CN1703447A - Heat-schrinkable film - Google Patents

Abstract

A heat shrinkable film and a heat shrinkable multilayer film excellent in balance of heat resistance, high shrinkability, high shrinkability particularly at a low temperature, resistance to spontaneous shrinkage, chemical resistance and rigidity, are provided. A heat shrinkable film and a heat shrinkable multilayer film obtained from a resin composition comprising an aromatic vinyl compound/conjugated diene block copolymer having a micro phase separation structure comprising a soft phase and a hard phase and further having a specific structure and a specific dynamic viscoelasticity spectrum and a styrene polymer having a syndyotactic structure, in a specific proportion.

Description

Heat-schrinkable film

Technical field

The present invention relates to the highly shrinkable under thermotolerance, highly shrinkable, the particularly low temperature, anti-natural shrinkability, transparency, rigidity, the good heat-schrinkable film of chemical sproof balance, packaging label and with this container of packing.

Background technology

In the past, the heat-schrinkable film that uses as the shrink packaging of container and shrink label, outward appearance after heat-shrinkable and contraction is good, and the aspect that can not produce the such problem of environmental pollution of polyvinyl chloride when discarded is considered, adopts the good vinylbenzene-butadiene-based segmented copolymer film of transparency.But this film has thermotolerance in the purposes that has and resistance is low, soft no rigidity, heat shrink rate are little, the big problem of contraction naturally.

Particularly in recent years because plastic bottle beverage (tea, coffee etc.) generally offers the human consumer with the state of heat, so the chance of preserving with the long-time heating state in vending machine, display window etc. increases greatly.In this purposes, require to be used from bottle one label of packing, promptly heat-schrinkable film has 60～80 ℃ even about as required 120 ℃ thermotolerance.

To improve thermotolerance, resistance and traumatic resistance etc. is purpose, and the prior art of the styrene polymer styrene polymer or the SPS of syndiotactic structure (below be sometimes referred to as) that is conceived to have syndiotactic structure is as described below.

About the oriented film of polystyrenic polymer (for example with syndiotactic structure, with reference to Japanese patent laid-open 5-200858 communique), the thermal contractive label that is got by the stretched polystyrene that contains syndiotactic polystyrene (for example, with reference to Japanese patent laid-open 7-020785 communique), the heat-schrinkable film that is got by the resin combination stretching that contains the polystyrenic polymer that possesses syndiotactic structure (for example, with reference to Japanese patent laid-open 7-032468 communique) various reports are arranged, though these films have good thermotolerance, particularly based on the styrene polymer with syndiotactic structure and the heat-schrinkable film of random polystyrene, as heat-schrinkable film, the highly shrinkable during its heat shrink, anti-natural shrinkability, the balance of transparency and flexibility etc. is desirable not enough.

To the resin combination of styrene polymer with syndiotactic structure and vinylbenzene-diolefin series segmented copolymer etc. and film etc. (for example, open the 2002-121355 communique with reference to the Japanese Patent spy), the multilayer stretched laminated film (for example, opening the 2002-086640 communique with reference to the Japanese Patent spy) that formed by styrenic polymer composition with syndiotactic structure etc. puts down in writing to some extent.For example, the specified range of the former fusing point and crystallized temperature is good, but they are as heat-schrinkable film, and the balance of the highly shrinkable when its thermotolerance and heat shrink, anti-natural shrinkability, transparency and rigidity etc. is not ideal enough.The multilayer stretched laminated film of putting down in writing in back-communique is like this too.

Manufacture method to syndiotactic structure polystyrene biaxially oriented film (is for example put down in writing to some extent, with reference to Japanese patent laid-open 6-087158 communique), but be configured as the condition of heat-schrinkable film as the specific resin composition that comprises the styrene polymer with syndiotactic structure, the balance of thermotolerance, highly shrinkable, anti-natural shrinkability, transparency and rigidity etc. is desirable not enough.

(for example put down in writing to some extent possessing styrenic and having stretching flap and the manufacture method thereof that the resin combination of composition of the styrenic of random structure obtains with syndiotactic structure, with reference to Japanese patent laid-open 10-067868 communique), but the purpose of this invention is to obtain the less stretching flap of percent thermal shrinkage, and is all different with the purpose and the means of heat-schrinkable film.

