the compounding ratio of the epoxy compound is too large, blocking of the molded product tends to occur, the effect of improving the color tone is lowered, or the gas barrier property of the film is lowered. When the compounding ratio of the epoxy compound is too small, the degree of plasticization of the PVDC resin is lowered, the processability is likely to be lowered, and the thermal stability tends to be lowered.

  The epoxy compound is blended with the PVDC resin powder resin, added to the monomer mixture in the polymerization step, polymerized, added to the slurry after polymerization, or a combination of these resin compositions. It can be contained. Among these, it is preferable that an epoxy compound is contained in the powder resin at the time of polymerization and added as necessary at the time of blending.

  As the glycidyl group-containing (meth) acrylic resin (B2), a copolymer containing, as a copolymerization component, a glycidyl ester of an unsaturated organic acid capable of vinyl polymerization is preferable. Since the copolymer typically contains a (meth) acrylic acid ester such as glycidyl (meth) acrylate or a (meth) acrylic acid ester not containing a glycidyl group as a copolymerization component, in the present invention, It is called a glycidyl group-containing (meth) acrylic resin. The glycidyl group-containing (meth) acrylic resin of the present invention is 10 to 50% by weight of a vinyl-polymerizable unsaturated organic acid glycidyl ester, 10 to 90% by weight of a (meth) acrylic acid ester not containing a glycidyl group, and these Copolymer of 0 to 40% by weight of at least one vinyl monomer selected from the group consisting of styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride and alkyl vinyl ether.

  Examples of vinyl-polymerizable unsaturated organic acid glycidyl esters include (meth) acrylic acid such as glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), β-methyl glycidyl methacrylate, and β-methyl glycidyl acrylate. And glycidyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid. These vinyl-polymerizable unsaturated organic acid glycidyl esters may be used alone or in combination of two or more. Among these, glycidyl group-containing (meth) acrylic acid esters such as glycidyl methacrylate are preferable.

  Examples of (meth) acrylic acid esters not containing a glycidyl group include alkyl acrylates (alkyl groups) such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and the like. Of methacrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms) such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, and the like. . Among these, methyl methacrylate and butyl acrylate are preferable. These (meth) acrylic acid esters can be used alone or in combination of two or more.

  Examples of other copolymerizable vinyl monomers include styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride, and alkyl vinyl ether. These vinyl monomers can be used alone or in combination of two or more. Among these, styrene is preferable.

  As the glycidyl group-containing (meth) acrylic resin, 10 to 50% by weight of a vinyl-polymerizable unsaturated organic acid glycidyl ester, and 50 to 90% by weight of at least one vinyl monomer copolymerizable therewith These copolymers are preferred. Among such copolymers, 10 to 50% by weight of a glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, 10 to 90% by weight of a (meth) acrylic acid ester not containing a glycidyl group, and other vinyl monomers A copolymer of 0 to 40% by weight is more preferable. It is preferable to prepare a coloring resin composition (colorant masterbatch) in which a pigment is dispersed in advance in such a copolymer because the pigment dispersibility can be improved.

  The content of the glycidyl group-containing monomer in the glycidyl group-containing (meth) acrylic resin, typically a glycidyl ester of an unsaturated organic acid capable of vinyl polymerization, is preferably 10 to 50% by weight. If the amount is too small, the compatibility with the PVDC resin may decrease, the thermal stability of the resin composition may decrease, or the color tone of the packaging film may easily change over time. When the content of the glycidyl group-containing monomer component is too large, poor dispersion in the resin composition or poor appearance such as fish eyes tends to occur in a molded product such as a film.

  Specific examples of the glycidyl group-containing (meth) acrylic resin include glycidyl methacrylate-methyl methacrylate-styrene-butyl acrylate copolymer, glycidyl methacrylate-methyl methacrylate copolymer, glycidyl methacrylate-methyl methacrylate. -Styrene copolymer, glycidyl methacrylate-ethyl acrylate copolymer, glycidyl methacrylate-butyl acrylate copolymer, and the like.

  The molecular weight of the glycidyl group-containing (meth) acrylic resin is not particularly limited, but the weight average molecular weight (Mw) is usually about 3,000 to 100,000, preferably about 5,000 to 50,000. If the weight average molecular weight (Mw) is too large, aggregates (fish eyes) are likely to be generated in the film, and if it is too small, blocking between the films is likely to occur, and suitability for packaging machinery is deteriorated.

  The epoxy value of the glycidyl group-containing (meth) acrylic resin is not particularly limited, and may be 0.3 or more. Particularly, when it is less than 0.3, pigment dispersibility, color tone, thermal stability , Workability, gas barrier properties, etc. are preferred because they are easily balanced. This epoxy value is preferably 0.25 or less, more preferably 0.2 or less. In many cases, good results can be obtained with an epoxy value of about 0.05 to 0.2. If the epoxy value of the glycidyl group-containing (meth) acrylic resin becomes too large, fish eyes and the like are likely to be generated, and the molded product tends to have poor appearance. On the other hand, if the epoxy value is too small, the effect of thermal stability is reduced.

