CN1240763C - Polyvinylidene chloride composition and its prepn - Google Patents

Abstract

This polyvinylene chloride resin composition is obtained by including an epoxy compound and a glycidyl group-containing (meth)acrylic resin as a heat stabilizer in a polyvinylidene chloride resin. The polyvinylidene chloride resin composition has excellent processability, heat stability, color tone, dispersibility of the pigment, gas barrier properties. The method for producing the resin composition is provided. The film comprises the resin composition. The resin composition for coloring comprises the glycidyl group-containing (meth)acrylic resin and the pigment.

Description

Polyvinylidene chloride based resin composition and manufacture method thereof

Technical field

The present invention relates to the polyvinylidene chloride based resin composition, more particularly, relate to good polyvinylidene chloride based resin compositions such as processibility, thermostability, tone, dispersing of pigments, barrier properties for gases.Polyvinylidene chloride based resin composition of the present invention can suppress the generation of thick foreign matter, pigment cohesion piece, color spot etc., have tone that feeling of high class is arranged, and can give stopping property, intensity, with the good packaging film of adaptation of food.

The invention still further relates to the novel manufacturing method of polyvinylidene chloride based resin composition, reach the film that the moulding of polyvinylidene chloride based resin composition is made.The invention still further relates to suitable polyvinylidene chloride is the painted resin combination of using of coloring resin.

Background technology

Polyvinylidene chloride is resin (being designated hereinafter simply as " PVDC is a resin "), generally is the multipolymer of vinylidene chloride monomer (being designated hereinafter simply as " VDC ") and other monomers (comonomer).The homopolymer of VDC, softening temperature and decomposition temperature are approaching, the melt-processed of very difficult employing extrusion moulding etc.In addition, the homopolymer of VDC and the intermiscibility of softening agent are little, are difficult to adopt plasticising to improve processibility.

Therefore, PVDC is a resin, is to carry out internal plasticization, give the multipolymer of processibility by VDC and other monomeric copolymerization.Most situation is to add softening agent in the resin to improve melt processable at PVDC also.As comonomer, vinylchlorid, acrylate etc. is representational monomer.

Generally, the PVDC that is shaped to the extrusion grade of film, sheet material, fiber etc. with the suspension polymerization manufacturing is a resin.The PVDC of extrusion grade is a resin, and is general as the powdered resin modulation with the median size about 40～600 μ m.PVDC is the powdered resin poor heat stability of resin, decomposes easily when carrying out melt-processed to produce hydrogen chloride gas.In addition, PVDC is the powdered resin of resin, is multipolymer even PVDC is a resin, and processing temperature and decomposition temperature are also quite approaching.Therefore, be that the melt-processed that the powdered resin of resin carries out extrusion moulding etc. is difficult only with PVDC.

Therefore, in order to satisfy the characteristic that requires of processibility and forming composition, generally adopting at PVDC is in the powdered resin of resin, the method that the various additives of interpolation thermostability, softening agent, lubricant etc. mix, modulate so-called composition (resin combination), said composition carried out extrusion moulding.With PVDC is that the film (also comprising sheet material) that makes of the composition extrusion moulding of resin is because excellences such as barrier, thermotolerance, heat-shrinkables, as single thin film or multilayer film, the uses such as wrapping material of processing food as fish sausage, poultry meat processed goods etc.

As PVDC is the thermo-stabilizer of resin, generally uses epoxy compounds.Yet, with PVDC the composition that is added with epoxy compounds in the powdered resin of resin when carrying out extrusion moulding, on the surface of forming composition, have along with the time changes and separates out the problem of epoxy compounds.Many more this problems of the addition of epoxy compounds Zhao significantly exists easily.In addition, in order to improve thermostability, when increasing the addition of epoxy compounds, the barrier properties for gases of PVDC based resin film reduces.

Packaging film, when epoxy compounds was separated out on the surface, film sliding (wrapping mechanism suitability), stopping property (heat sealability, high frequency stopping property etc.), printing suitability etc. often descended in storage.In addition, when the barrier properties for gases of packaging film reduces, reduce as the keeping quality of the food of packed article.In addition, when the packaging film that will contain epoxy compounds was used for the packing of fish sausage etc., it was painted promptly to use red pigment to carry out, and the also deepening easily of the tone of film brings bad influence often for the commodity value of packaged product.

As PVDC is the thermo-stabilizer of resin, has proposed to use (methyl) acrylic resin that contains glycidyl to replace the scheme of the epoxy compounds of epoxidized vegetable oil etc.For example, the spy open flat 5-148398 communique disclose as thermo-stabilizer contain the glycidyl methacrylate copolymer of oxirane value at least 0.3 vinylidene chloride copolymer composition, and adopt the sheet for packaging or the film of said composition.

Special public clear 46-42941 communique has proposed to make the edible meat boiling goods packaging box of the resin combination formation that contains unsaturated organic acid glycidyl ester (being total to) polymkeric substance in vinylidene chloride-vinyl chloride copolymer.The spy opens clear 59-89342 communique, has proposed in halogen-containing resin to add the resin combination that the weathering resistance of (methyl) acrylate (being total to) polymkeric substance that contains glycidyl is improved.

(methyl) acrylic resin that contains glycidyl has the function of catching hydrochloric acid, is that resin shows thermostabilization to VDC, and compares with general epoxy compounds to have the little advantage of the tendency separated out.

, using PVDC is when having mixed resin combination as (methyl) acrylic resin that contains glycidyl of thermostabilization requirement in the resin and carrying out form film, and the film of gained demonstrates the tendency that the transparency has decline slightly.In addition, add in the resin when containing (methyl) acrylic resin of glycidyl in order to give and having mixed the PVDC that contains carboxy resin for the adaptation of meat-based food etc., (methyl) acrylic resin that then contains glycidyl causes that PVDC is the crosslinking reaction of resin, and the gloss of film or the transparency are reduced.In addition, when increase contained the cooperation ratio of glycidyl (methyl) acrylic resin, the forming composition hardening of film etc. became the reason that resistance to cold reduces.And, if do not control mixing condition, also contain the condensation product of (methyl) acrylic resin self of glycidyl easily.

In addition, be in the resin of powder of resin at PVDC, mix when containing (methyl) acrylic resin of glycidyl, if do not control mixing condition, then be easy to generate the condensation product of (methyl) acrylic resin self that contains glycidyl.In addition, contain (methyl) acrylic resin of glycidyl, with PVDC be softening easily under the mixing condition of resin powdered resin.Therefore, make cohesions such as powdered resin or pigment particles easily.The particle of cohesion, for example, thereby the principal element that will become the film follicular rupture when inflatable method film forming reduces productive rate.And, contain the film of aggregated particle, cause the bad order due to the generation etc. of flake easily, stopping property is variation easily also.

On the other hand, to be that forming composition that resin is formed carries out using when painted pigment by PVDC, but pigment directly is added on when mixing in the powdered resin that PVDC is a resin, after the pigment particles cohesion, on the final molding thing of film etc., produces color spot, striped, pin hole etc. easily.Known have to make make the colour batch of colo(u)rant dispersion in the liquid component of epoxidized vegetable oil or softening agent etc., be that the powdered resin of resin carries out the blended method with itself and PVDC.But this masterbatch uses difficulty, also is difficult to improve pigment concentration, pollutes the problem of mixing machine inside in addition.

In the blended finishing operation, when the aggregated particle of volume is removed in screening,, produce the thermostability reduction of composition owing to contain (methyl) acrylic resin of glycidyl and a large amount of pigment is removed, maybe can not obtain improper parts such as desirable degree of staining.

Owing to there is aforesaid problem, though having proposed to contain (methyl) acrylic resin of glycidyl is the scheme of the thermo-stabilizer of resin as PVDC, practical situation are industrial very difficult employing, or, also need further research at present for industrialization.

The content of invention

The object of the present invention is to provide excellent polyvinylidene chloride based resin composition such as processibility, thermostability, tone, dispersing of pigments, barrier properties for gases.

In addition, the present invention also aims to provide the manufacture method of the polyvinylidene chloride based resin composition of these all excellents, and the film that the moulding of polyvinylidene chloride based resin composition is made.

In addition, the present invention also aims to provide the painted resin combination of using that is fit to make painted PVDC based resin composition.

The present inventor is in order to reach found that aforementioned purpose concentrates on studies, as PVDC is the thermostability of resin, also use with (methyl) acrylic resin that contains glycidyl by at least a kind of epoxy compounds that will be selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester and the epoxy prepolymer, can highly be kept thermostability, also be improved the PVDC based resin composition of processibility, tone, dispersing of pigments, barrier properties for gases etc. simultaneously.

The film that PVDC based resin composition of the present invention moulding is made and is only compared with the situation of epoxy compounds, and tone is white slightly, when using as packaging film, can give the goods feeling of high class.With the film that PVDC based resin composition of the present invention moulding makes, suppressed the generation of thick foreign matter, pigment cohesion piece, color spot etc., and stopping property, intensity, with the excellences such as adaptation of food.