The present invention in view of the above fact, it is good to relate to the highly shrinkable under thermotolerance, highly shrinkable, the particularly low temperature, anti-natural shrinkability, resistance, inflexible balance, particularly the good heat-schrinkable film of the balance of thermotolerance and highly shrinkable.

The announcement of invention

The present inventor conscientiously studies the back and finds in order to realize this purpose, the structure and the dynamic viscoelastic spectrum of the aromatic ethenyl compound-conjugated diene copolymer that uses as the raw material of heat-schrinkable film and combination with styrene polymer of syndiotactic structure, and to contain the oriented film that the resin combination of these constituents forms with specified proportion be thermotolerance, highly shrinkable, the particularly highly shrinkable under the low temperature, anti-natural shrinkability, resistance, the good heat-schrinkable film of inflexible balance, thus the present invention finished.

Promptly, the present invention relates to heat-schrinkable film, the feature of this film is, by following composition (A), (B) reaching the resin combination that (C) forms constitutes, at least stretch and get along the single shaft direction, 80 ℃, 10 seconds heat shrink rate is more than 20%, (A): the ratio of aromatic ethenyl compound is 50～90 quality %, form by aromatic ethenyl compound and conjugated diolefine, and segmented copolymer 50～95 quality % with micro phase separation structure that soft phase and hard form mutually, (B): have styrene polymer 5～50 quality % of syndiotactic structure, (C): with composition (A), (B) different styrenic 0～45 quality %.

The simple declaration of accompanying drawing

Fig. 1 is the test film in the thermotolerance mensuration and the synoptic diagram of cylinder.

Nomenclature: 1 is hot plate, and 2 is cylinder, and 3 is heat-schrinkable film, and 4 is adhesive tape.

The best mode that carries out an invention

Below, the present invention is described in detail.

Form and have the segmented copolymer of the micro phase separation structure that soft phase and hard form mutually as what composition of the present invention (A) used by aromatic ethenyl compound-conjugated diolefine, as long as the ratio of aromatic ethenyl compound is 50～90 quality %, have the micro phase separation structure that soft phase and hard form mutually, it is not particularly limited, but the measured value that obtains by Measurement of Dynamic Viscoelasticity preferably satisfies some certain conditions.

Segmented copolymer preferably possesses aromatic ethenyl compound and the random bonded structure of conjugated diolefine, or possesses the combination (so-called tapered configuration etc.) that both have mild concentration gradient velocity of variation, or possesses the structure that above these structures are mixed existence.

In addition, as the part of hard portion, preferably has the random bonded structure of aromatic ethenyl compound and conjugated diolefine.By the importing of random structure, can obtain that dynamic visco-elastic property is good, the maximum value temperature that makes loss tangent can low temperatureization, as the low temperature contractibility good film of heat-schrinkable film.As the block aromatic ethenyl compound of random bonded structure and the copolymerization ratio of conjugated diolefine, the mass ratio of aromatic ethenyl compound is preferably 60～95 quality %.If the mass ratio of aromatic ethenyl compound is less than 60%, it is big, undesirable that then natural shrinking percentage becomes, if surpass 95 quality %, and the heat shrink rate deterioration 80 ℃ time the then.

Here, the segmented copolymer that what is called has a micro phase separation structure that soft phase and hard form mutually by the high hard of vinylbenzene mass ratio mutually and low soft of vinylbenzene mass ratio form mutually, these micro phase separation structures for example can adopt by the infiltration type electron microscope and carry out the gimmick of image analysis or distinguish by the second-order transition temperature more than 2 kinds that DSC and dynamic viscoelastic spectrum mensuration obtain.

In the composition of the present invention (A) used aromatic ethenyl compound can exemplify vinylbenzene, o-methyl styrene, p-methylstyrene, to t-butyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, alpha-methyl styrene, vinyl naphthalene, vinyl anthracene etc., good especially is vinylbenzene.

Used conjugated diolefine can exemplify 1,3-butadiene, 2-methyl isophthalic acid in the composition of the present invention (A), 3-divinyl (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadienes etc., good especially is 1,3-butadiene, isoprene.

