CN1250641C

CN1250641C - Polyvinylidene chloride resin composition, tensile film and its mfg. method

Info

Publication number: CN1250641C
Application number: CNB021598045A
Authority: CN
Inventors: 菅野胜彦; 饭均; 田中保男; 柴田修作
Original assignee: Kureha Corp
Current assignee: Kureha Corp
Priority date: 2001-12-27
Filing date: 2002-12-27
Publication date: 2006-04-12
Anticipated expiration: 2022-12-27
Also published as: KR20030057390A; JP2003192861A; JP3881547B2; KR100899969B1; CN1428371A

Abstract

A scaly inorganic powder of polyvinylidene chloride-based resin composition contains polyvinylidene chloride-based resin, using as liquidus and solid adjuvant at room temperature and method therefor. A stretch film with more than ten reflectance and more than 8% of fog value is produced by scaly inorganic powder of polyvinylidene chloride-based resin composition and method for producing the stretch film using the composition.

Description

Polyvinylidene chloride resin composition, oriented film and manufacture method thereof

Technical field

The present invention relates to contain excellent polyvinylidene chloride resin composition and manufacture method thereof such as flakey inorganic powder, melt processable, stretch process, thermostability, tone.And then, the present invention relates to from the polyvinylidene chloride resin composition that contains the flakey inorganic powder oriented film and manufacture method thereof that form, the metalluster excellence.Oriented film of the present invention is fit to be used as the wrapping material of processed foods such as fish sausage or poultry meat processed goods etc.

Background technology

In order to obtain the formed products of metalluster, known have a method that the resin combination that added metal-powder in the thermoplastic resin is shaped that is used in.Yet, be shaped if be used in the resin combination that contains metal-powder among the polyvinyl chloride (PVC) RESINS chlorine-containing thermoplastic resins such as (hereinafter to be referred as " PVC ") of containing the chlorine atom in the molecule, be difficult to obtain the molding of excellent metalluster.

Can infer, if its reason is that then the micro-chlorine atom that takes place from the chlorine-containing thermoplastic resin this moment can make the cause of metal-powder variable color or blackening with the surface reaction of metal-powder owing to make the resin combination melt-processed at high temperature that contains chlorine-containing thermoplastic resin and metal-powder.

As the method for eliminating above-mentioned shortcoming, open the resin combination that has proposed in the chlorine-containing thermoplastic resin, to contain white pigment and/or transparent white pigment in the clear 54-138048 communique with metal-powder the spy.In this communique, put down in writing and for metal-powder 100 weight parts, added 1～30 weight part white pigment and/or transparent white pigment, just can prevent metal-powder variable color or blackening, thereby obtain the molding of excellent metalluster.

In the embodiment 1～3 of this communique, put down in writing in PVC the title complex that added titanium dioxide powder, Zinc oxide powder or lime carbonate/aluminum oxide mixed powder with aluminium powder and mixed in 150 ℃ with 2 hot-rollings and make the experimental example of the sheet material of metalluster after 10 minutes.In the embodiment 4 of this communique, shown that in PVC the title complex fusion of having added clay with aluminium powder is made of mixing pellet, and made the experimental example of tubing with this pellet with extruding machine.

Like this, in above-mentioned communique, only shown the embodiment as the chlorine-containing thermoplastic resin, and do not shown the embodiment that uses polyvinylidene chloride resin (hereinafter to be referred as " PVDC is a resin ") with PVC.In fact, be that resin and aluminium powder fusion are mixed and formed molding from the thing that mixes if use PVDC, even then interpolation white pigment and/or transparent white pigment also are difficult to obtain the molding of metalluster excellence.Particularly, use that to contain PVDC be that the resin combination of resin and aluminium powder is difficult to form oriented film.

PVDC is a resin because softening temperature and decomposition temperature are approaching, thereby causes decomposition under the melt-processed condition easily, and thermostability is poorer than PVC.Therefore, if with PVDC be resin as the chlorine-containing thermoplastic resin, then be difficult to prevent effectively the variable color or the blackening of the metal-powder that the reaction of the chlorine atom that the thermolysis owing to melt-processed the time takes place causes.If increase the addition of white pigment and/or transparent white pigment for the variable color that prevents metal-powder or blackening, then PVDC is that the shaping thing of resin becomes the tone of band white color head, thereby damages important metalluster.And then, if increase the addition of white pigment and/or transparent white pigment, then PVDC is that the melt processable of resin significantly descends, the resin that contains these pigment partly is trapped in die head exit, then, retentate is sneaked in the shaping thing as the resin resolvent, reduces formed article matter or forms strip pattern, thereby significantly damage the outward appearance of shaping thing.Therefore, the sheet material or the film that are difficult to extrusion molding shaping metalluster and outward appearance excellence.

Open in the flat 11-254607 communique the spy, proposed without mix method and the method for the coated film that vinylidene chloride copolymer that one deck contains 10～60 weight % flakey aluminium films is arranged with the coating method manufacturing of fusion.Specifically, proposed in this communique with weight ratio (a: the method (claim 1) that the dispersion liquid that contained vinylidene chloride copolymer (a) and flakey aluminium (b) in b) 90: 10～60: 40 is applied on the base material film, drying is made the coated film that vinylidene chloride copolymer that one deck contains flakey aluminium films.

Though the manufacture method of putting down in writing in the communique applicable to the manufacture method of the coated film that has vinylidene chloride copolymer to film on the basement membrane (being non-stretched film), can't be applicable to the manufacture method of other molding such as oriented film.

Filming like this can be by forming than lower temperature and short period of time drying after application step.Yet, the resin combination that also contains a large amount of flakey aluminium of 10～60 weight % in vinylidene chloride copolymer (being that PVDC is a resin) is that melt processable, stretch process etc. are bad and be difficult to make such as oriented film, even if made oriented film, bad order or film problem such as are peeled off and also can be revealed.And then in coating method, the flakey aluminium powder comes down to be present in filming with the state that keeps original shape, thereby flakey aluminium is dispersed in the resin imperceptibly.

On the other hand, promptly use the resin combination that has cooperated spherical metal-powder to form molding, also be difficult to obtain the molding of metalluster excellence owing to orientation effect is bad.

PVDC is a resin because the gas barrier excellence, thereby can be configured as the oriented film of single or multiple lift, is widely used for as the wrapping material of processed foods such as fish sausage or poultry meat processed goods etc.In the past, such wrapping material were used the red colour system pigment coloring as a rule, but along with the variation or the region of taste and preference needs etc., people also day by day demand the goods of metalluster such as silver color or metal are arranged.

Yet from above-mentioned usual technical level, even be to contain scaled metal powder end in the resin and make shaping thing such as oriented film at the PVDC of poor heat stability, also can't expect to obtain can gratifying metalluster and the shaping thing of outward appearance.In fact, up to now, also nobody's proposition is the scheme of the oriented film of resin formation metalluster excellence with PVDC.

Summary of the invention

The purpose of this invention is to provide make creating of oriented film with metalluster possible, excellent polyvinylidene chloride resin composition and manufacture method thereof such as melt processable, stretch process, thermostability, tone.

And then, the purpose of this invention is to provide the polyvinylidene chloride resin that has used excellences such as melt processable, the oriented film and the manufacture method thereof of metalluster excellence.

The result that present inventor etc. study with keen determination for achieving the above object, discovery is by to the PVDC that contains special additive being cooperation flakey inorganic powder in the resin, even do not add white pigment or transparent white pigment, also can obtain the oriented film of also non-discoloring resin combination of neither blackening and metalluster excellence.

Particularly, the PVDC that contains fluid additives such as epoxy compounds or softening agent when to polymerization adds solid additive and remaining fluid additive successively, when adding the flakey inorganic powder and prepare mixing material and use this mixing material to form oriented film then, can easily obtain the oriented film of metalluster excellence in the powdex of resin.

Oriented film of the present invention is a reflectivity more than 10, metalluster is excellent and haze value more than 8%, disguised excellent.Oriented film of the present invention can be formed in shrinking percentage at least one direction the heat-schrinkable film 10% or more of dipping in the time of 3 minutes in 100 ℃ the hot water.And then oriented film of the present invention not only has and results from the tone (for example silver color) of flakey inorganic powder, and can by and be adjusted to gold with pigment dyestuff and wait other tone.