Epoxy compoundss such as epoxidized vegetable oil generally are liquid at normal temperatures.In contrast, contain (methyl) acrylic resin of glycidyl owing to be powder, thus be difficult to separate out, and usability is good.Yet with epoxy compounds and (methyl) acrylic resin and the time spent of containing glycidyl, the powder that contains (methyl) acrylic resin of glycidyl when mixing sometimes condenses and the generation condensation product.At this moment, be easy to generate condensation product into the painted pigment particles that cooperates.The mixing condition of the temperature condition when therefore, preferably control mixes and the order by merging of each composition etc.

For this reason, for being to contain as the epoxy compounds of thermostability in the resin and contain (methyl) acrylic resin of glycidyl and the method for pigment is studied at PVDC.Its result, expect when polymerization making the powdered resin of the PVDC based resin composition that contains epoxy compounds, the manufacture method of the painted powder with resin combination that in this powdered resin, mixes (methyl) acrylic resin that contains glycidyl and pigment then.

In addition, also expected as requested under the intensification condition, in containing the powdered resin of epoxy compounds, mix various compositions after, the manufacture method of in process of cooling, mixing (methyl) acrylic resin powder that contains glycidyl.

According to these manufacture method, Yi Bian can suppress the generation of condensation product effectively, Yi Bian modulate uniform mixture.

The present invention just is being based on these opinions and the invention finished.

Therefore, according to the invention provides a kind of polyvinylidene chloride based resin composition, said composition is to contain the polyvinylidene chloride based resin composition that polyvinylidene chloride is resin (A) and thermo-stabilizer (B), it is characterized in that this thermo-stabilizer (B) contains at least a kind of epoxy compounds (B1) that is selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester and the epoxy prepolymer and (methyl) acrylic resin (B2) that contains glycidyl.

In addition, a kind of painted resin combination of using also is provided according to the present invention, but it contains by ethene is glycidyl ester 10～50 weight % of polymeric unsaturated organic acid and (methyl) acrylic resin (B2) and the pigment that contain glycidyl that can constitute with the multipolymer of at least a kind vinyl monomer 50～90 weight % of its copolymerization.

According to the present invention, when being provided at polymerization contain be selected from oxidation vegetables oil, epoxidation animal oil, epoxidized fatty acid ester, and epoxy prepolymer in the polyvinylidene chloride of at least a kind of epoxy compounds (B1) be in the powdered resin of resin (A), mix (methyl) acrylic resin (B2) that contains glycidyl and pigment (C) painted powder with resin combination, reach the manufacture method of the polyvinylidene chloride based resin composition of the epoxy compounds of adding as required (B1).

In addition, make it to contain when also being provided at polyvinylidene chloride according to the present invention and being the powdered resin of resin (A) or polymerization be selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, and epoxy prepolymer in the polyvinylidene chloride of at least a kind of epoxy compounds (B1) be in the powdered resin of resin (A), mix powder, pigment, and the manufacture method of the polyvinylidene chloride based resin composition of epoxy compounds (B1) or the epoxy compounds (B1) added as required of (methyl) acrylic resin (B2) that contains glycidyl.

In addition, also provide the film that the moulding of aforementioned polyvinylidene chloride based resin composition is made according to the present invention.

The preferred plan that carries out an invention

1. Polyvinylidene chloride is resin (A)

The polyvinylidene chloride that the present invention uses is resin (PVDC is a resin), be vinylidene chloride (VDC) 60～98% (quality %) but with the multipolymer of other monomers (comonomer) 2～40 quality % of copolymerization.

As comonomer, for example, can enumerate vinylchlorid; The alkyl acrylate (carbonatoms of alkyl is 1～18) of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, lauryl acrylate, stearyl acrylate ester etc.; Alkyl methacrylates (carbonatoms of alkyl is 1～18) such as methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), methacrylic acid stearyl ester; Vinyl cyanide such as vinyl cyanide, methacrylonitrile; Vinyl-arenes such as vinylbenzene; Carbonatomss such as vinyl acetate are the vinyl ester of 1～18 aliphatic carboxylic acid; Carbonatoms is 1～18 alkyl vinyl ether; The ethene of vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid etc. is polymerizable unsaturated carboxylic acids; The alkyl ester (carbonatoms that comprises part ester, alkyl is 1～18) of vinyl polymerized unsaturated carboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid; In addition, diene monomer, contain functional group monomer, multi-functional monomer etc.

These comonomer can be distinguished separately and to use, and also can or be used in combination more than 2 kinds 2 kinds.More preferably vinylchlorid, methyl acrylate, and lauryl acrylate in these comonomers.When the copolymerization ratio of comonomer was too small, internal plasticization was insufficient, and melt processable reduces.When the copolymerization ratio of comonomer was excessive, barrier properties for gases reduced.Preferred 3～35 weight % of the copolymerization ratio of comonomer, more preferably 10～25 weight %.

PVDC is the reduced viscosity [η sp/c] of resin, and the viewpoint of the processibility when being shaped to film, wrapping mechanism suitability, winter hardiness etc. is preferred 0.035～0.070, more preferably 0.040～0.065, most preferably 0.045～0.063.PVDC is that the reduced viscosity of resin is crossed processibility reduction when hanging down, and occurs painted tendency when too high, so any situation is all bad.Can reduced viscosity is different 2 kinds or be resin and usefulness, thus, can improve processibility more than 2 kinds PVDC.When 2 kinds or be resin and time spent more than 2 kinds PVDC, the reduced viscosity of hybrid resin is preferably in above-mentioned scope.

PVDC is a resin, can mix with other resin as required.As other resin, for example, can enumerate ethylene-vinyl acetate copolymer, (methyl) acrylate, the carbonatoms of preferred alkyl is (being total to) polymkeric substance [for example, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer], MBS of (methyl) alkyl acrylate of 1～18 etc.These other resins mix when modulation PVDC based resin composition, can make it maybe to be contained in that to be blended in PVDC be painted with in the resin combination in the resin.Other resin is resin 100 weight parts with respect to PVDC, generally can use in 20 weight parts or less than the ratio of 20 weight parts.

In these other the resin, preferred vinyl acetate content better is 20-40 weight %, be more preferably 28～35 weight %, and melt flow rate (MFR) (MFR) better is 1～50g/10 minute, be more preferably 10～40g/10 minute ethylene-vinyl acetate copolymer (being designated hereinafter simply as " EVA ").By mixing EVA, can improve and extrude processibility, sealing intensity, barrier properties for gases etc.Especially EVA is suitable as the improving agent of diaphragm seal intensity.The vinyl acetate content of EVA is crossed when hanging down, and the transparency and tone worsen, and for example, make foodstuff package and present unsuitable grey, also might reduce stopping property.When the vinyl acetate content of EVA was too much, the tendency of the color harmony style reduction of forming composition such as film appearred.

The cooperation ratio of EVA is resin 100 weight parts with respect to PVDC, and preferred 0.5～5 weight part is more preferably about 1～3 weight part.When the cooperation ratio of EVA is too small, extrude processibility to improve effect little.In addition, with the PVDC based resin composition during, be difficult to accomplish and improve fully that winter hardiness can suppress again to boil or the decline of stopping property during cooking disinfection as packing material.On the other hand, when the cooperation ratio of EVA was excessive, sealing intensity reduced, or caused easily that for the stretch orientation film layer peels off state.

It is in the resin that EVA is blended in PVDC usually, but the painted composition with resin combination that its all or part of conduct that cooperates ratio contains pigment is used.EVA when making the powder of painted usefulness resin combination (colour batch), in pulverizing process, also is effective preventing fine-powdered and carrying out in the granularity adjustment.

When mixing other resin, consider from the viewpoint of barrier properties for gases or thermotolerance etc., regulate containing of vinylidene chloride composition in the hybrid resin composition proportional reach 50 weight % or greater than 50 weight % for preferred.In addition, PVDC is the resin combinations capable of circulation such as scrap stock that produced in the time of can also being blended in PVDC based resin composition forming process in the resin.

The PVDC that uses among the present invention is a resin, it can be any polymerization process synthetic with suspension polymerization, emulsion polymerization, solution polymerization process etc., but the preferred resin that makes by suspension polymerization, because the resin that obtains like this when forming composition, does not need pulverizing process just to have granularity about 40～600 μ m as powdered resin.In addition, also can make PVDC when its polymerization, contain antioxidant, softening agent, epoxy compounds etc. in the resin.

Generally, PVDC is that the powdered resin of resin is the resin with 40～600 μ m left and right sides median sizes.Can use the powdered resin that when polymerization, makes it to contain additives such as epoxy compounds and softening agent among the present invention.Certainly, even do not contain the powdered resin of additives such as epoxy compounds and softening agent, also can use in the present invention.

The PVDC that contains additives such as epoxy compounds and softening agent when polymerization is the powdered resin of resin, it is the arbitrary at least moment before polymerization or in the polymerization or after the polymerization, these additives are added in the polymerization reaction system, and the PVDC that is included in generation be in the resin after, reclaim as powdered resin.

2. Thermo-stabilizer (B)

Among the present invention, as thermo-stabilizer, will be selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, reach at least a kind epoxy compounds (B1) and (methyl) acrylic resin (B2) that contains glycidyl and usefulness in the epoxy prepolymer.

Epoxidized vegetable oil that uses among the present invention and epoxidation animal oil, so long as the past is all can of using of the thermo-stabilizer of resin as PVDC, there is not special restriction, but can use natural animal-plant oil to carry out epoxidation, two key sex change be become the compound of oxirane ring by will have unsaturated link(age) with hydrogen peroxide or peroxyacetic acid.As preferred epoxidized vegetable oil epoxidised soybean oil, epoxidised linseed oil etc. are arranged.