As forming with conjugated diolefine and the copolymerization ratio of aromatic ethenyl compound with segmented copolymer of the soft micro phase separation structure that forms mutually with hard mutually is 50～90 quality % that composition of the present invention (A) uses, be preferably 60～85 quality % by aromatic ethenyl compound.

If the ratio of aromatic ethenyl compound is less than 50 quality %, then thermotolerance, rigidity and undercapacity are if surpass 90 quality %, then deficiencies such as the stretchiness of film and flexibility.

To forming with conjugated diolefine and molecular weight with segmented copolymer of the soft micro phase separation structure that forms mutually with hard mutually is not particularly limited of composition of the present invention (A) by aromatic ethenyl compound, for example, the number-average molecular weight (polystyrene conversion method) that records by gel permeation chromatography is preferably more than 10,000 less than 500,000, more preferably more than 30,000 less than 300,000.

Composition of the present invention (A) even the segmented copolymer that forms by aromatic ethenyl compound and conjugated diolefine by molecular weight, form the copolymer compositions that mixes with different segmented copolymers more than 2 kinds such as molecular structures, as long as satisfy above-mentioned condition, be equally applicable to the present invention.

Below, to forming with conjugated diolefine and preparation method with segmented copolymer of the soft micro phase separation structure that forms mutually with hard mutually describes of composition of the present invention (A) by aromatic ethenyl compound.

In organic solvent, be polymerization starter, make each compound more than a kind or 2 kinds that is selected from aforementioned aromatic ethenyl compound and the conjugated diolefine carry out active anionic polymerization and can make this multipolymer with the organolithium compound.

In this active anionic polymerization, as long as there is the polymerization activity end, as the aromatic ethenyl compound and the common full dose polymerization of conjugated diolefine of starting monomer, this monomer does not almost have residual.

In addition, have without by the feature on the inactivation of the reactive behavior end in the caused polymerization process of chain transfer reaction and the newly-generated polyreaction.Therefore, the molecular weight of the multipolymer among the present invention and molecular structure can pass through the addition that the used proton of the inactivation of appropriate change monomer, polymerization starter, randomizer, reactive terminal is supplied with property material (hereinafter referred to as polymerization retarder), and their interpolation opportunity and interpolation number of times, controlled according to various objectives.

For example, import the aromatic ethenyl compound chain with the isolating block type molecular structure of conjugated diolefine chain, be that what is called is separated under the situation of (Network リ ァ カ ッ ト) structure fully, the raw material that adds aromatic ethenyl compound and conjugated diolefine respectively adds another raw material again after a side reaction finishes.

In addition, when forming the chain of random structure, select to add differing from or making their identical randomizer of the reactivity ratio that can dwindle aromatic ethenyl compound and conjugated diolefine, perhaps make to the monomer feed speed of reaction system slower than speed of response, that is, adopt each a small amount of interpolation to make the polyreaction end often be in the method for starvation.

As long as in the presence of suitable randomizer, in reaction system, add aromatic ethenyl compound and conjugated diolefine simultaneously, just can generate multipolymer with tapered (taper) chain structure.

Polymer architecture is not particularly limited, can adopts straight catenate polymkeric substance or make straight catenate sheet end be combined into the multipolymer of star by known coupler.Known coupler can exemplify silicon tetrachloride, 1, chlorosilane based compounds such as two (methyl dichloro silyl) ethane of 2-, organoalkoxysilane based compounds such as tetramethoxy-silicane and tetraphenoxy-silicane alkane, tin tetrachloride, poly-halohydrocarbon, carboxylicesters, polyvinyl compound, epoxidised soybean oil and epoxidation linseed oil wet goods epoxidized oil fat etc., be preferably the epoxidation grease, be more preferably epoxidised soybean oil.

Organic solvent can use aliphatic hydrocarbons such as butane, pentane, hexane, iso-pentane, heptane, octane, octane-iso, ester ring type hydrocarbon such as pentamethylene, methylcyclopentane, hexanaphthene, methylcyclohexane, ethylcyclohexane or aromatic hydrocarbonss such as ethylbenzene, toluene etc.

Organolithium compound as polymerization starter is the compound that combines the lithium atom more than 1 in the molecule, for example can use simple function polymerization starters such as lithium ethide, n-propyl lithium, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium among the present invention, multi-functional polymerization starters such as hexa-methylene two lithiums, butadienyl two lithiums, prenyl two lithiums.