According to manufacture method of the present invention, contain the PVDC based resin composition of flakey inorganic powder by stretch process, just can obtain the squamous inorganic powder along surface orientation, texture exquisiteness, uniform hue, disguised high, oriented film that metalluster is arranged.Oriented film of the present invention is different because of orientation effect, demonstrates the heat-shrinkable of excellent metalluster and appropriateness.

The present invention finishes on the basis of these experiences finally.

Therefore,, provide a kind of polyvinylidene chloride resin composition, comprise according to the present invention

(A) polyvinylidene chloride resin,

(B) additive of liquid under at least a normal temperature of selecting form from epoxy compounds and softening agent one group,

(C) under at least a normal temperature of selecting form from the resin that contains epoxy group(ing), lubricant and weighting agent one group the solid additive and

(D) flakey inorganic powder,

Wherein (D) flakey inorganic powder contain proportionally, for polyvinylidene chloride resin 100 weight parts, be 0.03～4 weight part; And, from the epoxy compounds (B) composition with (C) to contain at least a epoxy of selecting in a group that the resin of epoxy group(ing) forms in the composition be that thermo-stabilizer is that ratio with 0.05～6 weight part for polyvinylidene chloride resin 100 weight parts contains.

And then, according to the present invention, provide a kind of oriented film, it is characterized in that it being the oriented film that forms from the polyvinylidene chloride resin composition, wherein

(1) the polyvinylidene chloride resin composition contains the flakey inorganic powder with the ratio of 0.03～4 weight part for polyvinylidene chloride resin composition 100 weight parts,

(2) reflectivity of film is more than 10, and

(3) haze value of film is more than 8%.

And then, according to the present invention, provide a kind of manufacture method of polyvinylidene chloride resin composition, promptly a kind of polyvinylidene chloride resin composition manufacture method that comprises following series of steps:

(I) make vinylidene chloride and can with the monomer copolymerization of its copolymerization, at this moment, in case of necessity under at least a normal temperature of one group that forms from epoxy compounds and softening agent, selecting the additive (B) of liquid in the presence of copolymerization, and then in case of necessity at the additive (B) that adds liquid under at least a normal temperature after the copolymerization, make the step of the powdex of polyvinylidene chloride resin (A)

(II) in this powdex, add the step of solid additive (C) under at least a normal temperature of selecting one group that forms from the resin, lubricant and the weighting agent that contain epoxy group(ing),

(III) in this powdex, add the surplus of the additive (B) of liquid under the normal temperature that uses in case of necessity in the total amount of the additive (B) of liquid under the normal temperature or the step (I) step and

(IV) step of interpolation flakey inorganic powder (D) in this powdex,

And, at least one step of above-mentioned steps (I)～(III), add from (B) composition epoxy compounds and (C) at least a epoxy that the resin that contains epoxy group(ing) in the composition is formed selects in one group be thermo-stabilizer.

And then, according to the present invention, provide a kind of oriented film manufacture method, promptly a kind of manufacture method of the oriented film that comprises following series of steps, forms from the polyvinylidene chloride resin composition:

(III) in this powdex, add the step of the surplus of the additive (B) of liquid under the normal temperature that uses in case of necessity in the total amount of the additive (B) of liquid under the normal temperature or the step (I),

(IV) in this powdex, add flakey inorganic powder (D) step and

(V) use the mixing material that obtains from above steps to make the step of oriented film,

Invent best example

1. polyvinylidene chloride resin (PVDC is a resin)

The PVDC that uses among the present invention be resin be vinylidene chloride (VDC) 60～98 weight % (quality %) and can with the multipolymer of other monomer (comonomer) 2～40 quality % of its copolymerization.The vinylidene chloride homopolymer is that softening temperature and decomposition temperature are extremely approaching, and is difficult to use elasticizer plasticizing.Therefore, by with other comonomer copolymerization, attempt to reach inner plasticising and thermostabilization.

As comonomer, can enumerate for example vinylchlorid; Alkyl acrylate (1～18 of alkyl carbon number) such as methyl acrylate, ethyl propenoate, butyl acrylate, lauryl acrylate; Alkyl methacrylate (1～18 of alkyl carbon number) such as methyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA); Vinyl cyanide bases such as vinyl cyanide; Aromatic ethenyls such as vinylbenzene; The aliphatic carboxylic acid vinyl acetate that carbon numbers such as vinyl-acetic ester are 1～18; The alkyl vinyl ether that carbon number is 1～18; Vinyl polymerizable unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid; But the alkane ester of vinyl polymerization unsaturated carboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid (comprising the part ester, 1～18 of the carbon number of alkyl) etc.

These comonomers can use separately separately, also can be used in combination more than 2 kinds.In these comonomers, be preferably vinylchlorid, methyl acrylate and lauryl acrylate.If the copolymerization ratio of comonomer is too little, and that then inner plasticising becomes is insufficient, melt processable descends, if the copolymerization ratio of comonomer is too big, and then gas barrier descends.The copolymerization ratio of comonomer better is 3～35 weight %, be more preferably 3～25 weight %.

The PVDC that uses among the present invention is the reduced viscosity (η sp/C) of resin, viewpoints such as the melt processable under the situation that is configured as film, stretch process, the suitable property of wrapping mechanism, winter hardiness better are 0.035～0.070 (l/g), be more preferably 0.040～0.067 (l/g), good especially be 0.045～0.063 (l/g).PVDC be the reduced viscosity of resin if too low, then stretch process decline, the mechanical property of oriented film also descends, thereby bad.PVDC is the reduced viscosity Ruo Taigao of resin, and then melt processable descends and can demonstrate painted tendency, thereby bad.

Can be used in combination the different PVDC more than 2 kinds of reduced viscosity is resin.PVDC is in the resin if add the flakey inorganic powder, then melt processable and stretch process decline, thereby in order to improve these performances, it is desirable to be produced on the interior different PVDC more than 2 kinds of reduced viscosity of above-mentioned reduced viscosity scope is the blend of resin.Therefore, can obtain the good oriented film of mechanical property excellence and metalluster.More particularly, for example can enumerate reduced viscosity be 0.035～0.055 so lower PVDC be resin and reduced viscosity be more than 0.055～be the combination of resin like this than higher PVDC below 0.070.

PVDC is a resin, if wish, also can with other resin alloy.As other resin, can enumerate for example vinyl-vinyl acetate copolymer, (methyl) acrylate (being total to) polymkeric substance, MBS etc.As (methyl) acrylate (being total to) polymkeric substance, be preferably (being total to) polymkeric substance of (methyl) alkyl acrylate of 1～18 of alkyl carbon number, be more preferably (methyl) methyl acrylate-(methyl) butyl acrylate copolymer.Other resin for PVDC is resin 100 weight parts, uses with the ratio below 20 weight parts usually.

In these other resins, be preferably vinyl-vinyl acetate copolymer (hereinafter to be referred as " EVA ").As EVA, be preferably vinyl acetate content be preferably 20～40 weight %, more preferably 28～35 weight %, melt flow rate (MFR) (MFR) be preferably 1～50g/10 minute, 10～40g/10 minute EVA more preferably.By being blend EVA in the resin at PVDC, can improve melt processable, sealing intensity etc.The cooperation ratio of EVA for PVDC is resin 100 weight parts, better is 0.5～5 weight part, be more preferably 1～3 weight part.

The PVDC that uses among the present invention is that resin can use any one polymerizations such as suspension polymerization, letex polymerization, solution polymerization synthetic, but in order to form mixing material as powdex, be preferably with suspension polymerization and obtain, viscosity (resin size) in 40～600 mu m ranges is arranged, do not need the resin of pulverising step.Resin size can use standard sieve, measure with the dry screen point-score.PVDC is in the resin, is preferably just to contain antioxidant or softening agent, epoxy compounds etc. when its polymerization.

2. the additive of liquid under the normal temperature

Use epoxy compounds and softening agent additive among the present invention as liquid under the normal temperature (23 ℃).These fluid additives are preferably and use.

As epoxy compounds, can enumerate the material as the thermo-stabilizer use of chlorine-containing resins such as epoxidized vegetable oil, epoxidation animal oil, epoxidized fatty acid ester, epoxy prepolymer.Select in the middle of these liquid down epoxy compounds of normal temperature to use separately separately or be used in combination more than 2 kinds.

As epoxidized vegetable oil that uses among the present invention and epoxidation animal oil, can use the natural animal-plant oil of unsaturated link(age) to carry out epoxidation with hydrogen peroxide or Peracetic Acid etc. and make two key modifications become oxyethane ring person.As epoxidized vegetable oil, be preferably epoxidised soybean oil, epoxidised linseed oil etc.