  The glycidyl group-containing (meth) acrylic resin is usually 0.3 to 5 parts by weight, preferably 0.4 to 3 parts by weight, more preferably 100 parts by weight of the PVDC resin in combination with the epoxy compound. Is 0.5 to 2 parts by weight. When this blending ratio is too small, the thermal stability is lowered or the color tone improving effect is lowered. When this blending ratio is too large, the gas barrier property and cold resistance of the molded product are lowered, and it becomes difficult to obtain a clear coloring degree. In many cases, good results can be obtained at a blending ratio of about 0.7 to 1.5 parts by weight.

  The use ratio of the epoxy compound (B1) and the glycidyl group-containing (meth) acrylic resin (B2) is usually 90:10 to 40:60, preferably 80:20 to 50:50, based on weight. By using the epoxy compound (B1) and the glycidyl group-containing (meth) acrylic resin (B2) in combination at such a use ratio, the thermal stability of the PVDC resin is highly maintained and caused by the epoxy compound. Bleeding can be suppressed and properties such as pigment dispersibility, color tone, processability, and gas barrier properties can be improved.

  Further, the total blending ratio of the epoxy compound (B1) and the glycidyl group-containing (meth) acrylic resin (B2) is usually 0.5 to 8 parts by weight, preferably 100 parts by weight of the PVDC resin. 1 to 5 parts by weight, more preferably 1.5 to 4 parts by weight. If the total blending ratio of these heat stabilizers is too large, inconveniences such as bleeding and a decrease in transparency are likely to occur, and if it is too small, the heat stability is lowered or the combined effect of both is sufficiently obtained. It may not be possible.

3. Other additives used in the production of polyvinylidene chloride resin compositions PVDC resin compositions include antioxidants, plasticizers, lubricants, dispersion aids, fillers, UV absorbers, surfactants, and other Various additives such as a stabilizer, a pH adjuster, and a pigment can be contained.

  Antioxidants include 2,6-di-tert-butyl-4-methyl-phenol (BHT), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate (Irganox 245, manufactured by Ciba Geigy), 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and mixtures thereof (Irganox 1141 manufactured by Ciba Geigy) Phenolic antioxidants; thioether antioxidants such as thiodipropionic acid and distearyl thiodipropionate; phosphite antioxidants such as trisnonylphenyl phosphite and distearyl pentaerythritol diphosphite; It is done. The antioxidant is usually used in a ratio of 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of the PVDC resin.

  Examples of the plasticizer include dioctyl phthalate, tributyl acetyl citrate, dibutyl sebacate, dioctyl sebacate, acetylated monoglyceride, acetylated diglyceride, acetylated triglyceride, and acetylated glycerides including two or three of them, adipic acid and Typical examples thereof include polyester plasticizers such as 1,3-butanediol, adipic acid and 1,4-butanediol, and mixtures of two or more thereof.

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

  As the lubricant, those suitable for melt processing of the PVDC resin composition include waxes such as oxidized polyethylene wax, paraffin wax, polyethylene wax, montanate ester wax and calcium montanate; fatty acid esters such as glycerin monoester. It is done. Further, examples of a material suitable for melt processing of a PVDC resin composition and secondary processing of a film include mono- or bisamide of a fatty acid such as stearamide. These lubricants are usually used in an appropriate amount of 2 parts by weight or less with respect to 100 parts by weight of the PVDC resin.

  As dispersion aids when dispersing the pigment, the above epoxy compounds and plasticizers, and lubricants such as paraffin wax, polyethylene wax, montanate wax, calcium montanate, glycerin fatty acid ester, sorbitan fatty acid ester, Examples include surfactants such as polyoxy / ethylene / sorbitan fatty acid esters, glycerin and propylene glycols, and aliphatic or aromatic hydrocarbon oligomers and polymers. Among these, an aliphatic hydrocarbon oligomer having 2 to 8 carbon atoms is preferable. In particular, a liquid aliphatic hydrocarbon oligomer having a weight average molecular weight of 300 to 5,000 is preferably used.

  The dispersion aid may be used when preparing the PVDC resin composition, but can also be used when manufacturing the coloring resin composition. The dispersing aid improves the dispersibility of the pigment, prevents the pigment from scattering, and lowers the processing temperature to facilitate the production of the coloring resin composition. The dispersion aid is usually used at a ratio of 2 parts by weight or less with respect to 100 parts by weight of the PVDC resin. When an excessive amount of the dispersion aid is used, the grindability of the colorant is deteriorated, and the barrier property of the PVDC resin is easily inhibited.