As epoxidized fatty acid ester, the epoxide of the unsaturated fatty acid ester of epoxidation octyl stearate etc. is arranged.As epoxy prepolymer dihydroxyphenyl propane glycidyl ether etc. is arranged.In these epoxy compoundss, at the preferred epoxidized vegetable oil in food product pack field.

Epoxy compounds, with (methyl) acrylic resin that contains glycidyl and with in, be resin 100 weight parts with respect to PVDC, usually by 0.1～5 weight part, preferred 0.5～4 weight part, the more preferably ratio use of 1～3 weight part.When the cooperation ratio of epoxy compounds is excessive, in storage, on the surface of the forming composition that forms by the PVDC based resin composition, separate out easily.In addition, when the cooperation ratio of epoxy compounds is excessive, the adhesion of forming composition taking place easily also, or reduce the effect of improving of tone, or reduces the barrier properties for gases of film.On the other hand, when the cooperation ratio of epoxy compounds was too small, PVDC can occur was the tendency that the plasticising degree descends, processibility reduces easily, thermostability also reduces of resin.

Epoxy compounds can be by being that the powdered resin of resin mixes with PVDC, or add in its polymerization process and carry out polymerization in the monomer mixture, or add in the slurries after the polymerization, or the method that makes up these modes is included in the resin combination.Among these, make during preferred polymeric and add epoxy compounds when containing epoxy compounds, blending in the powdered resin as required.

As (methyl) acrylic resin (B2) that contains glycidyl that uses among the present invention, be that the glycidyl ester of polymeric unsaturated organic acid is the multipolymer of copolymer composition but preferably contain with ethene.This multipolymer since (methyl) acrylate of (methyl) acrylate etc. that typically contains (methyl) glycidyl acrylate and do not contain glycidyl as copolymer composition, so be called (methyl) acrylic resin that contains glycidyl in the present invention.Preferably contain (methyl) of glycidyl but acrylic resin is an ethene be the glycidyl ester of polymeric unsaturated organic acid with (methyl) acrylate that does not contain glycidyl and/or can with the multipolymer of other vinyl monomers of their copolymerization.

But as ethene is the glycidyl ester of polymeric unsaturated organic acid, for example, can enumerate (methyl) acrylic acid glycidyl ester of glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), Beta-methyl glycidyl methacrylate, Beta-methyl glycidyl acrylate etc.; The ethene of toxilic acid, fumaric acid, methylene-succinic acid etc. is the glycidyl ester of polymerizable unsaturated carboxylic acids etc.But these ethene is the glycidyl ester of polymeric unsaturated organic acid, can distinguish separately and to use, or with 2 kinds or be used in combination more than 2 kinds.Among these, (methyl) acrylate that contains glycidyl of preferred glycidyl methacrylate etc.

As (methyl) acrylate that does not contain glycidyl, for example, can enumerate the alkyl acrylate (carbonatoms of alkyl is 1～18) of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, lauryl acrylate, stearyl acrylate ester etc.; The alkyl methacrylate of methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), methacrylic acid stearyl ester etc. (carbonatoms of alkyl is 1～18) etc.Wherein, preferable methyl methyl acrylate and butyl acrylate etc.These (methyl) acrylate can be distinguished separately and to use, perhaps with 2 kinds or be used in combination more than 2 kinds.

But, can enumerate vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride, alkyl vinyl ether etc. as other vinyl monomers of copolymerization.These vinyl monomer can be distinguished separately and to use, perhaps with 2 kinds or be used in combination more than 2 kinds.Among these, optimization styrene.

As (methyl) acrylic resin that contains glycidyl, but preferred ethene be the polymeric unsaturated organic acid glycidyl ester 10～15 weight % and can with the multipolymer of at least a kind vinyl monomer 50～90 weight % of its copolymerization.In such multipolymer, but more preferably ethene is glycidyl ester 10～50 weight % of polymeric unsaturated organic acid, (methyl) acrylate 10～90 weight % that do not contain glycidyl, and other the multipolymer of vinyl monomer 0～40 weight %.When making when pigment is dispersed in painted in such multipolymer in advance of resin combination (colour batch), so because can to improve pigment-dispersing be preferred.

Contain in (methyl) acrylic resin of glycidyl, contain the glycidyl monomer, typically but ethene is preferred 10～50 weight % of amount of the glycidyl ester of polymeric unsaturated organic acid, when this amount is very few, with PVDC be that the intermiscibility of resin reduces, or the thermostability of resin combination reduces, or the tone that is easy to generate packaging film changes in time and changes.Contain the amount of monomer component of glycidyl when too much, in resin combination, produce and disperse badly, or on the forming composition of film etc., be easy to generate the bad order of flake etc.

As the object lesson of (methyl) acrylic resin that contains glycidyl, can enumerate glycidyl methacrylate-methyl methacrylate-styrene-propene butyl acrylate copolymer, glycidyl methacrylate-methylmethacrylate copolymer, glycidyl methacrylate-copolymer of methyl methacrylatestyrene, glycidyl methacrylate-vinyl chloride copolymer, glycidyl methacrylate-ethyl acrylate copolymer, glycidyl methacrylate-butyl acrylate copolymer, glycidyl methacrylate-metachloroethylene copolymer etc.

The molecular weight that contains (methyl) acrylic resin of glycidyl does not have particular restriction, but weight-average molecular weight (Mw) is generally 3,000～100,000, and preferred about 5,000～50,000.When this weight-average molecular weight (Mw) is excessive, be easy to generate condensation product (flake) on the film, when too small, be easy to generate adhesion between the film, wrapping mechanism suitability variation.

Contain (methyl) of glycidyl though the oxirane value of acrylic resin does not have particular restriction can be 0.3 or greater than 0.3 yet, but particularly less than 0.3 o'clock, so balance is preferred owing to pigment-dispersing, tone, thermostability, processibility, barrier properties for gases etc. reach to heavens easily.This oxirane value preferred 0.25 or less than 0.25, more preferably 0.2 or less than 0.2.Most applications, oxirane value are about 0.05～0.2 can obtain good result.Contain the oxirane value of (methyl) acrylic acid series of glycidyl when excessive, be easy to generate the fish limit or make the outward appearance of forming composition become bad easily.Otherwise when oxirane value was too small, the effect of thermostability reduced.

The acrylic resin that contains glycidyl, with epoxy compounds and with in, be resin 100 weight parts with respect to PVDC, 0.3～5 weight part normally, preferred 0.4～3 weight part, more preferably 0.5～2 weight part.When this cooperation ratio is too small, or thermostability reduces or tone improves the effect reduction.When this cooperation ratio was excessive, the barrier properties for gases of forming composition, winter hardiness reduced and are difficult to obtain the degree of staining of distinctness.Most situation can obtain good result when this cooperation ratio is 0.7～1.5 weight part left and right sides.

Epoxy compounds (B1) and the usage ratio that contains (methyl) acrylic resin (B2) of glycidyl, benchmark is generally 90: 10～40: 60 by weight, preferred 80: 20～50: 50.With such usage ratio, by epoxy compounds (B1) and (methyl) acrylic resin (B2) that contains glycidyl and usefulness, can highly keep PVDC is the thermostability of resin, and suppress to result from separating out of epoxy compounds, can improve the characteristic of dispersing of pigments, tone, processibility, barrier properties for gases etc.

In addition, epoxy compounds (B1) and (methyl) acrylic resin (B2) that contains glycidyl add up to cooperates ratio, is resin 100 weight parts with respect to PVDC, is generally 0.5～8 weight part, preferred 1～5 weight part, more preferably 1.5～4 weight parts.When the cooperation ratio that these thermo-stabilizer adds up to is excessive, is easy to generate and separates out or improper problem such as the transparency reductions, when too small, the thermostability reduction perhaps can not fully obtain both combined effect sometimes.

3. Other additive

In PVDC based resin composition of the present invention, can contain antioxidant, softening agent, lubricant, dispersing auxiliary, weighting agent, UV light absorber, tensio-active agent, other the various additives of stablizer, pH regulator agent, pigment etc.

As antioxidant, can enumerate 2,6-di-t-butyl-4-methyl-phenol (BHT), triglycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester (Ciba-Geigy (チ バ ガ イ ギ-) corporate system, Irganox 245), 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, and their phenol of mixture (Ciba-Geigy corporate system Irganox 1141) etc. be antioxidant; The thioether of thiodipropionic acid, distearyl thiodipropionic acid ester etc. is an antioxidant; The phosphorous acid ester of trisnonyl phenyl phosphite, distearyl pentaerythrityl diphosphite etc. is an antioxidant etc.Antioxidant is resin 100 weight parts with respect to PVDC, uses in the ratio of 0.0001-0.05 weight part usually.

As softening agent; representational 2～3 kinds acetylize glyceride type, the hexanodioic acid and 1 of enumerating dioctyl phthalate (DOP), Tributyl O-acetylcitrate, Uniflex DBS, dioctyl sebacate, acetylated monoglyceride, acetylize two glyceryl ester, acetylize Witepsol W-S 55 and containing them; 3-butyleneglycol, hexanodioic acid and 1, the 4-butyleneglycol, and they 2 kinds or be softening agent more than the polyester of 2 kinds mixture etc.