Reactivity when the block rate of the aromatic ethenyl compound in the multipolymer can make aromatic series organic system compound and conjugated diolefine copolymerization by change is controlled than the interpolation concentration of the randomizer that changes.This randomizer is to have the polar molecule, can use amine and ethers, thioether class and sulphonamide, alkylbenzene sulfonate, also can use the alkoxide of potassium or sodium etc.

Suitable amine can use tertiary amine, and for example Trimethylamine 99, triethylamine, Tetramethyl Ethylene Diamine also can use cyclic tertiary amine etc.Ethers can exemplify dme, diethyl ether, phenyl ether, diglyme, diethyl carbitol, diethylene glycol dibutyl ether, tetrahydrofuran (THF) etc.Other can exemplify triphenyl phosphine, hexamethylphosphoramide, alkyl benzene sulphonate (ABS) potassium or sodium, butanols potassium or sodium etc.

When using randomizer, can adopt a kind or multiple.It adds concentration corresponding to monomer 100 mass parts as raw material, adds up to be preferably 0.001～10 mass parts.

Among the present invention,, in reaction system, add the polymerization that makes more than at least a kind that is selected from alcohol, mineral acid, organic acid and phenol system compound and stop as the polymerization retarder in the active anionic polymerization.

Alcohol as polymerization retarder can exemplify methyl alcohol, ethanol, butanols etc., can exemplify hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, carbonic acid etc. as mineral acid, carboxylic acids such as sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, linolenic acid, ricinoleic acid, docosoic can be exemplified as organic acid, also sulfonic acid,-sulfinic acid etc. can be exemplified.In addition, also can make water as polymerization retarder.

In addition, because the inactivation number of polymerization activity end and the stoichiometric number of added polymerization retarder are proportional, so can divide the polymerization retarder that adds the stoichiometric number that is less than the reactive terminal number for several times, only make a part of inactivation of the reactive terminal in the polymerization, the percent polymerization that utilizes residual reactive terminal continuation polymerization to reach regulation makes residual reactive terminal inactivation again, also can once make whole reactive terminal inactivations.But, when polymerization is finished, must add the polymerization retarder of q.s corresponding to the reactive terminal number of this moment, make the reactive terminal complete deactivation.

In the multipolymer of star synthetic, before adding deactivator, add aforementioned coupler, synthesize by carrying out coupled reaction.

Method as the copolymer solution that will finish the inactivation processing comes out from separated from solvent can exemplify (1) separates out it in Weak solvents such as methyl alcohol method; (2) supply with copolymer solution to warming mill etc., only make solvent evaporation and the method (drum drying method) of separating multipolymer; (3) will be supplied to continuously or off and on through segmented copolymer (composition) solution of heating in the cylinder of level of the equilibrium vapor pressure under this temperature that pressure remains below organic solvent contained in this solution, make the method for its devolatilization; (4) feed the method that the aeration type extrusion machine makes its devolatilization; (5) in warm water while stirring method (steam partition method) that is blown into copolymer solution and makes solvent evaporation etc., or aforesaid method is used in combination.

After utilization adds hot extrusion tested particle is pressed into the thick flap of 0.3mm, with this flap in the indoor preservation of 23 ℃ of temperature, relative humidity 50%RH more than 24 hours, after carrying out maturation process, this tested particle is applied stress and the deformation force that frequency is the draw direction of 1Hz, while make temperature improve the dynamic viscoelastic of measuring the used composition of the present invention (A) with 4 ℃/minute ratio.The loss tangent value of used multipolymer among the present invention, in the maximum value that preferably has at least in less than 100 ℃ temperature range more than 65 ℃ more than 1, its maximum value is preferably in 1.5 to less than in 4.0 the scope.In addition, the loss tangent value that is preferably under the temperature that is lower than 10 ℃ of temperature that obtain to become maximum maximum value is maximum below 40% of maximum value, and the loss tangent value that is lower than under the temperature of 30 ℃ of temperature that obtain to become maximum maximum value is maximum below 10% of maximum value.In addition, 30 ℃ loss tangent value be preferably in more than 0.01, less than in 0.4 the scope.