  Examples of the filler include silicon dioxide and calcium carbonate. Silicon dioxide and calcium carbonate also act as a satin finish, film slipperiness imparting (packaging machine suitability) agent, and the like. Silicon dioxide also acts as an inorganic lubricant. Silicon dioxide is effective for preventing aggregation of EVA when blending EVA. The filler is generally used in an appropriate amount of 1 part by weight or less, preferably 0.5 parts by weight or less, based on 100 parts by weight of the PVDC resin.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, and an appropriate amount is used as necessary.

  Examples of the surfactant include nonionic surfactants such as sorbitan fatty acid ester, polyglycerin fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, and an appropriate amount is used as necessary. Glycerin fatty acid monoester, sorbitan monobehenylate, sorbitan fatty acid ester and the like also act as meat stripping agents for packaging films.

  As other stabilizers, inorganic bases such as magnesium hydroxide, magnesium oxide and calcium hydroxyphosphate; organic weak acid salts such as citric acid and alkali metal citrate; ethylenediaminetetraacetate; be able to.

  Examples of the pH adjuster include sodium pyrophosphate and disodium dihydrogen pyrophosphate. An appropriate amount of 0.5 parts by weight or less is used with respect to 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. Among these, red pigments such as pigment red are widely used in the field of packaging films for processed foods such as fish sausages and processed meat products. The pigments can be used alone or in combination of two or more. The pigment is usually used in an appropriate amount of 1 part by weight or less with respect to 100 parts by weight of the PVDC resin. However, in the case of a titanium oxide pigment, it may be mixed up to 10 parts by weight.

  Some of these additives have various functions such as a plasticizer, a dispersion aid, and a lubricant. These additives are usually added to a PVDC resin powder resin and blended. If desired, these additives may be mixed with the slurry after the polymerization of the PVDC resin, or may be mixed before the polymerization. It may be added to the monomer mixture.

4). Coloring resin composition of the present invention (colorant masterbatch)
In the present invention, since a pigment is contained in the PVDC resin composition, it is used in the form of a resin composition containing a pigment in a high concentration in advance, that is, a colorant master batch. The colorant masterbatch contains a glycidyl group-containing (meth) acrylic resin (B2), a (meth) acrylic acid ester (co) polymer (F) that does not contain a glycidyl group, and a pigment (C).

The colored resin composition, if necessary, et styrene - vinyl acetate copolymer (D) can be further contained.
In addition, a plasticizer, a dispersion aid, and the like can be added to the coloring resin composition in order to enhance the dispersibility of the pigment.

  The coloring resin composition is pulverized and used as a powder for addition to a mixture of a polyvinylidene chloride resin powder resin and various additives such as an epoxy compound (B1). For the pulverization, an impact fine powder machine such as a jet mill pulverizer is used.

  As the glycidyl group-containing (meth) acrylic resin (B2) of the present invention, 10 to 50% by weight of glycidyl ester of unsaturated organic acid capable of vinyl polymerization, 10 to 90% by weight of (meth) acrylic acid ester not containing glycidyl group And a copolymer of 0 to 40% by weight of at least one vinyl monomer selected from the group consisting of styrene, acrylonitrile, acrylic acid, vinyl chloride, vinylidene chloride, and alkyl vinyl ether .

The coloring resin composition of the present invention contains a glycidyl group-containing (meth) acrylic resin in a proportion of preferably 20 to 90% by weight, more preferably 30 to 60% by weight. In the present invention, it is 30 to 60% by weight. If the blending ratio of the glycidyl group-containing (meth) acrylic resin is too large, fine powder is likely to be generated when the coloring resin composition is pulverized, and if it is too small, the pulverizability tends to decrease.

The pigment (C) is contained in an amount of usually 10 to 80% by weight, preferably 15 to 60% by weight, more preferably 20 to 40% by weight. In this invention, it is 15 to 60 weight%. When the blending ratio of the pigment is too large, the uniform dispersibility is lowered, and when it is too small, the effect of the colorant master batch is reduced. Since it is possible to obtain a PVDC-based resin composition having a desired degree of coloring with a small amount of the resin composition for coloring, increasing the content ratio of the pigment as much as possible within a range where the uniform dispersibility of the pigment can be maintained. This is particularly desirable from a cost standpoint.

  The coloring resin composition of the present invention may contain a dispersion aid. When a dispersion aid is contained, the content is usually 0.05 to 10% by weight, preferably 0.5 to 5% by weight, more preferably about 1 to 3% by weight. If the blending ratio of the dispersion aid is too large, the softening temperature of the coloring resin composition is lowered and the blocking becomes easy, and if it is too small, the effect of improving the dispersibility of the pigment is lowered.

  The coloring resin composition of the present invention can contain a plasticizer. In this case, an epoxidized vegetable oil such as epoxidized soybean oil can also be used as a plasticizer. However, since the blending ratio of the coloring resin composition in the PVDC resin composition is usually small, even if epoxidized vegetable oil is used as a plasticizer, the ratio of the epoxidized vegetable oil to the entire epoxy compound (B1) is It becomes quite small.