Softening agent is resin 100 weight parts with respect to PVDC, uses in the ratio of 0.05～10 weight part usually.Softening agent can be that the powdered resin of resin mixes with PVDC, or adds in polymerization process in the slurries after carrying out polymerization in the monomer mixture or adding polymerization to, perhaps by these combination, makes and contains softening agent in the resin combination.Among these, make during preferred polymeric and contain softening agent in the powdered resin, when mixing, mix the softening agent of adding as required.

As lubricant,, can enumerate the wax class of oxidized polyethlene wax, paraffin, polyethylene wax, montanic acid ester type waxes, montanic acid calcium etc. as the lubricant that is applicable to PVDC based resin composition melt-processed; The fatty acid ester of monoglyceride etc.In addition, as the lubricant of the secondary processing of melt-processed that is applicable to the PVDC based resin composition and film, can enumerate the monoamide of lipid acid of stearylamide etc. or bisamide etc.These lubricants are resin 100 weight parts with respect to PVDC, usually available 2 weight parts or be less than the amount of 2 weight parts.

Dispersing auxiliary during as dispersed color, can enumerate aforesaid epoxy compounds and softening agent, lubricant with paraffin, polyethylene wax, montanic acid ester type waxes, montanic acid calcium etc., the tensio-active agent of glycerol fatty acid ester system, sorbitan-fatty acid ester system, polyoxyethylene sorbitan fatty acid ester system etc., glycerol and propandiols, also have the oligopolymer and the polymkeric substance of aliphatics hydrocarbon system or aromatic series hydrocarbon system.Among these, preferably using carbonatoms is 2～8 aliphatic hydrocarbon oligopolymer.Most preferably using weight-average molecular weight is 300～5000 liquid aliphatic hydrocarbon oligopolymer.

Dispersing auxiliary also can use when modulation PVDC based resin composition, also can paintedly use during with resin combination making.Dispersing auxiliary can improve dispersing of pigments, prevent dispersing of pigment, reduce processing temperature simultaneously, carry out painted manufacturing easily, dispersing auxiliary with resin combination, with respect to PVDC is resin 100 weight parts, usually uses in 2 weight parts or the ratio that is less than 2 weight parts.When excessively using dispersing auxiliary, make the comminuted deterioration of tinting material, also hindering PVDC easily is the barrier properties for gases of resin.

Can enumerate silicon-dioxide, lime carbonate etc. as weighting agent.Moreover silicon-dioxide and lime carbonate are also given (wrapping mechanism suitability) agent as the agent of creasing, film sliding and are used.In addition, silicon-dioxide is also used as inorganic lubricant.Silicon-dioxide can effectively prevent the cohesion between the EVA when mixing EVA.Weighting agent is resin 100 weight parts with respect to PVDC, common available 1 weight part or be less than 1 weight part, preferred 0.5 weight part or be less than the dosage of 0.5 weight part.

As UV light absorber, can enumerate 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole etc., can adopt dosage as required.

As tensio-active agent, the nonionic that can enumerate sorbitan-fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid ester etc. is a tensio-active agent etc.Can adopt dosage as required. glycerol fatty acid monoester, sorbitan list docosoic ester, sorbitan-fatty acid ester etc. are made the layer stripper of packaging film and are used.

As other stablizer, also can suit, use in right amount the inorganic salts of magnesium hydroxide, magnesium hydride, alkali calcium phosphate etc.; The organic monoacid salt of citric acid, alkali metal citrates etc.; Edetate class etc.

As the pH regulator agent, can enumerate trisodium phosphate, Disodium pyrophosphate etc.With respect to PVDC is resin 100 weight parts, available 0.5 weight part or be less than the appropriate amount of 0.5 weight part.

As pigment, can be, phthalocyanine system, 2 pigment dyestuff of 3-quinoline a word used for translation ketone system etc. with azo; The mineral dye of titanium oxide, aluminium system, mica, carbon black etc.; The filler pigment of lime carbonate, magnesium oxide etc. etc.Among these, in the packaging film field of processed foods such as fish sausage, poultry meat processed goods, the red pigment of widely-used Pigment red etc.Pigment can be distinguished separately and to use, or with 2 kinds or be used in combination more than 2 kinds.Pigment is resin 100 weight parts with respect to PVDC, usually with 1 weight part or be less than the appropriate amount of 1 content part.But when using titanium oxide pigments, be mixed into 10 weight parts sometimes.

Among these the additive, for example, the various functions that have softening agent, dispersing auxiliary, lubricant etc. concurrently that have.In addition, these additives are added on PVDC usually and are in the powdered resin of resin and mix, and are in the slurries after the polymerization of resin is finished but also can be blended in PVDC as requested, can also be added in the monomer mixture before the polymerization.

4. Painted with resin combination (colour batch)

When making the PVDC based resin composition contain pigment among the present invention, can use the resin combination that contains pigment in advance with high density, promptly use with the form of colour batch.Preferably contain (methyl) acrylic resin (B2) of glycidyl and the painted resin combination of using of pigment (C) as colour batch.

Painted at this with in resin combination, also can be as required, contain (methyl) acrylate (being total to) polymkeric substance (F) of not containing glycidyl, ethylene-vinyl acetate copolymer (D) etc.

In addition, in order to improve dispersing of pigments etc., also can be painted with adding softening agent and dispersing auxiliary etc. in the resin combination.

The painted resin combination of using in the mixture for the powdered resin that is added on polyvinylidene chloride resin and epoxy compounds various additives such as (B1), be pulverized as powder and use.Pulverizing can be with the impact type pulverizing mill of jet mill pulverizer etc.

As (methyl) acrylic resin that preferably contains glycidyl, can enumerate, but ethene be the polymeric unsaturated organic acid glycidyl ester 10～50 weight % with, can with the multipolymer of at least a kind vinyl monomer 50～90 weight % of its copolymerization.(methyl) acrylic resin that contains glycidyl, but more preferably ethene be the polymeric unsaturated organic acid glycidyl ester 10～50 weight %, do not contain glycidyl (methyl) acrylate 10～90 weight % and can with other the multipolymer of vinyl monomer 0～40 weight % of their copolymerization.

The painted resin combination of using of the present invention preferably with the ratio of 20～90 weight %, more preferably contains (methyl) acrylic resin of glycidyl with the ratio of 30～60 weight %.Contain the cooperation ratio of (methyl) acrylic resin of glycidyl when excessive, be easy to generate fine powder when pulverizing, when very few, the tendency of comminuted reduction occurs with resin combination painted.

Usually with 10～80 weight %, preferred 15～60 weight %, more preferably the ratio of 20～40 weight % contains pigment.When the cooperation ratio of pigment was excessive, its uniformly dispersed reduction when very few, diminished as the effect of colour batch.To improve containing of pigment in can keeping the uniformly dispersed scope of pigment proportional as far as possible, so that can paintedly obtain to have the PVDC based resin composition of desired degree of staining with resin combination with a spot of, ideal from the viewpoint of cost.

Can paintedly contain dispersing auxiliary in resin combination of the present invention.When making it to contain dispersing auxiliary, it contains proportional normally 0.05～10 weight %, preferred 0.5～5 weight %, more preferably about 1～3 weight %.When the cooperation ratio of dispersing auxiliary was excessive, painted softening temperature with resin combination reduced, adhesion easily, and when too small, the effect that pigment-dispersing improves reduces.

Of the present invention painted with containing softening agent in the resin combination.This situation, the epoxidized vegetable oil of epoxidised soybean oil etc. also can be used as softening agent and use.But because painted less usually with the cooperation ratio of resin combination in the PVDC based resin composition, even as the softening agent epoxidized vegetable oil, the ratio that this epoxidized vegetable oil accounts in total epoxy compounds (B1) is also quite little.

Epoxidized vegetable oil and other softening agent, it contains proportional is benchmark with painted total amount with resin combination, is generally 0.5～10 weight %, preferred 1～7 weight %, more preferably 2～5 weight %.When the cooperation ratio of softening agent was excessive, painted softening temperature with resin combination reduced, adhesion easily, and when too small, the plastifying degree is not enough, is being the powdered resin of resin very difficult uniform mixing when mixing with PVDC.

The painted resin combination of using of the present invention is extruded the stabilization of processibility for it, can make it to contain (being total to) polymkeric substance (F) of (methyl) acrylate that does not contain glycidyl.As (methyl) acrylate, can enumerate methyl methacrylate, butyl methacrylate etc.Among these, preferable methyl methyl acrylate-butyl methacrylate copolymer.The cooperation ratio that does not contain (methyl) acrylate (being total to) polymkeric substance (F) of glycidyl is a benchmark with painted total amount with resin combination, preferred 10～40 weight %, more preferably 15～30 weight %.When this cooperation ratio was excessive, the high frequency stopping property reduced, and when too small, extruded processibility and became unstable sometimes.

Of the present invention painted with containing ethylene-vinyl acetate copolymer (EVA) in the resin combination.As previously mentioned, preferred 20～40 weight % of the vinyl acetate content among the EVA, more preferably 28～35 weight %.The melt flow rate (MFR) of EVA (MFR) preferred 1～50g/10 minute, more preferably 20～40g/10 minute.Painted containing of EVA is proportional with in the resin combination, preferred 50 weight % or be lower than 50 weight %, more preferably 30 weight % or be lower than 30 weight %, most preferably 20 weight % or be lower than 20 weight %.When containing EVA, usually contain with 1 weight % or greater than 1 weight %, preferred 5 weight % or greater than the ratio of 5 weight %.