About the dynamic viscoelastic of composition (A), if its visco-elasticity spectrum outside the scope of the invention, then descends as highly shrinkable, low temperature contractibility and the anti-natural shrinkability (0 ℃～50 ℃, for example, 40 ℃ natural shrinking percentage is lower) of heat-schrinkable film sometimes.

The temperature that obtains the maximum value of loss tangent value is below 65 ℃ the time, and natural shrinking percentage improves, and more than 100 ℃ the time, 80 ℃ heat shrink rate descends.If this maximum value surpasses 1.5～scope less than 4.0, and then stretching condition becomes harsh.

In addition, if the loss tangent value that is lower than under the temperature of 10 ℃ of temperature that obtain maximum maximum value surpasses 40% of maximum maximum value, then 80 ℃ heat shrink rate descends, if the loss tangent value that is lower than under the temperature of 30 ℃ of temperature that obtain to become maximum maximum value surpasses 10% of maximum maximum value, then natural shrinking percentage increases.In addition, if 30 ℃ loss tangent value more than 0.4, then natural shrinking percentage increases.

Below, the styrenic with syndiotactic structure as composition of the present invention (B) is described.

Syndiotactic structure is that its stereochemical structure has corresponding to the main chain that is formed by carbon-carbon bond, alternately is positioned at the structure of rightabout three-dimensional arrangement as the phenyl of side chain, and its tacticity is quantitative by the nuclear magnetic resonance method (13C-NMR) of isotropic substance carbon.Utilize the tacticity that the 13C-NMR method measures continuous a plurality of component units have a ratio, for example can represent with diad 2 the time, can represent with triad in the time of 3, can represent with five unit groups in the time of 5.Styrene polymer with syndiotactic structure of the present invention be the racemize diad more than 75%, better be more than 85% or racemize five unit groups more than 30%, better be at the syndiotactic polymer more than 50%.If outside the scope of this value, then styrene polymer does not possess sufficient legislate, and crystallization is insufficient, and the thermotolerance of heat-schrinkable film and rigidity etc. are insufficient.

Monomer can exemplify vinylbenzene, ring-alkylated styrenes, halogenated styrenes, haloalkyl vinylbenzene, alkoxystyrene and their hydride.Comprise these polymer of monomers and composition thereof or as the multipolymer of principal constituent.

Here, but the vinylbenzene replacement of ring-alkylated styrenes exemplified by methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl etc., and vinyl naphthalene, vinylstyrene etc., halogenated styrenes can exemplify chloro-styrene, bromstyrol, fluorobenzene ethene etc.In addition, haloalkyl vinylbenzene can exemplify 1-chloro-4-methyl-benzene etc., and alkoxystyrene can exemplify methoxy styrene, phenetole ethene etc.

Wherein, the good especially styrene polymer with syndiotactic structure is, as monomer contain vinylbenzene, p-methylstyrene, a vinyl toluene, ethyl styrene, Vinylstyrene, to t-butyl styrene, to chloro-styrene, m-chlorostyrene, fluorobenzene ethene, hydrogenated styrene etc. are constituted the unit, satisfy the homopolymer or the multipolymer of above-mentioned condition.

The styrene polymer with syndiotactic structure of composition of the present invention (B) is preferably the multipolymer of vinylbenzene and p-methylstyrene.The copolymerization ratio of p-methylstyrene is 1～70 mole of %, is preferably 3～50 moles of %, more preferably 5～30 moles of %.For example fruit is less than 1 mole of % for copolymerization ratio, and then the crystalline melt point height must be set the shaping processing temperature higher, easily causes the thermolysis that is present in other composition in the resin combination and gelation etc.Copolymerization ratio for example fruit surpasses 30 moles of %, does not then possess the styrene polymer crystallization property originally with syndiotactic structure, and the thermotolerance of heat-schrinkable film descends, sometimes with resin combination in the intermiscibility of other composition also descend.

This styrene polymer with syndiotactic structure, for example in inertia hydrocarbon solvent or under the non-existent situation of solvent, condensation resultant with titanium compound and water and trialkylaluminium is a catalyzer, make styrene monomer (above-mentioned monomer) polymerization can make (for example, opening clear 62-187708 communique) with reference to the Japanese Patent spy corresponding to styrene polymer.In addition, poly-(haloalkyl vinylbenzene) and hydropolymer thereof can make (with reference to Japanese patent laid-open 1-46912 communique, the spy opens flat 1-178505 communique) by known method etc.