As epoxidized fatty acid ester, can enumerate the epoxide of unsaturated fatty acid esters such as epoxidation octyl stearate.As epoxy prepolymer, dihydroxyphenyl propane glycidyl ether etc. is arranged.In these epoxy compoundss, in the packaging material for food field, good especially is epoxidized vegetable oil.

Under the situation of using the epoxy compounds of liquid under the normal temperature, for PVDC is resin 100 weight parts, use with the cooperation ratio of 0.1～6 weight part, better 0.5～5 weight part, better 1～4 weight part usually.If the cooperation ratio of epoxy compounds is too big, then be easy to generate ooze move, adhesion, gas barrier descend, if the cooperation ratio of degradation shortcoming, epoxy compounds then makes the abundant plastifying effect of PVDC diminish or makes melt processable or effect that thermostability is improved diminishes too little under the tone.

Epoxy compounds is to be that PVDC that the polymerization procedure of resin generates contains in the powdex of resin or is the powdex blend of resin or the method for these combinations covered in the resin combination with PVDC by making it at PVDC.In order to make epoxy compounds can be to contain in the powdex that generates in the polymerization procedure of resin at PVDC, can make vinylidene chloride and can with the copolymerization and/or after copolymerization, add epoxy compounds and make the powdex that PVDC is a resin like this in the presence of epoxy compounds of the monomer of its copolymerization.Make vinylidene chloride and can with the monomer of its copolymerization under the situation of copolymerization in the presence of the epoxy compounds, be in polymerization initial stage, polymerization way and add epoxy compounds and carry out copolymerization any one above period in polymerization later stage.In order to add epoxy compounds, generally be epoxy compounds to be added to contain in the soup compound that generates multipolymer to some extent in copolymerization.

In the middle of these, be resin and the blend stably of flakey inorganic powder, be preferably and in PVDC is the polymerization procedure of resin, contain epoxy compounds and preparation powdex in order to make PVDC, and the surplus of when blend, in powdex, appending epoxy compounds.If wish, also the total amount of employed epoxy compounds can be added when the polymerization or is blended in the powdex.

As softening agent; dioctyl phthalate (DOP), Tributyl O-acetylcitrate, Uniflex DBS, dioctyl sebacate, acetylize monoglyceride, acetylated diglycerides, acetylize triglyceride level be can enumerate and these central 2～3 kinds acetylize glyceride types, hexanodioic acid and 1 contained; 3-butyleneglycol, hexanodioic acid and 1,4-butyleneglycol and these central polyester such as mixture more than 2 kinds are that softening agent is as representative.Use and be the liquid person in these softening agent under the normal temperature.Under the situation of using softening agent, for PVDC is resin 100 weight parts, use with the cooperation ratio of 0.05～10 weight part usually.

Softening agent is to be that PVDC that the resin polymerization step generates contains in the powdex of resin or is the powdex blend of resin or the method for these combinations covered in the resin combination with PVDC by making it at PVDC.In order to make softening agent can be to contain in the powdex that generates in the polymerization procedure of resin at PVDC, can make vinylidene chloride and can with the copolymerization and/or after copolymerization, add softening agent and make the powdex that PVDC is a resin like this in the presence of softening agent of the monomer of its copolymerization.Make vinylidene chloride and can with the monomer of its copolymerization under the situation of copolymerization in the presence of the softening agent, be in polymerization initial stage, polymerization way and add softening agent and carry out copolymerization any one above period in polymerization later stage.In order after copolymerization, to add softening agent, generally be softening agent to be added to contain in the soup compound that generates multipolymer to some extent.

In the middle of these, be preferably at polymerization procedure softening agent is contained in PVDC is the powdex of resin, and the softening agent that blend is appended when blend, good especially is when the blend also remaining softening agent of blend.If wish that the total amount of employed softening agent both can be added, and also can be blended in the powdex when polymerization.

In the present invention,, can use any one party or two sides in epoxy compounds and the softening agent, it is desirable to use two sides as the additive of liquid under the normal temperature.

3. solid additive under the normal temperature

In the present invention, as the following solid additive of normal temperature (23 ℃), use select one group that forms from the resin, lubricant and the weighting agent that contain epoxy group(ing) at least a.The solid resin that contains epoxy group(ing) works as thermo-stabilizer at normal temperatures, and generally uses with powder morphology.

The resin that contains epoxy group(ing) is the resin that contains at least one epoxy group(ing), is preferably (methyl) acrylic resin (hereinafter to be referred as " GMA ") that contains glycidyl in the middle of these.(methyl) acrylate that contains glycidyl has the better characteristic as thermo-stabilizer.

As (methyl) acrylic resin that contains glycidyl, but be preferably the glycidyl ester that contains the vinyl polymerization unsaturated organic acid multipolymer as copolymer composition.(methyl) acrylate of (methyl) acrylate etc. that this multipolymer typically contains (methyl) glycidyl acrylate or do not contain glycidyl is as copolymer composition, thereby is referred to as to contain (methyl) acrylic resin of glycidyl among the present invention.Be noted that, vinyl polymerization means the method that obtains polymkeric substance by the repetition addition reaction of the compound that carbon-to-carbon double bond is arranged, and " but glycidyl ester of vinyl polymerization unsaturated organic acid " extensively comprises vinyl compound for example, vinylidene compound etc. has the compound of carbon-to-carbon double bond partially.

Contain preferably glycidyl (methyl) but acrylic resin be the glycidyl ester of vinyl polymerization unsaturated organic acid and (methyl) acrylate that does not contain glycidyl and/or can be the multipolymer of unsaturated monomer with other ethene of these copolymerization.

But, can enumerate for example (methyl) glycidyl acrylate of glycidyl methacrylate, glycidyl acrylate, methacrylic acid Beta-methyl glycidyl ester, vinylformic acid Beta-methyl glycidyl ester etc. as the glycidyl ester of vinyl polymerization unsaturated organic acid; The glycidyl ester of unsaturated carboxylic acids such as toxilic acid, fumaric acid, methylene-succinic acid; Deng.But the glycidyl ester of these vinyl polymerization unsaturated organic acids can use separately or be used in combination more than 2 kinds separately.Be preferably (methyl) acrylate that glycidyl methacrylate etc. contains glycidyl in the middle of these.

As (methyl) acrylate that does not contain glycidyl, can enumerate for example alkyl acrylate (1～18 of the carbon number of alkyl) such as methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, vinylformic acid lauric acid, stearyl acrylate ester; Alkyl methacrylate such as methyl methacrylate, butyl methacrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate(LMA), methacrylic acid stearyl ester (1～18 of the carbon number of alkyl) etc.In the middle of these, be preferably methyl methacrylate or methyl acrylate etc.These (methyl) acrylate can be used singly or two or more kinds in combination separately.

But other ethene as copolymerization is unsaturated monomer, can enumerate vinylbenzene, vinyl cyanide, vinylformic acid, vinylchlorid, vinylidene chloride, alkyl vinyl ether etc.These ethene are that unsaturated monomer can be used singly or two or more kinds in combination separately.In the middle of these, be preferably vinylbenzene.

As (methyl) acrylic resin that contains glycidyl, but be preferably glycidyl ester 10～50 weight % of vinyl polymerization unsaturated organic acid and can be the multipolymer of unsaturated monomer 50～90 weight % with at least a ethene of its copolymerization.In such multipolymer, but be more preferably glycidyl ester 10～50 weight % of vinyl polymerization unsaturated organic acid, (methyl) acrylate 0～90 weight % and other ethene that does not contain glycidyl is the multipolymer of unsaturated monomer 0～50 weight %, but good especially be that glycidyl ester 10～50 weight % of vinyl polymerization unsaturated organic acid, (methyl) acrylate 10～90 weight % and other ethene that does not contain glycidyl are the multipolymer of unsaturated monomer 0～40 weight %.Disperseed the painted of pigment then can improve pigment-dispersing in such multipolymer in advance if be produced on resin combination (tinting material masterbatch), thereby better.

Contain (methyl) of glycidyl the glycidyl monomer that contains in the acrylic resin is but that the content of representational vinyl polymerization unsaturated organic acid glycidyl ester better is 10～50 weight %, this content then is compatibility decline or the thermostability decline of resin combination or the tone generation variation of passing in time easily of packaging film of resin with PVDC as if very little.If the content that contains the glycidyl monomer component is too many, then occurs in to disperse bad in the resin combination or produce bad order such as flake easily in oriented film.