When the amount of EVA was too much, the melt viscosity of colored resin composition diminished, dispersing of pigments reduction, or become rubber-like at normal temperatures and be difficult to pulverize, and thermotolerance reduces, be easy to generate be clamminess, adhesion.When the amount of EVA was very few, when pulverizing colored resin composition, the granularity of gained powder was meticulous.

Of the present invention painted with in the resin combination, as required, also can contain the various additives of the lubricant, antioxidant etc. of organic or inorganic in an amount of scope.

The painted resin combination of using is modulated by the method for each composition being mixed, mixture is added hot milling.The painted resin combination of using is pulverized usually and is used as powder.Preferably mixing thing is melt extruded slabbing, after chilling obtains sheet material, this sheet material is ground into powder.The granularity of this powder, from PVDC be that the dispersed viewpoint of the powdered resin etc. of resin is considered, the preferred powder by the #20 mesh sieve, the more preferably powder by the #40 mesh sieve.

The painted resin combination of using of the present invention, because the Heat stability is good of himself, so also can be added in the common thermoplastic resin.

5. The manufacture method of PVDC based resin composition

Generally, when modulation contains PVDC and is the resin combination of resin and various additives, with PVDC be that the powdered resin of resin is mixed together various additives, make the resin combination (mixture) of powder shaped.By mixing, the fluid additive of epoxidized vegetable oil and softening agent etc. is that the powdered resin of resin absorbs by PVDC, and the additive adhesion of powder at PVDC be resin powdered resin around.

When this mixing, cause the cohesion of additive component easily, cause pigment particles especially easily and contain the cohesion of (methyl) acrylic resin powder etc. of glycidyl.When having condensation product in a large number in the PVDC based resin composition, processibility, extrudability, film-forming properties, extensibility etc. are destroyed, also cause bad order owing to generate flake etc. on the forming composition of film etc.In order to improve dispersing of pigments, in the condensation product that suppresses pigment and additive component generates, preferably grasp the addition means of each composition.

First manufacture method of the present invention, be that the polyvinylidene chloride that is containing at least a kind the epoxy compounds (B1) that is selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester and the epoxy prepolymer when polymerization is in the powder of resin (A), mixing contains (methyl) acrylic resin (B2) of glycidyl and the painted powder with resin combination of pigment (C), and the manufacture method of mixing the polyvinylidene chloride based resin composition of the epoxy compounds of adding (B1) as required.

Polyvinylidene chloride is the powdered resin of resin (A), contains during preferably except that polymerization the epoxy compounds (B1), goes back the resin of plasticizer-containing (E).Moreover, make PVDC when polymerization, contain epoxy compounds (B1) and/or softening agent (E) in the powdered resin of resin, or add these in the monomer mixture before polymerization, or in polymerization, add in the polymerization reaction system, or in the slurries after the adding polymerization, the PVDC that makes generation is after resin contains these, reclaims as powdered resin.

The amount of epoxy compounds in the powdered resin (B1) and/or softening agent (E) can mix epoxy compounds (B1) and/or the softening agent of adding (E) after a little while as required in mixed processes.During mixing, mixed ethylene-vinyl acetate copolymer (D), other additive as requested.As painted powder, can use aforesaid powder composition with resin combination.

According to first manufacture method of the present invention, can mix each composition at normal temperatures.In order to make PVDC is in the powdered resin of resin, contains the main liquid component of epoxy compounds (B1) and softening agent etc. when prepolymerization, can mix with painted powder with resin combination at normal temperatures, thus, can modulate and form uniform composition.

Second manufacture method of the present invention, be when polyvinylidene chloride is the powdered resin of resin (A) or polymerization, make it to contain be selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, and epoxy prepolymer in the polyvinylidene chloride of at least a kind epoxy compounds (B1) be in the powdered resin of resin (A), powder, pigment and the epoxy compounds (B1) that mix (methyl) acrylic resin (B2) that contains glycidyl, or the manufacture method of the polyvinylidene chloride based resin composition of the epoxy compounds of adding as required (B1).

Preferably making polyvinylidene chloride is that the powdered resin of resin (A) contains epoxy compounds (B1) and/or softening agent (E) when prepolymerization.But mixed ethylene-vinyl acetate copolymer during mixing (D), other additive.When powdered resin does not contain epoxy compounds (B1), hybrid epoxidized compound (B1) during mixing.In addition, even make powdered resin when polymerization, contain epoxy compounds (B1) and/or softening agent (E), but these amount after a little while, also can when mixing, mix epoxy compounds (B1) and/or the softening agent of adding (E) as required.

In second manufacture method of the present invention, at polyvinylidene chloride is that the powdered resin of resin (A) or the polyvinylidene chloride that contains epoxy compounds (B1) are in the powdered resin of resin (A), add the powder composition in addition of (methyl) acrylic resin (B2) that contains glycidyl, after mixing under the intensification condition, the powder that in process of cooling, mixes (methyl) acrylic resin (B2) contain glycidyl, this in the generation that suppresses condensation product, modulation mixes on each mixture of ingredients equably is ideal.

More particularly, be in the powdered resin of resin (A) at polyvinylidene chloride, after the powder additives of the fluid additive of interpolation epoxy compounds (B1), softening agent (E) etc., lubricant etc., under the intensification condition, mix.As the mixing under the intensification condition, usually, while the preferred temperature that is warmed up to 65～85 ℃ is carried out the blended method.

Preferably dropping into PVDC in mixing machine is the powdered resin of resin, after the powder additives of interpolation lubricant etc., adds the fluid additive of softening agent (E), epoxy compounds (B1), dispersing auxiliary etc. more as required, adds pigment thereafter immediately.These mixture is warmed up to 85 ℃ temperature (for example, about 80 ℃) on one side Yi Bian mix.

Aforementioned mixture cools off usually immediately if be warmed up to the temperature of setting, and the powder that adds the metha crylic resin (B2) that contains glycidyl in this process of cooling mixes.In the interpolation period of containing (methyl) acrylic resin (B2) powder of glycidyl, the temperature of preferred mixture is to drop to 70 ℃ or be lower than 70 ℃, be more preferably 60 ℃ or be lower than 60 ℃, when preferably dropping to normal temperature again.Contain (methyl) acrylic resin (B2) of glycidyl if 80 ℃ of mixing temperatures of powder or when being higher than 80 ℃ are easy to generate the condensation product of pigment particles.

The PVDC based resin composition (mixture) that makes is so preferably removed oversize particle with sieve apparatus owing to contain oversize particle slightly sometimes.

When other method is mixed EVA, preferably will mix with the powder of EVA with the resin combination that the aforementioned approaches method makes.Preferred EVA mixes at normal temperatures.This situation, oversize particle is removed with sieving in the preferred back of mixing.

Each composition can mix with the mixing machine of wing mixer, ribbon mixer, Henschel mixer etc.In addition, making paintedly when using resin combination, also can carry out mixing with two roller Banbury mixeies, 3 roller Banbury mixeies.

Adopt manufacture method of the present invention, can suppress the generation of the condensation product of pigment particles and the condensation product of (methyl) acrylic resin that contains glycidyl etc., thereby can obtain the PVDC based resin composition of processibility and all physical properties excellent.

Among the present invention, so-called " normal temperature " means normally 5～45 ℃, preferred 10～40 ℃, more preferably 15～35 ℃.

6. The moulding of PVDC based resin composition

PVDC based resin composition of the present invention (mixture) may be molded to stretching or non-stretched film, sheet material etc. after melt extruding.As the forming method of film, for example can adopt the inflatable extrusion moulding of annular die etc.The oriented film that stretch, preferred two-way stretch makes has heat-shrinkable, but and is suitable as the heat-resistant film of boiling.Preferred vertical 2～5 times, horizontal 2～5 times of stretching ratio.

Film thickness is as single thin film normally 5～50 μ m, preferred 10～30 μ m.Also can make bilayer film according to purposes uses.The percent thermal shrinkage of oriented film preferably vertically, laterally all is about 30～60% (120 ℃ glycerol bath, 3 minutes).As the main using method of food packing film, be the inflatable moulding after, 2 overlapping bilayer films that make, overlap (ear) part at rip cutting film two ends, while make cylindric the sealing with wrapping mechanism, then, fill content, clamp two ends and get wrapping body.Packaging film is suitable as the wrapping material of processed foods such as fish sausage, poultry meat processed goods.

With the film of PVDC based resin composition of the present invention moulding, with scope (about 1.5m of any 100g ²) expressly do not select 10 places, when observing the colo(u)rant dispersion state with magnifying glass, 0.4mm or be 10 or during less than 10, pigment-dispersing is good significantly greater than the number of the cohesion piece of 0.4mm.This means that PVDC based resin composition of the present invention has suppressed the generation of condensation product, thermostability might as well.