  Epoxidized vegetable oil and other plasticizers are usually contained at a ratio 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 resin composition for coloring. Let When 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, and when it is too small, the degree of plasticization becomes insufficient, and the powder resin of the PVDC resin Uniform blending becomes difficult during blending.

The colored resin composition of the present invention, because of its extrudability of stabilization does not contain a glycidyl group-containing (meth) Ru is contained in acrylic acid ester (co) polymer (F). Examples of (meth) acrylic acid esters include methyl methacrylate and butyl methacrylate. 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 coloring resin composition. It is. If the blending ratio is too large, the high frequency sealing property is lowered, and if it is too small, the extrusion processability may become unstable.

  The coloring resin composition of the present invention may contain an ethylene-vinyl acetate copolymer (EVA) (D). As described 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 desirable that EVA is contained in the coloring resin composition in a proportion of preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 20% by weight or less. When EVA is contained, it is usually contained in a proportion of 1% by weight or more, preferably 5% by weight or more.

If the content of EVA is too large, the melt viscosity of the colored resin composition will be reduced, the dispersibility of the pigment will be reduced, it will become rubbery at room temperature, and it will be difficult to grind, and the heat resistance will be reduced. It becomes easy to cause stickiness and blocking. If the content of EVA is too small, the particle size of the resulting powder becomes too fine when the colored resin composition is pulverized.
In the coloring resin composition of the present invention, various additives such as organic or inorganic lubricants and antioxidants can be contained in an appropriate amount range as necessary.

The coloring resin composition of the present invention is prepared by mixing each component and heating and kneading the mixture. The coloring resin composition is usually pulverized and used as a powder. Preferably, the kneaded product is melt-extruded into a sheet shape, rapidly cooled to obtain a sheet, and then the sheet is pulverized to form a powder. The particle size of this powder is preferably one that passes a # 20 mesh sieve, from the viewpoint of dispersibility with a powder resin of a PVDC resin, etc., and that it passes a # 40 mesh sieve. Is more preferable.
Since the coloring resin composition of the present invention is excellent in its own thermal stability, it can also be added to a normal thermoplastic resin.

5. Method for Producing PVDC Resin Composition Using Coloring Resin Composition of the Present Invention Generally, when preparing a resin composition containing a PVDC resin and various additives, various additives are added together with a PVDC resin powder resin. Blend to produce a powdery resin composition (compound). By the blending, liquid additives such as epoxidized vegetable oil and plasticizer are absorbed by the powder resin of the PVDC resin, and the powder additive adheres around the powder resin of the PVDC resin.

  In this blending, aggregation of the additive component is likely to occur, and aggregation of pigment particles and glycidyl group-containing (meth) acrylic resin powder is particularly likely to occur. If a large amount of agglomerates are present in the PVDC resin composition, the processability, extrudability, film formability, stretchability, etc. are impaired, and further, poor appearance due to the formation of fish eyes in a molded article such as a film. Bring. In order to increase the dispersibility of the pigment and suppress the formation of aggregates of the pigment and additive components, it is preferable to devise a method for adding each component.

The method for producing a polyvinylidene chloride-based resin composition using the coloring resin composition of the present invention is at least one selected from the group consisting of epoxidized vegetable oil, epoxidized animal oil, epoxidized fatty acid ester, and epoxy resin prepolymer during polymerization. Polyvinylidene chloride resin (A) powder resin containing various epoxy compounds (B1), glycidyl group-containing (meth) acrylic resin (B2), and glycidyl group-free (meth) acrylic acid ester This is a method of blending a powder of a coloring resin composition containing a (co) polymer (F) and a pigment (C), and if necessary, an additional epoxy compound (B1).

  It is preferable that the powder resin of the polyvinylidene chloride resin (A) further contains a plasticizer in addition to the epoxy compound (B1) at the time of polymerization. In order to include the epoxy compound (B1) and / or the plasticizer in the powder resin of the PVDC resin at the time of polymerization, they are added to the monomer mixture before polymerization or added to the polymerization reaction system during polymerization. In addition to the slurry after polymerization, the resultant PVDC resin is contained and then recovered as a powder resin.

  When the content of the epoxy compound (B1) and / or the plasticizer (E) in the powder resin is low, an additional epoxy compound (B1) and / or a plasticizer (E) is added as necessary in the blending process. Can be blended. At the time of blending, an ethylene-vinyl acetate copolymer (D) and other additives can be blended as desired. As the powder of the coloring resin composition, those described above are used.

  According to the method for producing a polyvinylidene chloride resin composition using the coloring resin composition of the present invention, each component can be blended at room temperature. PVDC-based resin powder resin contains major liquid components such as epoxy compound (B1) and plasticizer in advance during polymerization, so it can be blended with coloring resin composition powder at room temperature. Thereby, a compound of uniform composition can be prepared.