As the concrete example 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-vinylidene chloride copolymer etc.

The molecular weight that contains (methyl) acrylic resin of glycidyl is not particularly limited, but weight-average molecular weight (Mw) is 5,000～50 normally 3,000～100,000, better, and about 000.A fortune weight-average molecular weight (Mw) condensation product (flake) then takes place in the oriented film easily, and if too little, then oriented film adhesion each other takes place easily if too big, and wrapping mechanism is fitted the property variation.

The oxirane value that contains (methyl) acrylic resin of glycidyl is not particularly limited, can be more than 0.3, but especially under the situation of less than 0.3, pigment-dispersing, tone, thermostability, processibility, gas barrier etc. are carried out balance to heavens easily, thereby better.This oxirane value more fortunately below 0.25, better below 0.2.As a rule, oxirane value can obtain good result when 0.05～0.2 left and right sides.If the oxirane value of (methyl) acrylic resin that contains glycidyl is too big, flake takes place easily then or the shaping beyond the region of objective existence that becomes is easily seen bad.Otherwise if oxirane value is too little, and then the effect of thermostability descends.

The acrylic resin that contains glycidyl, for PVDC is resin 100 weight parts, normally 0.05～5 weight part, better be 0.08～3 weight part, be more preferably 0.1～2 weight part.If this cooperation ratio is too little, and then melt processable or thermostability reduce easily.If this cooperation ratio is too big, and then the gas barrier of oriented film or winter hardiness descend, and is difficult to obtain distinct metalluster.

PVDC based resin composition of the present invention must contain that either party or two sides are thermo-stabilizer as epoxy in the resin that solid under the epoxy compounds of liquid under the normal temperature and the normal temperature contains epoxy group(ing).Epoxy is the content of thermo-stabilizer, for PVDC is resin 100 weight parts, is at 0.05～6 weight part, 0.08～5 weight part, better in the scope of 0.1～4 weight part more fortunately.Epoxy be the content of thermo-stabilizer if too little, the thermostability variation of PVDC based resin composition then, the processing that the is shaped difficulty that becomes also becomes the reason of blackening simultaneously, and significantly damages the metalluster of oriented film.Epoxy is if that containing of thermo-stabilizer is proportional too big, and the then gas barrier of oriented film or winter hardiness decline perhaps has to become the former therefore anxiety that produces flake.

As lubricant, with regard to being suitable for melt-processed person that PVDC is a resin, can enumerate wax classes such as oxidized polyethlene wax, paraffin, polyethylene wax, montanic acid ester type waxes, montanic acid calcium; Fatty acid esters such as monoglyceride.And with regard to those are particularly suitable for melt-processed person that PVDC is a resin, can enumerate the monoamide of lipid acid such as stearylamide or diamide etc.Under situation about making with lubricator, can be used singly or two or more kinds in combination separately, and common cooperation ratio with 0.001～2 weight part, better 0.05～1 weight part is used for PVDC is resin 100 weight parts.

As weighting agent, can enumerate silicon-dioxide, lime carbonate etc.Silicon-dioxide or lime carbonate as the satin face agent, give film medicament etc. and work with the oilness on wrapping mechanism.Silicon-dioxide also plays the effect of inorganic lubricant.And then silicon-dioxide can prevent effectively that when blend EVA EVA from condensing each other.Under the situation of using these weighting agents, for PVDC is resin 100 weight parts, use with the cooperation ratio of 0.001～1 weight part, better 0.03～0.5 weight part usually.

4. flakey inorganic powder

As the flakey inorganic powder, can enumerate mica, flaky graphite, scaled metal powder end etc.In the middle of these, be preferably the flakey metal, be more preferably the flakey aluminium powder.

By using the flakey inorganic powder, can obtain the resin combination and the oriented film of desirable tone, metalluster.The flakey inorganic powder demonstrates the extremely thin shape of thickness direction size (b) for the face direction size (a) of its powder particle.Its ratio (a/b) more fortunately more than 10 times, better more than 30 times, its upper limit is about 100 times.

The average particle thickness of flakey inorganic powder better is 0.15～0.70 μ m, be more preferably 0.18～0.60 μ m.The median size of flakey inorganic powder better is 1～100 μ m, be more preferably 3～40 μ m.The flakey inorganic powder it is desirable to, during with the standard sieve screening of nominal size 45 μ m, the sieve percent of pass more fortunately more than 70%, better more than 80%.The median size of flakey inorganic powder etc. can be measured with laser diffractometry.In laser diffractometry, can disperse sample, measure with ethanol with a day machine dress corporate system particle size distribution device Microtrack FRA9220 type.

Flakey inorganic powders such as flakey aluminium powder can carry out surface treatment when it is made or after making.Representational in the surface treatment is that higher fatty acid is handled.Higher fatty acid is preferably C such as stearic acid or oleic acid ₁₄～C ₂₂Lipid acid.Higher fatty acid is preferably under the normal temperature and is solid, and can give the PVDC based resin composition with appropriate oilness with improve melt processable.Flakey inorganic powder with higher fatty acid is handled with under the situation of pigment dyestuff, can improve the dispersiveness of pigment dyestuff also.And then, by carrying out the surface treatment of flakey inorganic powder, can suppress the oxidation stain of this flakey inorganic powder or the variable color that causes with the chlorine atomic reaction etc.

The flakey inorganic powder for PVDC is resin 100 weight parts, uses with the cooperation ratio of 0.03～4 weight part, better 0.05～3 weight part.The cooperation ratio of flakey inorganic powder then is difficult to obtain the molding such as oriented film of desired metalluster as if too little.If the cooperation ratio of flakey inorganic powder is too big, and then the processibility of melt processable or stretch process etc. descends.And then if the cooperation ratio of flakey inorganic powder is too big, and the lip-deep thin layer that then is easy to generate molding such as oriented film is peeled off or shortcoming such as the puckery sense of powder.The cooperation ratio that makes the flakey inorganic powder just can obtain the molding such as oriented film of the metalluster excellence of tones such as silver color in above-mentioned scope.And then the cooperation ratio that makes the flakey inorganic powder is also used a small amount of pigment dyestuff simultaneously in above-mentioned scope, can give the metalluster of desired tones such as gold.

Even metal-powder, if adopt spherical metal-powder, then except that the operability of itself is had any problem, the melt processable that also demonstrates the PVDC based resin composition has downtrending and stretch process deterioration and then can not obtain the oriented film of metalluster excellence.Spherical metal-powder like this is scattered in the gasoline usually.

5. pigment dyestuff

According to the present invention, can obtain a kind of molding that metalluster is arranged, it not only has the tone of flakey inorganic powder in the shaping things such as being attributable to oriented film, and has the gold because of also producing with flakey inorganic powder and pigment dyestuff to wait other tone.

As pigment dyestuff, can enumerate pigment dyestuffs such as azo system, phthalocyanine system, quinacridone.Be preferably organic red pigment, yellow organic pigment and the two combination in the middle of these.

And if with flakey inorganic powder and pigment dyestuffs such as organic red pigment and/or yellow organic pigment such as flakey aluminium powders, then can obtain having for example golden metalluster of tone that results from beyond the tones such as silver color of flakey inorganic powder and the oriented film of more bright-coloured color harmony feeling of high class is arranged.

Adding under the situation of pigment dyestuff, its cooperation ratio better is 0.001～3 weight part for PVDC is resin 100 weight parts, be more preferably 0.05～2 weight part.

6. other additive

Can also add other pigment, other thermo-stabilizer, tensio-active agent, antioxidant, other stablizer, UV light absorber, DH adjustment agent etc. in resin combination of the present invention or the oriented film in case of necessity.As other pigment, can enumerate for example zinc oxide, magnesium oxide, clay, talcum etc.

As tensio-active agent, can enumerate for example nonionic surface active agent such as sorbitan fatty acid esters, glycerol fatty acid ester, polyglycerol fatty acid ester, polyoxyethylene sorbitan fatty acid esters etc., can use in right amount in case of necessity.Glycerol fatty acid ester (ester, diester, three esters), sorbitan fatty acid esters (ester, diester, three esters) etc. play the effect of wrapping material with the meat stripper of oriented film.These can be used singly or two or more kinds in combination separately.