Film with PVDC based resin composition of the present invention moulding, being used alone as the product that thermo-stabilizer makes with past epoxy compounds that epoxidised soybean oil and epoxidised linseed oil etc. is general compares, tone improves significantly, demonstrates white slightly feeling of high class than the dead color sense of past product.Therefore, feeling of high class is arranged, can help to improve commodity value with the processed food of the fish sausage of this film packaging, poultry meat processed goods etc.

With the film of PVDC based resin composition of the present invention moulding, good with the adaptation of edible meat etc.For example, if the surface treatment of enforcement Corona discharge Treatment etc. is filled when eating meat, raising is bigger with the effect of film adaptation, can reduce effusive generations from eat meat such as gravy.

If at PVDC is the epoxy compounds that contains epoxidised soybean oil and epoxidised linseed oil etc. in the resin, the tendency of the barrier properties for gases reduction of film generally appears.Yet, PVDC based resin composition of the present invention, when moulding since the dispersive epoxy compounds with contain the effect of (methyl) acrylic resin of glycidyl, so Heat stability is good.Intermiscibility because of (methyl) acrylic resin that contains glycidyl and epoxy compounds after moulding is good, fine dispersive contains the epoxy compounds that glycidyl (methyl) acrylic resin absorbs liquid, its result still keeps thermostability, barrier properties for gases improves with the adaptation of meat-based food etc.Therefore, with the film of PVDC based resin composition of the present invention moulding, its barrier properties for gases is good.

If mix EVA, except helping to extrude the raising of processibility and sealing intensity, after moulding, also absorb epoxy compounds with (methyl) acrylic resin that contains glycidyl, help the raising of barrier properties for gases.Epoxy compounds, owing to when the melt-processed of extrusion moulding etc., help thermostability, after moulding,, can bad influence not arranged to the thermostability of the forming composition of film etc. even contained absorptions such as (methyl) acrylic resin of glycidyl and EVA yet.

Embodiment

Below, enumerate embodiment and comparative example, be described more specifically the present invention.But the present invention is not limited to these embodiment.Evaluation method among the present invention is as follows.

(1) reduced viscosity

In order to methyl alcohol is that tired (Soxhlet) extractor of Suo Kesi of solvent is after resin carries out extraction treatment with PVDC, with dried resin as test portion, with Wu Bailaode (Ubbelohde) viscometer, be that hexanaphthene, resin concentration are 4g/L, to measure temperature be to obtain reduced viscosity under 30 ℃ the condition at solvent.

(2) extrude stable evaluation (thermostability, processibility)

Use the forcing machine (motor 15KW) of screw diameter 90mm, PVDC based resin composition (mixture) is melt extruded.Write down the mobility scale of this forcing machine motor load.And situation is extruded in observation.Estimate with following standard.

Zero: ± 3A or less than ± 3A (processibility is stable)

△: ± 5A or less than ± 5A (, can make) or the adhesion (decomposition) of resin often takes place in the mouth mould exit that molten resin is extruded by forcing machine though processibility is stable poor.

*: surpass ± 5A (making difficulty)

(3) composition yield

The PVDC based resin composition is mixed with resin combination under the situation about using the back with painted,, also sieve with the #50 purpose except that with the #10 purpose sieve.After the screening, the weight of the mixture of sieve is not passed through in metering, estimates by following standard.

Zero: residual amount is 0.2 weight % less than input amount on the sieve.

*: residual amount is 0.2 weight % of input amount or greater than 0.2 weight % of input amount on the sieve

(4) tone

Adult that please 10 health observes the wrapping body of cooking disinfection, compares with the product in past, judges whether tone or style improve.Judgement criteria is as follows.With 7 people or estimate consistent situation more than 7 people and judge.

Zero: tone, feel are better than the past product, and feeling of high class is arranged.

△: turn white, opaque slightly.

*: beige, black slightly.

(5) the oversize particle number in the film

With the dispersion state in the magnifying glass viewing film, to the scope of 100g (about 1.5m arbitrarily ²) expressly do not observe 10 places, investigation 0.4mm or greater than the number of 0.4mm cohesion piece as opinion scale, estimate by following standard.

Zero: 10 or be less than 10

*: above 10

(6) evaluation of high frequency stopping property (wrapping mechanism suitability, film sliding)

The former film of wide 1m is cut into wide 70mm, make the former film that batches once more, use the automatic filling apparatus for ligating (Wu Yu type KAP500 type, Wu Yu chemical industrial company system) of membrane supplying part, high frequency hermetic unit, automatic filling part, ligation sectoral integration, press the goods length (between metal clip) of 400g, 100/minute of filling speeds, wrapping body to set under the condition of 200mm at current value 70mA, electrode surface, fill the raw meat that pork sausage is used.The high frequency stopping property is estimated by following standard.

Zero: the right film sliding of bag is good, do not swing, do not have the film of profiled sheeting to come off, the inequality of no folding length, high frequency sealing that can be stable.And, the goods length of wrapping body, by set(ting)value ± 2.5mm processing.

*: the film sliding during bag is poor, swing is arranged, have the film of profiled sheeting to come off, the inequality of folding length is arranged, sealing that can not be stable, and the goods length of wrapping body by set(ting)value ± 2.5mm or greater than ± 2.5mm with interior processing.

(7) the broken body rate (breaking from hermetic unit during cooking disinfection) of wrapping body

Gauge pressure 2.0kg/cm in heating tank ², under 120 ℃ of conditions of temperature, 100 of the wrapping bodies of above-mentioned gained were carried out the heating and pressurizing sterilization 20 minutes, pressurize unchangeably and be cooled to 25 ℃ keeping pressure, open then and jar from heating tank, take out.By the number of the broken body of the hermetic unit of wrapping body investigation, obtain brokenly body rate 1%.

[embodiment 1]

1. Painted modulation with resin combination

As shown in table 1, will contain (methyl) acrylic resin [glycidyl methacrylate-methyl methacrylate-styrene-propene acid butyl ester (30/31/31/8 weight %)] 41 weight %, methyl methacrylate-butyl methacrylate multipolymer 23 weight %, Pigment red mixture (pigment) 25 weight %, the silicon-dioxide (inorganic lubricant of glycidyl; Median size 5.2 μ m) 5 weight %, epoxidised soybean oil 3 weight %, aliphatic hydrocarbon oligopolymer (Mw=2,100) 2 weight %, and montanic acid calcium 1 weight %, under normal temperature (23 ℃), stirred 5 minutes with Henschel mixer, make the painted resin combination of using.Composition is shown in table 1.

Table 1

The painted resin combination of using	Form	2 weight parts
			Weight %	Detailed catalogue
	(methyl) acrylic resin glycidyl methacrylate-methyl methacrylate-styrene-propene acid butyl ester=30/31/31/8 (weight %) oxirane value=0.19 of containing glycidyl	41			0.82
The methyl methacrylate-butyl methacrylate multipolymer			23	0.46
	Pigment red (mixture)	25			0.50
Silicon-dioxide			5	0.10
	Epoxidised soybean oil	3			0.06
The aliphatic hydrocarbon oligopolymer			2	0.04
	Montanic acid calcium	1			0.02

(notes) are resin 100 weight parts with respect to PVDC in an embodiment, by this painted resin combination of using of mixed of 2.0 weight parts, so list the detailed catalogue of each composition in this 2.0 weight part for ease of reference.

With the painted resin combination of using of gained, be set at 2 heating drums (φ=200mm) added hot milling 10 minutes of 150 ℃ with surface temperature.After mixing, mixing thing chilling is made sheet material.Use jet mill pulverizer (impact pulverizing mill) that this sheet material is pulverized, make crushed material pass through #40 purpose sieve, make painted powder with resin combination.

2. The modulation of PVDC based resin composition

As PVDC is resin, uses each powdered resin of PVDC (1) [vinylidene chloride (VD)/vinylchlorid (VC)=88/12 (weight %), reduced viscosity=0.063] and PVDC (2) [VD/VC=83/17 (weight %), reduced viscosity=0.052].During each powdered resin polymerization, be resin 100 weight parts, contain epoxidised linseed oil (O-180) 2.4 weight parts and the such ratio of Uniflex DBS 3.5 weight parts is modulated with respect to PVDC.

At above-mentioned 2 kinds PVDC is in the powdered resin of resin, adds aforementioned synthetic painted powder and various additive with resin combination, and modulation has the PVDC based resin composition of forming shown in the table 2.For the expression of each composition, situation about containing when situation that (during polymerization) contains in the time of can being distinguished into the powdered resin manufacturing and mixing.In addition,, comprise paintedly, express the total amount with situation about containing in the resin combination about epoxy compounds and softening agent.

At first, be the powdered resin of resin with wing mixer with PVDC and paintedly mix modulation PVDC based resin composition (mixture) with resin combination and EVA and various additive.Mixing time is 15 minutes, and mixing temperature is normal temperature (23 ℃) (normal temperature mixing), with #10 purpose sieve screening PVDC based resin composition, removes oversize particle.

3. Making of film

Use the forcing machine (adjusting to vacuum pressure=pact-680mm Hg mercury column) of the diameter 90mm of band vacuum hopper, after melt extruding the PVDC based resin composition circlewise, chilling in 7 ℃ cooling tank then, makes it the warm water bath by 20 ℃, and being pressed into air between the different pinch roll of 2 groups of surface of revolution speed makes it to expand, carry out stretch orientation, about 2.5 times of its longitudinal stretching, laterally about 4.2 times, make oriented film, evaluation result is shown in table 2.