  The PVDC resin composition (compound) thus obtained may contain a small amount of coarse particles, but it is preferable to remove the coarse particles using a sieving machine.

  In the case of separately blending EVA, it is preferable to blend the resin composition obtained by the above-described methods and the EVA powder. EVA is preferably blended at room temperature. Also in this case, after blending, it is preferable to sieve using a sieve to remove coarse particles.

  Each component can be mixed using blenders, such as a blade blender, a ribbon blender, and a Henschel mixer. Moreover, when manufacturing the resin composition for coloring, it can also knead | mix using a 2 roll machine and a 3 roll machine.

According to the method for producing a polyvinylidene chloride resin composition using the coloring resin composition of the present invention, it is possible to suppress the generation of aggregates of pigment particles, aggregates of glycidyl group-containing (meth) acrylic resins, A PVDC resin composition having excellent processability and various physical properties can be obtained.
In the present invention, “normal temperature” usually means a temperature of 5 to 45 ° C., preferably 10 to 40 ° C., more preferably 15 to 35 ° C.

6). Molding of a PVDC resin composition using the coloring resin composition of the present invention A PVDC resin composition (compound) using the coloring resin composition of the present invention is melt extruded and molded into a stretched or unstretched film, sheet or the like. can do. As a film forming method, for example, an inflation extrusion molding method using a circular die is applied. An oriented film obtained by stretching, preferably biaxial stretching, has heat shrinkability and is suitably used as a heat-resistant film that can be retorted. The draw ratio is preferably 2 to 5 times in the longitudinal direction and 2 to 5 times in the transverse direction.

  The film thickness is usually 5 to 50 μm, preferably 10 to 30 μm, as a single film. It is also used as a double film depending on the application. The stretch film has a heat shrinkage ratio of preferably about 30 to 60% in both length and width (120 ° C. glycerin bath, 3 minutes). The main use as a food packaging film is that after inflation, the two pieces are stacked as a double film, the ears at both ends of the film are slit, sealed in a cylindrical shape with a packaging machine, and the contents are filled Then, both ends are gripped to obtain a package. The packaging film is suitable as a packaging material for processed foods such as fish sausages and processed meat products.

The film formed from the PVDC-based resin composition using the coloring resin composition of the present invention is randomly selected at 10 locations within a 100 g range (about 1.5 m ² ) and dispersed with a magnifying glass. When the state is observed, the pigment dispersibility is remarkably excellent when the number of aggregates of 0.4 mm or more is 10 or less. This means that the PVDC resin composition using the coloring resin composition of the present invention is suppressed in the generation of aggregates and is excellent in thermal stability.

  A film molded from a PVDC resin composition using the coloring resin composition of the present invention is a conventional product obtained by using a general-purpose epoxy compound such as epoxidized soybean oil or epoxidized linseed oil alone as a heat stabilizer. Compared to, the color tone is clearly improved, showing a slightly white luxury from the dark feeling of the conventional product. Therefore, processed foods such as fish sausages and livestock meat products packaged with the film have a high-class feeling and can contribute to the improvement of commercial value.

  The film formed from the PVDC resin composition using the coloring resin composition of the present invention is excellent in adhesion to meat and the like. For example, when surface treatment such as corona discharge treatment is applied, the meat is filled. In the case of moderation, the effect of improving the adhesion to the film is further increased, and the occurrence of drip such as gravy from meat can be reduced.

  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 tends to decrease. However, the PVDC resin composition using the coloring resin composition of the present invention is excellent in thermal stability due to the action of the dispersed epoxy compound and glycidyl group-containing (meth) acrylic resin during molding. Later, since the compatibility between the glycidyl group-containing (meth) acrylic resin and the epoxy compound is good, the finely dispersed glycidyl group-containing (meth) acrylic resin absorbs the liquid epoxy compound, and as a result The gas barrier property and the adhesion to meat are improved while maintaining the thermal stability. Therefore, a film formed from the PVDC resin composition using the coloring resin composition of the present invention is excellent in gas barrier properties.

  When EVA is blended, it contributes to improvement of gas barrier property by absorbing epoxy compound together with glycidyl group-containing (meth) acrylic resin after molding, in addition to contributing to extrudability and seal strength improvement. . Epoxy compounds contribute to thermal stability during melt processing such as extrusion molding, so even if they are absorbed by glycidyl group-containing (meth) acrylic resins or EVA after molding, the thermal stability of molded products such as films Will not be adversely affected.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, reference examples, and comparative examples. However, the present invention is not limited to these examples. The evaluation method used in the present invention is as follows.

(1) Reduced viscosity:
After extracting the PVDC resin with a Soxhlet extractor using methanol as a solvent, the dried product is used as a sample, and using a Ubbelohde viscometer, the solvent is cyclohexane, the resin concentration is 4 g / liter, and the measurement temperature is 30 ° C. The reduced viscosity was determined under the conditions.