As antioxidant, can enumerate various tocopherols, 2 such as α, β, γ, δ, 6-di-tert-butyl-4-methy phenol (BHT), two (3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid) triethyleneglycol ester (Ciba-Geigy corporate system, Irganox 245), 2,4-dimethyl-6-S-alkylphenol, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol and these mixture phenol such as (Ciba-Geigy corporate systems, Irganox 1141) are antioxidant; Thiodipropionic acid, thiodipropionic acid distearyl ester thioethers such as (DSTDP) are antioxidant; Phosphorous acid esters such as dimerization phosphorous acid distearyl ester pentaerythritol ester are antioxidant etc.Antioxidant for PVDC is resin 100 weight parts, uses with the ratio of 0.0001～0.05 weight part usually.

As other stablizer, can enumerate inorganic bases such as magnesium hydroxide, magnesium oxide, Linoleic acid dimer calcium salt, calcium phosphate powder; Organic monoacid salts such as citric acid, limonin metal-salt; Edetate classes etc. can be used under each comfortable suitably situation in right amount.

As UV light absorber, can enumerate 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole etc., can use in right amount in case of necessity.

Adjust agent as pH, can enumerate trisodium phosphate, Sodium Acid Pyrophosphate etc., for PVDC was resin 100 weight parts, ratio that can 0.5 weight part was used.PH adjusts agent and uses when PVDC is resin polymerization usually.

Above-mentioned epoxy compounds, softening agent, tensio-active agent etc. work as the dispersing auxiliary of the dispersiveness that is used for improving flakey inorganic powder or pigment dyestuff etc., but in addition, as dispersing auxiliary, can also enumerate glycerine or propandiols; The oligopolymer of aliphatics hydrocarbon system or aromatic series hydrocarbon system or polymkeric substance etc.In the middle of these, be preferably C ₂～C ₈The aliphatic hydrocarbon oligopolymer.The good especially aqueous aliphatic hydrocarbon oligopolymer that is to use weight-average molecular weight 300～5000.Dispersing auxiliary not only has the dispersiveness that improves flakey inorganic powder or pigment dyestuff and prevents the effect of airborne dust, and the effect that reduces melt processing temperature is arranged.Dispersing auxiliary for PVDC is resin 100 weight parts, uses with the ratio below 2 weight parts usually.

These additives add usually, are blended in the powdex that PVDC is a resin, but except that such blend step or together with the blend step, can also make it to cover in the PVDC based resin composition by in the soup compound after in its polymerization procedure, adding polymerization in the monomer mixture to or adding polymerization to or the method for these combinations.

7.PVDC based resin composition and manufacture method thereof

PVDC based resin composition of the present invention is a kind of resin combination that contains following ingredients: (A) polyvinylidene chloride resin, (B) additive of liquid under at least a normal temperature of selecting form from epoxy compounds and softening agent one group, (C) solid additive and (D) flakey inorganic powder under at least a normal temperature of selecting form from the resin that contains epoxy group(ing), lubricant and weighting agent one group.

In the PVDC based resin composition of the present invention (D) flakey inorganic powder to contain proportional be 0.03～4 weight part for polyvinylidene chloride resin 100 weight parts.And then PVDC based resin composition of the present invention is that to contain the epoxy compounds from (B) composition and (C) contain at least a epoxy of selecting in a group that the resin of epoxy group(ing) forms in the composition be thermo-stabilizer as must composition.Epoxy is the amount of thermo-stabilizer, as mentioned above, for polyvinylidene chloride resin 100 weight parts, is 0.05～6 weight part.PVDC based resin composition of the present invention can further contain (E) pigment dyestuff and (F) EVA etc. in case of necessity.

In PVDC based resin composition of the present invention, the flakey inorganic powder is preferably the flakey aluminium powder.And then PVDC based resin composition of the present invention is preferably, and PVDC is that resin is a powdex, and the form of resin combination is a mixing material.Before melt-processed, if each composition fusion is mixed, then PVDC is that resin becomes and decomposes easily, and is easy to generate shortcomings such as the variable color of flakey inorganic powder or blackening.From PVDC is the thermostability viewpoint of resin, can contain the epoxy compounds of (B) composition and (C) either party or two sides in the resin that contains epoxy group(ing) of composition in the PVDC based resin composition.

According to the present invention, better can make the PVDC based resin composition with following step (I)～(IV):

(III) in this powdex, add the total amount of the additive (B) of liquid under the normal temperature or under the normal temperature that step (I) is used in case of necessity the surplus of the additive (B) of liquid step and

(IV) step of interpolation flakey inorganic powder (D) in this powdex.

Adding the epoxy compounds from (B) composition and (C) contain at least a epoxy of selecting in a group that the resin of epoxy group(ing) forms in the composition at least one step of above-mentioned steps (I)～(III) is thermo-stabilizer.Epoxy is that the interpolation of thermo-stabilizer is or is present in the copolymerization system, or implements in the powdex by adding to.The usage ratio of each composition is identical with above-mentioned PVDC based resin composition.

PVDC is that resin is preferably the additive that adds liquid under the normal temperature when synthetic in monomer composition and carries out polymeric.Even in this case, be preferably the additive that when blend, also appends liquid under the normal temperature.Generally speaking, be preferably, adding as an agent part of liquid used when the polymerization under the normal temperature, and rest part uses when blend.But the total amount of the additive of liquid also can be when polymerization or once add during blend under the normal temperature.The cooperation ratio of each composition is better selected in above-mentioned scope.

Better other manufacture method of PVDC based resin composition of the present invention is, making PVDC is the powdex and the various additive blend of resin, and is that resin is kept the shape resin combination (mixing material) that makes powder under the condition as the form of powdex making PVDC.Blending temperature is better adjusted to below 85 ℃, is better adjusted to below 80 ℃.By blend, the additive of liquid under the normal temperature such as epoxidized vegetable oil or softening agent is absorbed in the powdex.Under the normal temperature additive of powder when blend, be attached to powdex around.

In step (I) with (III), at normal temperatures under the situation of the additive portion-wise addition of liquid, the interpolation ratio (weight ratio) of fluid additive it is desirable in each step, be preferably 10: 90～90: 10, more preferably 20: 80～80: 20, good especially be 30: 70～70: 30.

In order to adjust tone, in step (IV), flakey inorganic powder (D) can be added together with pigment dyestuff (E).In addition, in step (III), also can use conducts such as containing (methyl) pigment dyestuff, that contain glycidyl acrylic resin composition to contain the resin of epoxy group(ing).As flakey inorganic powder (D), be preferably the flakey aluminium powder.And then, in step (IV) afterwards, can also dispose the step of further interpolation vinyl-vinyl acetate copolymer (F).

PVDC based resin composition of the present invention, because excellences such as melt processable, stretch process, thermotolerance, thereby can wait to be shaped by melt extrusion, stretch process and make various molding.PVDC based resin composition of the present invention be applicable to usually oriented film shaping, can make the heat-schrinkable film of metalluster excellence.

8. the manufacture method of oriented film

From the oriented film that PVDC based resin composition of the present invention forms,, just can make preferably by comprising the manufacture method of following steps (I)～(V):

(III) in this powdex, add the total amount of the additive (B) of liquid under the normal temperature or under the normal temperature that step (I) is used in case of necessity the step of the surplus of the additive (B) of liquid,

(IV) in this powdex, add flakey inorganic powder (D) step and

(V) mixing material that obtains with above steps is made the step of oriented film.

Adding the epoxy compounds from (B) composition and (C) contain at least a epoxy of selecting in a group that the resin of epoxy group(ing) forms in the composition at least one step of above-mentioned steps (I)～(III) is thermo-stabilizer.The usage ratio of each composition is identical with above-mentioned PVDC based resin composition.

Step (I)～(IV) with the same condition of above-mentioned PVDC based resin composition manufacture method under implement.At step (I), the PVDC that contains the additive of liquid under at least a normal temperature of selecting one group that forms from epoxy compounds and softening agent when being preferably synthesized polymer is the powdex of resin, and epoxy compounds and softening agent both are included in the powdex that PVDC is a resin.

In step (II), add the resin, lubricant, weighting agent or these the mixture that contain epoxy group(ing).At step (III), add the surplus of epoxy compounds and/or softening agent, add the two but be preferably.

The additive of liquid also can use its total amount under the normal temperature in step (I) or step (III), but also can use in each step in batches.In this case, the interpolation ratio (weight ratio) of these fluid additives it is desirable in step (I) and step (III), better 10: 90～90: 10, better 20: 80～80: 20,30: 70 especially～70: 30.By at step (III) annex solution body additives, can significantly improve the dispersiveness of flakey inorganic powder, and can suppress the variable color or the blackening of flakey inorganic powder.