[comparative example 1]

When the polymerization of each powdered resin, be that resin 100 weight parts make it to contain epoxidised linseed oil (O-180) 3.4 weight parts and the such ratio of Uniflex DBS 3.5 weight parts is modulated with respect to PVDC.Use these powdered resins, and painted with resin combination and contain (methyl) acrylic resin of glycidyl except not using, other are operated similarly to Example 1.Show the result in table 2.

[embodiment 2]

When the polymerization of the powdered resin of PVDC (1), be resin 100 weight parts with respect to PVDC, these ratios that make it to contain epoxidised linseed oil (O-180) 0.3 weight part and Uniflex DBS 4.0 weight are modulated.Press powdered resin, powder additives, the fluid additive (order of tributyl acetylcitrate, epoxidised linseed oil and pigment of PVDC (1), composition beyond (methyl) acrylic resin that contains glycidyl in each composition shown in the table 2 is dropped in the wing mixer, be warmed up to about 80 ℃ (heat up and mix) while mix.Cooling immediately after the intensification, the powder that drops into (methyl) acrylic resin that contains glycidyl when temperature drops to about 65 ℃ mix (mix the back of heating up).After the cooling, with obtaining resin combination (mixture) after the screening of #50 purpose sieve.Except with this resin combination beyond the region of objective existence, other make oriented film similarly to Example 1, estimate.Show the result in table 2.

[comparative example 2]

When the polymerization of the powdered resin of PVDC (1),, make it to contain the such ratio of Uniflex DBS 4.0 weight parts and modulate by being resin 100 weight parts with respect to PVDC.Use this powdered resin, and except when mixing (methyl) acrylic resin that contains glycidyl with other powder additives is once added, other are operated similarly to Example 2.Show the result in table 2.

[embodiment 3]

When the polymerization of each powdered resin,, make it to contain epoxidised linseed oil (O-180) 2.46 weight parts and the such ratio of Uniflex DBS 3.5 weight parts is modulated by being resin 100 weight parts with respect to PVDC.With these powdered resin, and press powdered resin.The order of powder additives and pigment drops into the composition beyond (methyl) acrylic resin that contains glycidyl in each composition shown in the table 2 and the EVA in the wing mixer, is warmed up to about 80 ℃ (heat up and mix) while mix.Cooling immediately after the intensification, when temperature dropped to about 65 ℃, the powder that drops into (methyl) acrylic resin that contains glycidyl mixed (heat up and mix).Then, mix EVA (normal temperature mixing) at normal temperatures.With the resin combination of gained, make oriented film similarly to Example 1.Show the result in table 2.

Table 2

Form (weight part)		Interpolation period	Embodiment 1	Comparative example 1	Embodiment 2	Comparative example 2	Embodiment 3
								Resin	PVDC(1)	-	85	85	100	100	85
PVDC(2)	-	15	15	-	-	15
							Softening agent		Uniflex DBS	During polymerization	3.5	3.5	4.0	4.0	3.5
Tributyl acetylcitrate	Heat up and mix	-	-	4.0	4.0	-
								Thermo-stabilizer	Epoxidised linseed oil	During polymerization	2.4	3.4	0.3	-	2.46
Heat up and mix	-	-	1.0	-	-
						(methyl) third that contains glycidyl helped sour generation and analysed fat (GMA)	Heat up and mix			-	-	-	2.3	-
Normal temperature mixes	0.18 (0.8)*1	-	-	-	-
							The back mixing heats up		-	-	1.0	-	1.0
Lubricant thin film		Heat up and mix	-	-	0.2									0.2	0.1
						Normal temperature mixes	(0.1)*1	0.2	-	-	-
		Sealing intensity improving agent (EVA)		Normal temperature mixes	2.5							2.5	-	-	2.5
Pigment						Normal temperature mixes	-	-	0.35	0.35	0.5
		Normal temperature mixes	(0.5)*1	0.5	-							-	-
						The painted resin combination of using		Normal temperature mixes	2.0	-	-			-	-
Thermo-stabilizer	Epoxy compounds (total amount)		2.46	3.4	1.3							0	2.46
						(methyl) acrylic acid that contains glycidyl is resin (GMA) (a total amount)		1.0	0	1.0	2.3			1.0
	Extrude stability (thermostability, processibility)			○	△							○	×		○
The composition yield						○	○	○	×	○
			The film tone								○	×	○	△	○
Oversize particle number in the film						○	×	○	×	○
			High frequency stopping property (wrapping mechanism suitability, film sliding)								○	×	○	×	○
The broken bag rate of wrapping body (during cooking disinfection, breaking from hermetic unit) (%)						＜0.5	5＜	＜1	5＜	＜0.5

(notes)

* the painted parts by weight of the numeric representation 1:() with each contained in resin combination 2.0 weight parts composition.

Among the embodiment 1, drop into epoxy compounds and softening agent during polymerization, do not drop into during mixing.When not having fluid additive during mixing,, then do not need the mixing that heats up, can carry out normal temperature and mix, and mixing time shortens because PVPC is the powdered resin absorption liquid body additives of resin.In addition, painted powder with resin combination can be carried out normal temperature and mix, and suppress the generation of condensation product.In contrast, comparative example 1 mixes owing to need not paintedly carrying out normal temperature with resin combination, so the broken bag rate of the oversize particle number in the film, high frequency stopping property, wrapping body is bad.

Embodiment 2, powder and usefulness with epoxy compounds and (methyl) acrylic resin that contains glycidyl, and the powder of (methyl) acrylic resin by will containing glycidyl in process of cooling mixes, and does not have the generation of condensation product, and tone is also good.In contrast, comparative example 2 is owing to contain the input difference in period of (methyl) acrylic resin of glycidyl, the broken bag rate inequality of the oversize particle number in composition yield, the film, high frequency stopping property, wrapping body, and, owing to only use (methyl) acrylic resin that contains glycidyl, so the film tone is unsatisfactory, it is also bad to extrude stablizer.

Embodiment 3 is not that normal temperature mixes, and adopts intensification similarly to Example 2 to mix the resin combination and the film that can obtain having the characteristic that requires.

[embodiment 4]

When the polymerization of each powdered resin of PVDC (1) and PVDC (2),, make it to contain epoxidised linseed oil (O-180) 0.4 weight part and the such ratio of Uniflex DBS (DBS) 3.5 weight parts is modulated by being resin 100 weight parts with respect to PVDC.By the powdered resin of PVDC (1) and PVDC (2), powder additives, fluid additive (epoxidised linseed oil), and the order of pigment (methyl) acrylic resin (GMA) that contains glycidyl in each composition shown in the table 3 and ethylene-vinyl acetate copolymer (EVA) composition are in addition dropped in the wing mixer, mixes being warmed up to about 80 ℃ (intensification mixing) on one side.Cooling immediately after the intensification, when temperature dropped to about 65 ℃, the powder that drops into (methyl) acrylic resin that contains glycidyl mixed (mix the back of heating up).Then, mix EVA at normal temperatures.After the cooling, with obtaining resin combination (mixture) after the screening of #50 purpose sieve.Except with this resin combination, other make film similarly to Example 1, estimate.Show the result in table 3.

[comparative example 3]

In embodiment 4, the use level of the epoxidised linseed oil when mixing except heating up is transformed into 3.0 weight parts by 2.2 weight parts, and, after the intensification, do not mix contain glycidyl (methyl) acrylic resin (GMA) in addition, make oriented film similarly to Example 4.The results are shown in the table 3.

[comparative example 4]

Do not use the epoxidised linseed oil during except polymerization in embodiment 4 and when heat up mixing, other make oriented film similarly to Example 4.Show the result in table 3.

[embodiment 5]

Except do not mix EVA in embodiment 4, other make oriented film similarly to Example 4.Show the result in table 3.

[embodiment 6]

When the polymerization of each powdered resin of PVDC (1) and PVDC (2),, make it to contain epoxidised linseed oil (O-180) 0.4 weight part and the such ratio of Uniflex DBS (DBS) 3.5 weight parts is modulated by being resin 100 weight parts with respect to PVDC.Powdered resin and epoxidised linseed oil 2.2 weight parts of PVDC (1) and PVDC (2) are dropped in the blade and blade mixing machine, be warmed up to about 80 ℃ (heat up and mix) while mix.Cooling immediately after the intensification, when being as cold as normal temperature (23 ℃), mixed film lubricant (silicon-dioxide) 0.1 weight part, painted with resin combination 2.0 weight parts, and EVA 2.5 weight parts (normal temperature mixing).Then, sieve with the #50 purpose and obtain resin combination (mixture).Except with this resin combination, other are made oriented film similarly to Example 1, estimate.Show the result in table 3.

[embodiment 7]

In embodiment 6, except at normal temperatures with powdered resin, epoxidised linseed oil 2.2 weight parts, film lubrication agent (silicon-dioxide) 0.1 weight part, painted with resin combination 2.0 weight parts, and EVA 2.5 weight parts mix (normal temperature mixing), other are made oriented film similarly to Example 6, estimate.Show the result in table 3.

[comparative example 5]

Except in embodiment 7, respectively epoxidised linseed oil 2.2 weight parts being made into 3.0 weight parts, lubricant thin film (silicon-dioxide) 0.1 weight part makes 0.2 weight part into, paintedly makes into beyond pigment 0.5 weight part with resin combination 2.0 weight parts, other make oriented film similarly to Example 7, estimate.Show the result in table 3.