(2) Evaluation of extrusion stability (thermal stability, processability):
The PVDC resin composition (compound) was melt-extruded using an extruder (motor 15 KW) having a screw diameter of 90 mm. The fluctuation range of the motor load of the extruder was recorded. Also, the extrusion situation was observed. Evaluation was made according to the following criteria.
○: ± 3 A or less (stable workability)
Δ: ± 5 A or less (processability is poor, but can be produced), or a lot of resin adhesion (decomposition) occurs at the die exit where the molten resin is extruded from the extruder.
X: exceeds ± 5 A (manufacturing is difficult).

(3) Compound yield:
When the PVDC resin composition and the coloring resin composition were blended and used, sieving was performed using a # 10 mesh sieve, and otherwise a # 50 mesh sieve. After sieving, the material that did not pass through the sieve was weighed and evaluated according to the following criteria.
○: The amount remaining on the mesh is less than 0.2% by weight of the input amount,
X: The amount remaining on the mesh is 0.2% by weight or more of the input amount.

(4) Color tone:
Ten healthy adults observed the retort-sterilized package, and judged whether the color tone and texture were improved as compared with the conventional product. The evaluation criteria are as follows. Judgment was made when the evaluations of 7 or more people matched.
○: Color tone and texture are better than conventional products and have a high-class feeling.
Δ: Whitish and slightly opaque,
X: A dark blue, slightly darkened.

(5) Number of coarse particles in the film:
The dispersion state in the film is observed with a magnifying glass, and an arbitrary 100 g range (about 1.5 m @ 2) is randomly observed at 10 locations. The number of aggregates of 0.4 mm or more is investigated and used as an evaluation scale. Evaluated by criteria.
○: 10 or less,
X: Exceeding 10 pieces.

(6) Evaluation of high frequency sealing properties [suitability for packaging machine, film slipperiness]:
A 1 m width of the original fabric was cut into a width of 70 mm, and an original fabric was wound up again. Using an automatic filling and ligating apparatus (Kureha type KAP500 type, manufactured by Kureha Chemical Industry Co., Ltd.) in which the film supply unit, high frequency sealing unit, automatic filling unit, and ligating unit are integrated, a current value of 70 mA, an electrode surface pressure of 400 g, and a filling speed The raw material meat for pork sausage was filled at 100 pieces / minute and the product length (between all the clips) of the package was set to 200 mm. High frequency sealability was evaluated according to the following criteria.
○: Film slipperiness at the time of bag making is good, there is no meandering, the film of the forming plate does not come off, there is no unevenness in folding width, stable high frequency sealing is possible, and the product length of the package is the set value Finished within ± 2.5mm of
×: Film slipperiness at the time of bag making is poor, there is meandering, the film of the forming plate is dislodged, the folding width is uneven, stable high frequency sealing is not possible, and the product length of the package is set Finished with a value of ± 2.5 mm or more.

(7) Destruction rate of the package (from the seal part during retort sterilization):
100 packages obtained above are sterilized by heating and pressure sterilization at a gauge pressure of 2.0 kg / cm ² and a temperature of 120 ° C for 20 minutes, and the pressure is cooled to 25 ° C while maintaining the pressure. Then, it was opened and taken out from the heating can. The number of broken pieces from the seal part of the package was investigated, and the broken percentage (%) was obtained.

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

(Footnote) In Example 1, since this coloring resin composition is blended at a ratio of 2.0 parts by weight with respect to 100 parts by weight of the PVDC-based resin, each component in the 2.0 parts by weight is blended. The breakdown is shown for reference.

  The obtained coloring resin composition was heat-kneaded for 10 minutes with a biaxial heating roller (φ = 200 mm) set at a surface of 150 ° C. After kneading, the kneaded product was quenched to obtain a sheet. The sheet was pulverized using a jet mill pulverizer (impact fine pulverizer), and the pulverized product was passed through a # 40 mesh screen to obtain a 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 (% by weight), reduced viscosity = 0.063] and PVDC (2) Each powder resin of [VD / VC = 83/17 (wt%), reduced viscosity = 0.052] was used. 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 are in these ratios with respect to 100 parts by weight of the PVDC resin. Contained.

  The powder of resin composition for coloring prepared above and various additives were added to the above-mentioned two types of PVDC resin powder resins to prepare PVDC resin compositions having the compositions shown in Table 2. . About each component, what was contained at the time of powder resin manufacture (at the time of superposition | polymerization) and what was contained at the time of blending were distinguished and shown. Moreover, about the epoxy compound and the plasticizer, the total amount was displayed including what was contained in the resin composition for coloring.

  First, a PVDC resin powder resin, a coloring resin composition, EVA, and various additives were mixed using a blade blender to prepare a PVDC resin composition (compound). The mixing time was 15 minutes. The mixing temperature was normal temperature (23 ° C.) (normal temperature blending). The PVDC resin composition was sieved with a # 10 mesh sieve to remove coarse particles.