Add the flakey inorganic powder in step (IV).Like this, just prepared powdery resin composition (mixing material).Therefore, in step (II)～(IV), having adopted and having made PVDC is the temperature condition that the powdex of resin can keep its powder shape.The preparation of mixing material can be undertaken by for example using blending machines such as oar blade type blending machine, strip-type blending machine, Han Xieer mixing machine that each composition is mixed.

At step (IV), the flakey inorganic powder is added together with pigment dyestuff.And then pigment dyestuff also can add as the resin that contains epoxy group(ing) with containing resin combination pigment dyestuff, that contain epoxy group(ing) in step (III) except that step (IV) is added in the powdex.The step of further interpolation vinyl-vinyl acetate copolymer (F) can be set in step (IV) afterwards.

At step (V), form oriented film with mixing material.Before stretch process, also mixing material can be sieved, remove the oversize particle of cohesion.As the manufacturing process of oriented film, the blow extrusion moulding method that better employing is for example carried out with the round mouth die head according to well-established law etc.

Stretching can be carried out at least one direction of principal axis, but better carries out biaxial stretch-formed.Biaxially oriented film demonstrates heat-shrinkable, thereby, be suitable as the heat shrinkable package material.And then, but biaxially oriented film is suitable as the heat-resistant film of boiling.Under biaxial stretch-formed situation, be preferably the stretching ratio that reaches vertical (MD) 2～5 times, horizontal (TD) 2～5 times.Laterally the stretching ratio of (TD) is as if the stretching ratio greater than vertical (MD), and then stretch process is carried out easily.Therefore, under with the situation of oriented film, tightly wrap weighting materials such as processed food because of thermal contraction, can bring into play bright-coloured metalluster as wrapping material.

Oriented film thickness, with regard to single thin film, normally 5～50 μ m, better be 10～30 μ m.Oriented film, different because of purposes, also can be used as bilayer film and use.

9. oriented film

Oriented film of the present invention is the oriented film that forms from the PVDC based resin composition that contains the flakey inorganic powder.In the oriented film of the present invention, containing of flakey inorganic powder is proportional, for polyvinylidene chloride resin 100 weight parts, is 0.03～4 weight part.Oriented film of the present invention has characteristic as described below, thereby better.

(1) oriented film of the present invention is that reflectivity of optical thin film is more than 10, more fortunately more than 15.Reflectivity of optical thin film is high more, shows that metalluster is big more.As a rule, reflectivity is about 20～55.The upper limit of reflectivity normally about 60.

(2) oriented film of the present invention is that the film haze value is more than 8%, more fortunately more than 10%.The film haze value is high more, shows that hidden rate is high more.The upper limit of haze value is about 95%.As a rule, haze value is 15～90%.

(3) oriented film of the present invention, the shrinking percentage that is preferably when flooding 3 minutes in 100 ℃ hot water is more than 10% at least one direction.When oriented film of the present invention is biaxially oriented film, be preferably that vertically (MD) percent thermal shrinkage is 20～30%, laterally (TD) percent thermal shrinkage is 15～25%.The percent thermal shrinkage of oriented film of the present invention is that appropriateness is high, thereby can wrap tightly weighting material under as the situation of wrapping material, thereby the commodity of metalluster excellence can be provided.

(4) oriented film of the present invention under the situation of observing with scanning electronic microscope (SEM) photo, is preferably, and flakey inorganic powders such as flakey aluminium powder are as the microparticulate in particle diameter 1～50 μ m, better 1～35 mu m range.According to manufacture method of the present invention, when mixing material prepares or add man-hour flakey inorganic powder can be by fine pulverizing.Because the miniaturization of such flakey inorganic powder, when evenly spreading in the PVDC based resin composition, can obtain metalluster excellence, oriented film that disguise is high with a small amount of flakey inorganic powder.

(5) oriented film of the present invention when containing flakey inorganic powders such as flakey aluminium powder, shows the metalluster of silver color tone usually.If contain flakey inorganic powder and pigment dyestuff simultaneously, then can obtain having the oriented film of the metalluster of desired tone in addition.For example, when using organic red pigment and/or yellow organic pigment, can obtain the oriented film of golden metalluster as pigment dyestuff.Pigment dyestuff for PVDC is resin 100 weight parts, uses with the ratio of 0.001～3 weight part usually.

(6) oriented film of the present invention is the gas barrier excellence, better is 10～25cm according to ASTM D 3985 at the oxygen permeability of 23 ℃ of mensuration ³/ m ²About 24 hours atm.

It is thermo-stabilizer that oriented film of the present invention, the ratio with 0.05～6 weight part of being preferably for polyvinylidene chloride resin 100 weight parts contain at least a epoxy of selecting a group that resin that solid under the epoxy compounds of liquid under normal temperature and the normal temperature contains epoxy forms.

Oriented film of the present invention no matter as single thin film or multilayer film, all is applicable to the wrapping material of processed foods such as fish sausage, poultry meat processed goods etc.Owing to can and use flakey inorganic powder and pigment dyestuff, thereby can make the wrapping material desired tone, the metalluster excellence that have except that silver color.

The main using method of oriented film is overlappingly to become two films with 2 pieces behind inflation, and the edge section at film two ends is cut, and forms cylindric limit with the wrapping mechanism limit and seals, and fills content and clamping two ends then and obtains the wrapping material of wrapping body.Oriented film is fit to be used as the wrapping material of processed foods such as fish sausage, poultry meat processed goods etc.

Embodiment

Below show embodiment and comparative example, be described more specifically the present invention, but the present invention is not limited to these embodiment.The evaluation method of using among the present invention is as follows:

(1) reduced viscosity

PVDC is that resin is after solvent carries out extraction treatment with Soxhlet's extractor, to be sample with dry thing with methyl alcohol, uses ubbelohde viscometer, is being that solvent, resin concentration are 4g/L, to measure temperature be to measure reduced viscosity under 30 ℃ the condition with the hexanaphthene.Than dense degree is to show that PVDC is an index of the polymerization degree of resin, and its value is big more, shows that the polymerization degree is high more.

(2) extrudable property

Resin combination (mixing material) the extruding machine melt extrusion of screw diameter 40mm.Observe it and extrude situation, by the extrudable property of following benchmark evaluation.

Zero: the change of motor load or extrusion capacity is few, can stably extrude,

△: the change instability of motor load or extrusion capacity.

(3) tensility

Preheating is flooded in the blank that melt extrudes into tubulose and obtain cold water quenching then in normal-temperature water.Then, blank carries out biaxial stretch-formed with the stretching ratio that vertical and horizontal are respectively 3.0 times and 4.5 times with inflation method.The biaxially oriented film that obtains like this folds, reels with up-coiler with the lax of certain %.Tensility is by following benchmark evaluation.

Zero: no stretching inequality or tone inequality, stably stretch process;

*: the flake as the pigment condensation product takes place in a large number, is difficult to stretch process stably.

(4) metalluster

Film sample is placed on the table, estimate metalluster with visual method.Judge with the evaluation more than 7 people.Metewand is as follows.

Zero: disguised excellent, show bright-coloured metalluster;

△: disguise or metalluster are arranged, though practical no problem, poor slightly;

*: do not have metalluster, film surface is coarse, does not have light.

(5) reflectivity (700nm)

With spectrophotometer (Colorcomc type, the industrial's system of refining big day),,, ask its mean value with the L value (n=5) of black-envelope (Black pack) reflection method mensuration 700nm to being cut into the film sample of the square size of 5mm.The value of reflectivity is big more, shows that the metalluster of film is big more.

(6) haze value (%)

With turbidometer (NDH-300A type, Japanese electric look industrial system),, measure haze value (mean value of n=5) to being cut into the film sample of the square size of 5mm.The value of haze value is big more, shows that disguise is big more.

(7) thin layer is peeled off

On the length direction of film sample, behind the scotch tape of stickup length 10cm, scotch tape is peeled off from film.The situation of peeling off on viewing film sample surface is pressed following benchmark evaluation at this moment.The film that easy generation thin layer is peeled off is difficult to become the film that bright-coloured metalluster is arranged.

Zero: even stripping tape, film is not stripped from yet;

△: during stripping tape, the thin layer on stripping film surface partly;

*: during stripping tape, thin layer all takes place whole film surface peels off.

(8) hot water shrinkage

Film sample floods in 100 ℃ hot water after 3 minutes and takes out, and measures vertically (MD) and the laterally shrinking percentage of (TD) respectively.