Table 3

	Form (weight part)			Interpolation period	Embodiment 4	Comparative example 3	Comparative example 4	Embodiment 5	Embodiment 6	Embodiment 7	Comparative example 5
												Create conditions	Resin		PVDC(1)	-	85	85	85	85	85	85	85
PVDC(2)	-	15	15	15	15	15	15	15
									Softening agent		Uniflex DBS				During polymerization	3.5	3.5	3.5	3.5	3.5	3.5	3.5
Thermo-stabilizer	Epoxidised linseed oil		During polymerization	0.4	0.4	-	0.4	0.4					0.4	0.4
									Heat up and mix	2.2	3.0				-	2.2	2.2	-	-
			Normal temperature mixes	-	-	-	-	-					2.2	3.0
									(methyl) acrylic resin (GMA) that contains glycidyl		Normal temperature mixes				-	-	-	-	(0.8)*1	(0.8)*1	-
	The back mixing heats up	0.8	-	3.4	(0.8)	-	-	-
											Lubricant thin film			Heat up and mix	0.2	0.2	0.2	0.2	-	-	-
Normal temperature mixes	-	-	-	-	0.1 (0.1)*1	0.1 (0.1)*1	0.2
								Sealing intensity improving agent (EVA)						Normal temperature mixes	2.5	2.5	2.5	-	2.5	2.5	2.5
Pigment			Heat up and mix	0.5	0.5	0.5	0.5				-	-	-
								Normal temperature mixes	-	-				-	-	(0.5)*1	(0.5)*1	0.5
			The painted resin combination of using			Normal temperature mixes	-				-	-	-						2.0	2.0	-
Evaluation result	Extrude stability (thermostability, processibility)							○	△	△				○	○	○	×
					The composition yield						○	○	○					○	○	○	○
	The film tone								○	×				△	○	○	○					×
					Oversize particle number in the film						○	×	△					○	○	○	△
	High frequency stopping property (wrapping mechanism suitability, film sliding)								○	△				△	×	○	○					△
					The broken bag rate of wrapping body (during cooking disinfection, breaking from hermetic unit) (%)						＜0.5	5＜	＜1					5＜	＜0.5	＜0.5	5＜

(notes)

* the painted parts by weight of the numeric representation 1:() with each contained in resin combination 2.0 weight parts composition.

Utilize possibility on the industry

According to the excellent Vingon based resin composition such as the dispersiveness that the invention provides processability, heat endurance, tone, pigment, barrier properties for gases. In addition, also provide according to the present invention these all excellents Permalon composition manufacture method and with the film of this Vingon based resin composition moulding.

In addition, also provide the painted resin combination of using that is fit to painted PVDC based resin composition manufacturing according to the present invention. The film that makes with PVDC based resin composition of the present invention because tone and style excellence have feeling of high class, and is suitable as the packaging material etc. of the processed food of fish meat sausage, poultry meat processed goods etc.

Claims (22)

1. polyvinylidene chloride based resin composition, said composition is to contain the polyvinylidene chloride based resin composition that polyvinylidene chloride is resin (A), thermo-stabilizer (B) and pigment (C),

It is characterized in that this thermo-stabilizer (B) is that resin (A) 100 weight parts contain with respect to this polyvinylidene chloride:

(1) be selected from least a kind epoxy compounds (B1) 1～3 weight part in epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester and the epoxy prepolymer, and

(2) but to comprise ethene be glycidyl ester 10～50 weight % of polymeric unsaturated organic acid, the acrylate that does not contain glycidyl and/or methacrylic ester 10～90 weight % and the multipolymer that is selected from vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride and the alkyl vinyl ether other vinyl monomers 0～40 weight % of at least a kind, and oxirane value is less than 0.3 the acrylic resin that contains glycidyl (B2) 0.5～2 weight part more than 0.05

And epoxy compounds (B1) and the part by weight of acrylic resin (B2) that contains glycidyl are in 90: 10～40: 60 scope.

2. the resin combination of claim 1 record, it is characterized in that, be that the polyvinylidene chloride that makes it to contain epoxy compounds (B1) when containing (i) polymerization is the powdered resin of resin (A), (ii) contains painted powder with resin combination, and the mixture of the epoxy compounds (B1) (iii) added as required of glycidyl acrylic resin (B2) and pigment (C).

3. the resin combination of claim 1 record, it is characterized in that, be to contain (i) polyvinylidene chloride to be the powdered resin of resin (A), (ii) to contain the powder of the acrylic resin (B2) of glycidyl, (iii) pigment (C), and the (iv) mixture of epoxy compounds (B1).

4. the resin combination of claim 1 record, it is characterized in that, be that the polyvinylidene chloride that makes it to contain epoxy compounds (B1) when containing (i) polymerization is the powdered resin of resin (A), (ii) contains the powder of the acrylic resin (B2) of glycidyl, (iii) pigment (C), and the mixture of the epoxy compounds (B1) (iv) added as required.

5. the resin combination of claim 1 record is characterized in that, also contains ethylene-vinyl acetate copolymer (D).

6. the resin of claim 1 record is formed, and it is characterized in that, also contains softening agent (E).

7. the painted resin combination of using is characterized in that, contains:

But the multipolymer that comprises ethene and be glycidyl ester 10～50 weight % of polymeric unsaturated organic acid, the acrylate that does not contain glycidyl and/or methacrylic ester 10～90 weight % and be selected from vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride and the alkyl vinyl ether other vinyl monomers 0～40 weight % of at least a kind, and oxirane value be more than 0.05 less than 0.3 contain glycidyl acrylic resin (B2), and

Pigment (C).

8. the painted resin combination of using of claim 7 record is characterized in that, also contains the acrylate that do not contain glycidyl and/or the polymkeric substance or the multipolymer (F) of methacrylic ester.

9. the painted resin combination of using of claim 7 record is characterized in that, also contains ethylene-vinyl acetate copolymer (D).

10. the manufacture method of a polyvinylidene chloride based resin composition is characterized in that,

Contain during with (1) polymerization be selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, and epoxy prepolymer in the polyvinylidene chloride of at least a kind of epoxy compounds (B1) be resin (A) powdered resin,

(2) but contain that to comprise ethene be glycidyl ester 10～50 weight % of polymeric unsaturated organic acid, the acrylate that does not contain glycidyl and/or methacrylic ester 10～90 weight % and the multipolymer that is selected from vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride and the alkyl vinyl ether other vinyl monomers 0～40 weight % of at least a kind, and oxirane value be more than 0.05 less than 0.3 the painted powder that contains glycidyl acrylic resin (B2) and pigment (C) with resin combination, and

(3) epoxy compounds of adding as required (B1) mixes.

11. the manufacture method of claim 10 record is characterized in that polyvinylidene chloride is the powdered resin of resin (A), also contains the resin of softening agent (E) when being polymerization.

12. the manufacture method of claim 10 record is characterized in that, also mixed ethylene-vinyl acetate copolymer (D).

13. the manufacture method of claim 10 record is characterized in that, mixes each composition at normal temperatures.

14. the manufacture method of a polyvinylidene chloride based resin composition is characterized in that,

The polyvinylidene chloride that makes it to contain at least a kind the epoxy compounds (B1) that is selected from epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester and the epoxy prepolymer when (1) polyvinylidene chloride is the powdered resin of resin (A) or polymerization be the powdered resin of resin (A),

(2) but to comprise ethene be glycidyl ester 10～50 weight % of polymeric unsaturated organic acid, the acrylate that does not contain glycidyl and/or methacrylic ester 10～90 weight % and the multipolymer that is selected from vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride and the alkyl vinyl ether other vinyl monomers 0～40 weight % of at least a kind, and oxirane value be more than 0.05 less than 0.3 the powder that contains glycidyl acrylic resin (B2),

(3) pigment, and

(4) epoxy compounds (B1) or the epoxy compounds (B1) added as required mix.

15. the manufacture method of claim 14 record is characterized in that, goes back plastic binder (E).

16. the manufacture method of claim 14 record is characterized in that polyvinylidene chloride is the powdered resin of resin (A), makes it to contain the resin of softening agent (E) when being polymerization.

17. the manufacture method of claim 16 record is characterized in that, also mixes the softening agent of adding as required (E).

18. the manufacture method of claim 14 record, it is characterized in that, (I) be that the powdered resin of resin (A) or the polyvinylidene chloride that contains epoxy compounds (B1) are in the powdered resin of resin (A) at polyvinylidene chloride, add the powder composition in addition that contains glycidyl acrylic resin (B2), after mixing under the intensification condition, (II) in process of cooling, mix the powder that contains glycidyl acrylic resin (B2).

19. the manufacture method of claim 14 record is characterized in that, also mixed ethylene-vinyl acetate copolymer (D).

20. the manufacture method of claim 18 record is characterized in that, after mixing contains the powder of glycidyl acrylic resin (B2) in process of cooling, is cooled to normal temperature, then, and the remix ethylene-vinyl acetate copolymer.

21. being the polyvinylidene chloride based resin composition moulding with each record of claim 1～6, a film, this film form.

22. the film of claim 21 record is characterized in that this film is a biaxially oriented film.