3. Production of Film After using a 90 mm diameter extruder equipped with a vacuum hopper (vacuum pressure = adjusted to about −680 mmHg mercury column), the PVDC-based resin composition was melt-extruded in a ring shape, and then rapidly cooled in a cooling bath at 7 ° C., It is passed through a hot water bath at 20 ° C., and air is injected between two pairs of pinch rollers having different rotating surface speeds to expand them, so that the length is about 2.5 times and the width is about 4.2 times. Stretched and oriented to produce a stretched film. 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 are in these ratios with respect to 100 parts by weight of the PVDC resin. Contained. The same operation as in Example 1 was performed except that these powder resins were used, and the coloring resin composition and the glycidyl group-containing (meth) acrylic resin were not used. The results are shown in Table 2.

[Reference Example 1]
At the time of polymerizing 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 are added to 100 parts by weight of PVDC resin. It contained so that it might become a ratio. Among the components shown in Table 2, components other than the glycidyl group-containing (meth) acrylic resin are mixed with PVDC (1) powder resin, powder additive, liquid additive (acetylbutyl citrate, epoxidized linseed oil) ) And pigment in this order in a blade blender, and the temperature was raised to about 80 ° C. while mixing (temperature rise blending). After the temperature rise, the mixture was immediately cooled, and when the temperature dropped to about 65 ° C., the glycidyl group-containing (meth) acrylic resin powder was added and mixed (blend after temperature rise). After cooling, the mixture was sieved with a # 50 mesh sieve to obtain a resin composition (compound). A stretched film was prepared 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 polymerizing the powder resin of PVDC (1), 4.0 parts by weight of dibutyl sebacate was contained at this ratio with respect to 100 parts by weight of the PVDC resin. The same operation as in Reference Example 1 was carried out except that this powder resin was used and the glycidyl group-containing (meth) acrylic resin was added together with other powder additives at the time of blending. The results are shown in Table 2.

[Reference Example 2]
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 are in these ratios with respect to 100 parts by weight of the PVDC resin. Contained. Using these powder resins, and among the components shown in Table 2, the components other than the glycidyl group-containing (meth) acrylic resin and EVA are mixed in the order of the powder resin, the powder additive, and the pigment. The mixture was put into the inside and heated to about 80 ° C. while mixing (temperature rising blending). After the temperature rise, the mixture was immediately cooled, and when the temperature dropped to about 65 ° C., the glycidyl group-containing (meth) acrylic resin powder was added and mixed (blend after temperature rise). Thereafter, EVA was blended at room temperature (normal temperature blending). A stretched film was prepared in the same manner as in Example 1 using the obtained resin composition. The results are shown in Table 2.

(footnote)
* 1: The numerical value in () represents the number of parts by weight of each component contained in 2.0 parts by weight of the coloring resin composition.

  In Example 1, the epoxy compound and the plasticizer were added at the time of polymerization, but not at the time of blending. If there is no liquid additive at the time of blending, it is not necessary to carry out temperature rising blending so that the liquid additive is absorbed by the powder resin of the PVDC resin, and it is possible to perform normal temperature blending and to shorten the blending time. Moreover, the powder of the coloring resin composition can be blended at room temperature, and the generation of aggregates is suppressed. On the other hand, in Comparative Example 1, since the blending at room temperature is performed without using the coloring resin composition, the number of coarse particles in the film, the high frequency sealing property, and the bag breaking rate of the package are poor.

  In Reference Example 1, an epoxy compound and a glycidyl group-containing (meth) acrylic resin powder are used in combination, and the glycidyl group-containing (meth) acrylic resin powder is blended in the cooling process to obtain an agglomerate. The color tone is also good. On the other hand, in Comparative Example 2, the compound yield, the number of coarse particles in the film, the high frequency sealing property, the bag breaking rate of the package is poor, depending on the timing of introduction of the glycidyl group-containing (meth) acrylic resin, Since the glycidyl group-containing (meth) acrylic resin is used alone, the film color tone is unsatisfactory and the extrusion stability is not good.

  In Reference Example 2, not the normal temperature blend but the same temperature rising blend as in Reference Example 1 is adopted, but it is understood that a resin composition and a film having desired characteristics are obtained.