Embodiment 1

(1) preparation of mixing material

Powdex with PVDC (2) (vinylidene chloride (VD)/vinylchlorid (VC)=88/12 (weight %), reduced viscosity=0.058) is a resin as PVDC.During the powdex polymerization, for PVDC is resin 100 weight parts, contain epoxidised linseed oil (O-180) 0.3 weight part and Uniflex DBS 3.5 weight parts, thereby reached these ratios.

In the blending machine, drop into powdex, add lubricant (montanic acid calcium) 0.15 weight part as solid additive under the normal temperature.Add the additive of epoxidised linseed oil 1.7 weight parts then as liquid under the normal temperature.Then, flakey aluminium powder (median size 14 μ m, the ratio (a/b) of face direction size (a) and thickness direction size (b)=about 36, stearic acid surface treatment product) 0.8 weight part is added on heated and stirred limit, limit.Each composition is warming up to while mixing after 85 ℃, makes the mixture cooling.Then, mixture is removed coagulated particles with the screening of 10 mesh sieves.The addition of each composition is listed in the table 1.The sorbitan fatty acid esters of the distearylthiodi-propionate of Irganox 245,0.01 weight part of use 0.02 weight part and 0.1 weight part is as other additive for PVDC is resin 100 weight parts.

(2) manufacturing of oriented film

With the diameter 90mm extruding machine that has the vacuum funnel (after adjusting to vacuum pressure=pact-680mmHg), melt extruding the mixing material of above-mentioned preparation circlewise, use the cooling tank quenching, then by the warm water bath, being pressed into air then between 2 groups of different nip rolls of surface rotating speed makes it to expand, carry out with vertical 2.5 times, horizontal 4.2 times stretching ratio biaxial stretch-formed, thereby make oriented film.Evaluation result is listed in the table 1.

Embodiment 2

Remove (VD/VC=88/12 (weight %) with PVDC (1), reduced viscosity=0.063) 85 weight parts and PVDC (3) (VD/VC=83/17 (weight %), reduced viscosity=0.052) each powdex of 15 weight parts (adding up to 100 weight parts) replacement PVDC (2) is outside the resin as PVDC, equally carry out with embodiment 1, prepared mixing material, made biaxially oriented film then.The results are shown in Table 1.

Embodiment 3

Remove with (methyl) acrylic resin (GMA that contains glycidyl; Glycidyl methacrylate-methyl methacrylate-styrene-propene acid butyl ester (30/31/31/8 weight %) multipolymer) 1 weight part replaces lubricant 0.15 weight part as solid additive under the normal temperature, and when making blend the addition of epoxy linseed oil outside 1.7 weight parts become 0.7 weight part, equally carry out with embodiment 1, prepare mixing material, made biaxially oriented film then.The results are shown in Table 1.

Embodiment 4

Except that replacing lubricant as the solid additive under the normal temperature with weighting agent (lime carbonate), equally carry out with embodiment 1, prepared mixing material, make biaxially oriented film then.The results are shown in Table 1.

Comparative example 1

The addition of de-scaling flake aluminum equally carries out with embodiment 1 outside 0.8 weight part becomes 0.01 weight part, has prepared mixing material, makes biaxially oriented film then.The results are shown in Table 1.

Comparative example 2

The addition of de-scaling flake aluminum equally carries out with embodiment 1 outside 0.8 weight part becomes 5 weight parts, has prepared mixing material, makes biaxially oriented film then.The results are shown in Table 1.

Table 1

Form (weight part)	Embodiment				Comparative example
	Embodiment				Comparative example		1	2	3	4	1	2
	PVDC(1)	-	85	-	-	-	1	2	3	4	1	2	-
PVDC(2)	PVDC(1)	-	85	-	-	-	100	-	100	100	100	100	-
PVDC(2)	PVDC(3)	-	15	-	-	-	100	-	100	100	100	100	-
Fluid additive (during polymerization) epoxidised linseed oil Uniflex DBS	PVDC(3)	-	15	-	-	-	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	-
	Solid additive CMA lubricant weighting agent	- 0.15 -	- 0.15 -	1 - -	- - 0.15	- 0.15 -	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	- 0.15 -
Fluid additive (during blend) epoxidised linseed oil	Solid additive CMA lubricant weighting agent	- 0.15 -	- 0.15 -	1 - -	- - 0.15	- 0.15 -	1.7	1.7	0.7	1.7	1.7	1.7	- 0.15 -
Fluid additive (during blend) epoxidised linseed oil	The flakey aluminium powder	0.8	0.8	0.8	0.8	0.01	1.7	1.7	0.7	1.7	1.7	1.7	5
Pigment dyestuff (red system/Huang system)	The flakey aluminium powder	0.8	0.8	0.8	0.8	0.01	-	-	-	-	-	-	5
Pigment dyestuff (red system/Huang system)	Spherical aluminium powder	-	-	-	-	-	-	-	-	-	-	-	-
EVA	Spherical aluminium powder	-	-	-	-	-	-	-	-	-	-	-	-
EVA	Extrudable property	○	○	○	○	○	-	-	-	-	-	-	△
Tensility	Extrudable property	○	○	○	○	○	○	◎	○	○	○	×	△
Tensility	Metalluster	○	○	○	○	×	○	◎	○	○	○	×	○
Reflectivity	Metalluster	○	○	○	○	×	43	42	43	42	14	54	○
Reflectivity	Haze value (%)	63	62	63	61	5	43	42	43	42	14	54	90
Thin layer is peeled off	Haze value (%)	63	62	63	61	5	○	○	○	○	○	×	90
Thin layer is peeled off	Hot water shrinkage (100 ℃/3 minutes) MD (%) TD (%)	23 16	22 18	24 17	22 17	25 19	○	○	○	○	○	×	- -

In (footnote) table 1, "-" symbolic representation of the hot water shrinkage of comparative example 2 does not have owing to the tensility of resin combination is bad to measure.

Embodiment 5

The addition of de-scaling flake aluminum becomes 0.4 weight part from 0.8 weight part, and when the flakey aluminium powder adds, add outside organic red pigment 0.026 weight part and yellow organic pigment 0.36 weight part, equally carry out with embodiment 1, prepared mixing material, make biaxially oriented film then.The results are shown in Table 2.

Embodiment 6

The addition of flakey aluminium powder among the embodiment 1 is become 0.5 weight part from 0.8 weight part.And then the limit is warmed up to each composition mixing limit after 85 ℃, with the mixture cooling, adds vinyl-vinyl acetate copolymer (EVA then; Vinyl acetate content=20 weight %) 2.5 weight parts.Mixture is removed coagulated particles with the screening of 10 mesh sieves.Then, equally carry out, make biaxially oriented film with embodiment 1.The results are shown in Table 2.

Embodiment 7

Except that using the GMA composition (GMA: organic red pigment: yellow organic pigment=1: 0.026: 0.36 (weight ratio)) replace containing (methyl) acrylic resin (GMA) of glycidyl among the embodiment 3 that contains pigment dyestuff, equally carry out with embodiment 3, make biaxially oriented film.The results are shown in Table 2.

Comparative example 3

Except that replacing the flakey aluminium powder as the metal-powder with spherical aluminium powder (median size=about 40 μ m), equally carry out with embodiment 1, prepared mixing material, make biaxially oriented film then.The results are shown in Table 2.

Comparative example 4

Except that the addition of epoxidised linseed oil from the addition that adds up to 2.0 weight parts and become 0.03 weight part, Uniflex DBS from 3.5 weight parts become 5 weight parts, equally carry out with embodiment 1, prepared mixing material, make biaxially oriented film then.The results are shown in Table 2.

Comparative example 5

Except that the addition of epoxidised linseed oil from the addition that adds up to 2.0 weight parts and become 0.03 weight part, Uniflex DBS from 3.5 weight parts become 5 weight parts, equally carry out with embodiment 4, prepared mixing material, make biaxially oriented film then.The results are shown in Table 2.

Table 2

Form (weight part)	Embodiment			Comparative example
	Embodiment			Comparative example			5	6	7	3	4	5
	PVDC(1)	-	-	-	-	-	5	6	7	3	4	5	-
PVDC(2)	PVDC(1)	-	-	-	-	-	100	100	100	100	100	100	-
PVDC(2)	PVDC(3)	-	-	-	-	-	100	100	100	100	100	100	-
Fluid additive (during polymerization) epoxidised linseed oil Uniflex DBS	PVDC(3)	-	-	-	-	-	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.01 5	0.01 5	-
	Solid additive CMA lubricant weighting agent	- 0.15 -	- 0.15 -	1 - -	- 0.15 -	- 0.15 -	0.3 3.5	0.3 3.5	0.3 3.5	0.3 3.5	0.01 5	0.01 5	- - 0.15
Fluid additive (during blend) epoxidised linseed oil	Solid additive CMA lubricant weighting agent	- 0.15 -	- 0.15 -	1 - -	- 0.15 -	- 0.15 -	1.7	1.7	0.7	1.7	0.02	0.02	- - 0.15
Fluid additive (during blend) epoxidised linseed oil	The flakey aluminium powder	0.4	0.5	0.8	-	0.8	1.7	1.7	0.7	1.7	0.02	0.02	0.8
Pigment dyestuff (red system/Huang system)	The flakey aluminium powder	0.4	0.5	0.8	-	0.8	0.026/ 0.36	-	0.026/ 0.36	-	-	-	0.8
Pigment dyestuff (red system/Huang system)	Spherical aluminium powder	-	-	-	0.8	-	0.026/ 0.36	-	0.026/ 0.36	-	-	-	-
EVA	Spherical aluminium powder	-	-	-	0.8	-	-	2.5	-	-	-	-	-
EVA	Extrudable property	○	○	○	○	×	-	2.5	-	-	-	-	×
Tensility	Extrudable property	○	○	○	○	×	○	○	○	○	-	-	×
Tensility	Metalluster	○	○	○	×	-	○	○	○	○	-	-	-
Reflectivity	Metalluster	○	○	○	×	-	34	47	41	15	-	-	-
Reflectivity	Haze value (%)	36	56	61	6	-	34	47	41	15	-	-	-
Thin layer is peeled off	Haze value (%)	36	56	61	6	-	○	○	○	○	-	-	-
Thin layer is peeled off	Hot water shrinkage (100 ℃/3 minutes) MD (%) TD (%)	22 17	24 19	21 17	21 16	- -	○	○	○	○	-	-	- -

(footnote)

(1) "-" symbolic representation does not have owing to the extrudable property of each resin combination is bad to measure in the comparative example 4 and 5.

(2) use the GMA composition that contains pigment dyestuff among the embodiment 7.

The possibility of utilizing on the industry

According to the present invention, provide and contained excellent polyvinylidene chloride resin composition and the manufacture method thereof such as flakey inorganic powder, melt processable, stretch process, heat endurance, tone. And then, according to the present invention, provide the polyvinylidene chloride resin that uses the excellences such as melt processable, the oriented film of metallic luster excellence.

According to the present invention, provide the manufacture method of using the oriented film of polyvinylidene chloride resin, metallic luster excellence. Oriented film of the present invention has the bright-coloured metallic luster of tone, be heat-shrinkable, the gas barrier excellence, thereby be fit to be used as the packaging material etc. of the processed foods such as fish meat sausage, poultry meat processed goods.

Claims

1. a polyvinylidene chloride resin composition comprises

(A) polyvinylidene chloride resin,

(D) flakey inorganic powder,

Wherein (D) flakey inorganic powder contain proportionally, for polyvinylidene chloride resin 100 weight parts, be 0.03～4 weight part; And, from the epoxy compounds (B) composition with (C) to contain at least a epoxy of selecting in a group that the resin of epoxy group(ing) forms in the composition be that thermo-stabilizer must be present in the said composition with the ratio of 0.05～6 weight part for polyvinylidene chloride resin 100 weight parts.

2. the polyvinylidene chloride resin composition of claim 1 record, wherein, (A) polyvinylidene chloride resin is made up of the combination of 2 kinds of different polyvinylidene chloride resins of reduced viscosity at least.

3. the polyvinylidene chloride resin composition of claim 1 record, wherein, (D) the flakey inorganic powder is the flakey aluminium powder.

4. the polyvinylidene chloride resin composition of claim 1 record wherein, further contains (E) pigment dyestuff.

5. the polyvinylidene chloride resin composition of claim 4 record, wherein, (E) pigment dyestuff is made up of the combination of organic red pigment and yellow organic pigment.

6. the polyvinylidene chloride resin composition of claim 1 record wherein, for polyvinylidene chloride resin 100 weight parts, further contains (F) vinyl-vinyl acetate copolymer with the ratio of 0.5～5 weight part.

7. the polyvinylidene chloride resin composition of claim 1 record, wherein, (A) polyvinylidene chloride resin is the powdex of resin size in 40～600 mu m ranges, and the polyvinylidene chloride resin composition is the mixing material form.

8. oriented film, this film are that the polyvinylidene chloride resin composition of any one record in the Accessory Right requirement 1～7 forms.

9. an oriented film is characterized in that it being the oriented film that forms from the polyvinylidene chloride resin composition according to claim 1, wherein

(1) reflectivity of film is more than 10, and

(2) haze value of film is more than 8%.

10. the oriented film of claim 9 record, this film be a kind of in 100 ℃ hot water the shrinking percentage during 3 minutes dippings be heat-schrinkable film more than 10% at least one direction.

11. the oriented film of claim 9 record, wherein, the flakey inorganic powder is the flakey aluminium powder.

12. the oriented film of claim 9 record, wherein, thickness is in 5～50 mu m ranges.

13. according to the manufacture method of the polyvinylidene chloride resin composition of claim 1, this method comprises following series of steps:

(I) make vinylidene chloride and can with the monomer copolymerization of its copolymerization, at this moment, randomly under at least a normal temperature of one group that forms from epoxy compounds and softening agent, selecting the additive (B) of liquid in the presence of copolymerization, and randomly at the additive (B) that further adds liquid under at least a normal temperature after the copolymerization, make the step of the powdex of polyvinylidene chloride resin (A)

(III) in this powdex, add the surplus of the additive (B) of liquid under the normal temperature that randomly uses in the total amount of the additive (B) of liquid under the normal temperature or the step (I) step and

(IV) step of interpolation flakey inorganic powder (D) in this powdex,

14. the manufacture method of claim 13 record, wherein, in described step (I), make polyvinylidene dichloride and can make the powdex of polyvinylidene chloride resin (A) with the copolymerization in the presence of the additive (B) of liquid under at least a normal temperature of the monomer of its copolymerization.

15. the manufacture method of claim 13 record wherein, in described step (IV), is also added pigment dyestuff (E) when adding flakey inorganic powder (D).

16. the manufacture method of claim 13 record wherein, in described step (III), is added the resin that the conduct of epoxy composition contains epoxy group(ing) that contains that contains pigment dyestuff.

17. the manufacture method of claim 13 record wherein, in described step (IV), is added the flakey aluminium powder as flakey inorganic powder (D).

18. the manufacture method of claim 13 record is included in the step that described step (IV) is further added vinyl-vinyl acetate copolymer (F) afterwards.

19. an oriented film manufacture method, described oriented film are to be made of the polyvinylidene chloride resin composition according to claim 1, this manufacture method comprises following series of steps:

(III) in this powdex, add the step of the surplus of the additive (B) of liquid under the normal temperature that randomly uses in the total amount of the additive (B) of liquid under the normal temperature or the step (I),

(IV) in this powdex, add flakey inorganic powder (D) step and

20. the manufacture method of claim 19 record, wherein, in described step (I), make polyvinylidene dichloride and can make the powdex of polyvinylidene chloride resin (A) with the copolymerization in the presence of the additive (B) of liquid under at least a normal temperature of the monomer of its copolymerization.

21. the manufacture method of claim 19 record wherein, in described step (IV), is also added pigment dyestuff (E) when adding flakey inorganic powder (D).

22. the manufacture method of claim 19 record wherein, in described step (III), is added the resin that the conduct of epoxy composition contains epoxy group(ing) that contains that contains pigment dyestuff.

23. the manufacture method of claim 19 record wherein, in described step (V), is carried out biaxial stretch-formed with vertical 2～5 times and horizontal 2～5 times stretching ratio.

24. the manufacture method of claim 19 record wherein, in described step (IV), is added the flakey aluminium powder as flakey inorganic powder (D).

25. the manufacture method of claim 19 record, wherein, in described step (IV) afterwards, step (V) comprises the step of further interpolation vinyl-vinyl acetate copolymer (F) before.

26. the manufacture method of claim 19 record, wherein, in step (V), obtain reflectivity of optical thin film more than 10, the film haze value is at the oriented film more than 8%.