[Reference Example 3]
At the time of polymerization of each powder resin of PVDC (1) and PVDC (2), 0.4 parts by weight of epoxidized linseed oil (O-180) and dibutyl sebacate (DBS) 3 with respect to 100 parts by weight of PVDC resin .5 parts by weight was contained so as to have these ratios. Among the components shown in Table 3, components other than glycidyl group-containing (meth) acrylic resin (GMA) and ethylene-vinyl acetate copolymer (EVA) are used as powder resins of PVDC (1) and PVDC (2). The powder additive, the liquid additive (epoxidized linseed oil), and the pigment were charged in this order into the blade blender, and the temperature was raised to about 80 ° C. while mixing (temperature increase blending). After the temperature rise, the mixture was immediately cooled, and when the temperature dropped to about 65 ° C., the glycidyl group-containing (meth) acrylic resin powder was added and mixed (blend after temperature rise). Thereafter, EVA was blended at room temperature. After cooling, the mixture was sieved with a # 50 mesh sieve to obtain a resin composition (compound). A stretched film was prepared 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 Reference Example 3, the blending amount of the epoxidized linseed oil at the time of temperature rising blending was changed from 2.2 parts by weight to 3.0 parts by weight, and after temperature rising, a glycidyl group-containing (meth) acrylic resin (GMA) A stretched film was prepared in the same manner as in Reference Example 3 except that was not blended. The results are shown in Table 3.

[Comparative Example 4]
In Reference Example 3, a stretched film was prepared in the same manner as in Reference Example 3 except that epoxidized linseed oil was not used during polymerization and temperature-blending. The results are shown in Table 3.

[Reference Example 4]
In Reference Example 3, a stretched film was prepared in the same manner as Reference Example 3 except that EVA was not blended. The results are shown in Table 3.

[Example 2]
At the time of polymerization of each powder resin of PVDC (1) and PVDC (2), 0.4 parts by weight of epoxidized linseed oil (O-180) and dibutyl sebacate (DBS) 3 with respect to 100 parts by weight of PVDC resin .5 parts by weight was contained so as to have these ratios. A powder resin of PVDC (1) and PVDC (2) and 2.2 parts by weight of epoxidized linseed oil were charged into a blade blender, and the temperature was raised to about 80 ° C. while mixing (temperature increase blending). Immediately after the temperature rise, it is cooled, and at the time of normal temperature (23 ° C.), 0.1 parts by weight of a film slip agent (silicon dioxide), 2.0 parts by weight of a coloring resin composition, and 2.5 parts by weight of EVA are mixed. (Normal temperature blending). Thereafter, the mixture was sieved with a # 50 mesh sieve to obtain a resin composition (compound). A stretched film was prepared 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 3]
In Example 2, a powder resin, 2.2 parts by weight of epoxidized linseed oil, 0.1 parts by weight of a film slip agent (silicon dioxide), 2.0 parts by weight of a resin composition for coloring, and 2.5 parts by weight of EVA A stretched film was prepared and evaluated in the same manner as in Example 2 except that it was mixed at room temperature (normal temperature blending). The results are shown in Table 3.

[Comparative Example 5]
In Example 3, 2.2 parts by weight of epoxidized linseed oil was added to 3.0 parts by weight, 0.1 part by weight of a film slip agent (silicon dioxide) was added to 0.2 part by weight, and a coloring resin composition 2.0 A stretched film was prepared and evaluated in the same manner as in Example 3 except that the weight part was changed to 0.5 part by weight of the pigment. The results are shown in Table 3.

(footnote)
* 1: The numerical value in () represents the number of parts by weight of each component contained in 2.0 parts by weight of the coloring resin composition.

  The polyvinylidene chloride-based resin composition using the coloring resin composition of the present invention has a high-grade color tone with suppressed generation of coarse foreign matters, pigment agglomerates, color spots, and the like. The film for packaging excellent in property, strength, and adhesion to foods can be provided. Thus, since the film obtained using this polyvinylidene chloride resin composition is excellent in color tone and texture and has a high-class feeling, it is suitable as a packaging material for processed foods such as fish sausages and processed meat products. .

Claims (2)

(1) 10 to 50% by weight of glycidyl ester of unsaturated organic acid capable of vinyl polymerization, 10 to 90% by weight of (meth) acrylic acid ester not containing glycidyl group, and styrene, acrylonitrile, acrylic copolymerizable therewith A glycidyl group-containing (meth) acrylic resin which is a copolymer of 0 to 40% by weight of at least one vinyl monomer selected from the group consisting of acid, vinyl chloride, vinylidene chloride and alkyl vinyl ether , Sometimes glycidyl group-containing (meth) acrylic that is not copolymerized in the presence of a tackifying resin selected from rosin acid esters, terpene resins, coumarone resins, styrene resins, xylene resins, petroleum resins, or tammers Glycidyl group-containing (meth) acrylic resin (B2) 30-60% by weight of resin ,
(2) 10 to 40% by weight of (meth) acrylic acid ester (co) polymer (F) containing no glycidyl group, and
(3) Pigment (C) 15-60% by weight
Containing, 60-98 wt% of vinylidene chloride and another copolymerizable monomer 2-40% by weight of the copolymer and is polyvinylidene chloride-based resin composition wearing color resin composition. Ethylene - vinyl acetate copolymer (D) further claim 1 Symbol placement of polyvinylidene chloride-based resin composition wearing color resin composition containing.