In addition, corresponding to styrene polymer with syndiotactic structure, as comonomer, except above-mentioned various polymkeric substance, also can exemplify olefinic monomers such as ethene, propylene, butylene, hexene, octene, diene monomers such as divinyl, isoprene, cyclic diolefine monomer and methyl methacrylate, maleic anhydride, vinyl cyanide isopolarity vinyl monomer etc.Good especially is that employing vinylbenzene repeating unit is that 30～100 moles of %, p-methylstyrene repeating unit are the styrene polymer with syndiotactic structure of 0～70 mole of %, and being more preferably and adopting the vinylbenzene repeating unit is that 70～100 moles of %, p-methylstyrene repeating unit are the styrene polymer with syndiotactic structure of 0～30 mole of %.

Molecular weight with styrene polymer of syndiotactic structure of the present invention is not particularly limited, and weight-average molecular weight is preferably 5～1,000,000, and more preferably 7～500,000, good especially is 10～300,000.

If weight-average molecular weight is less than 50,000, deficiencies such as the thermotolerance of heat-schrinkable film, rigidity and intensity then, if surpass 500,000, then melt viscosity improves, shaping processability descends.Molecular weight distribution is not particularly limited, but weight-average molecular weight (Mw)/number-average molecular weight (Mn) better is more than 1.5 below 8.If outside the scope of above-mentioned value, then shaping processability and tensile properties descend sometimes.

The crystalline melt point of the styrene polymer with syndiotactic structure of composition of the present invention (B) is 160 ℃～260 ℃, is preferably 200 ℃～250 ℃.If crystalline melt point is less than 160 ℃, then the thermotolerance deficiency of heat-schrinkable film if surpass 260 ℃, then must be established the shaping processing temperature higher, gelation that the two keys of easy generation cause and thermal degradation when etc.

The crystallization fusion that is used for the styrene polymer with syndiotactic structure of resin combination can be preferably more than the 5J/g more than 1J/g, more preferably more than the 20J/g.The higher limit of crystallization fusion energy for example is the 53J/g equivalence, and this is known, is preferably in below the 53J/g among the present invention.These values depend on composition, tacticity etc.If the crystallization of styrenic fusion can be less than 1J/g, then the thermotolerance of heat-schrinkable film becomes not enough.

Composition of the present invention (B) preferably homogeneous is scattered in composition, the heat-schrinkable film, exists as a zone (domain) structure.

In addition, having with raising that the degree of crystallinity of polystyrene of syndiotactic structure or crystallization control directly wait is purpose, also can adopt various nucleators.This nucleator can be selected for use arbitrarily with two (p-tert-butyl benzoic acid) aluminium and be the metal-salt of the carboxylic acid of representative, is the known nucleator such as phosphate metal salt, talcum powder, phthalocyanine derivates of representative with methylene-bis (2, the 4-DI-tert-butylphenol compounds) peroxophosphoric acid sodium.These nucleators can be used in combination more than a kind or 2 kinds separately.

Below, describe being used for composition of the present invention (C).Composition (C) is and composition (A), styrenic that (B) is different, can exemplify composition (A) but multipolymer, the hydropolymer of these polymkeric substance and their mixture etc. of other vinyl monomer more than a kind of segmented copolymer that in addition aromatic ethenyl compound and conjugated diolefine form, the polymkeric substance that is formed by the aromatic ethenyl compound more than a kind or aromatic ethenyl compound more than a kind and copolymerization.

Here, as the polystyrene compound, can use more than a kind or 2 kinds of vinylbenzene, alpha-methyl styrene, vinyl toluene, ethyl styrene, isopropyl benzene ethene, t-butyl styrene, styryl phenyl, vinylstyrene, chloro-styrene, bromstyrol, fluorobenzene ethene, 1-chloro-4-methyl-benzene, methoxy styrene, phenetole ethene etc.Wherein, preferably aromatic ethenyl compound can exemplify vinylbenzene, p-methylstyrene, a vinyl toluene, ethyl styrene, to t-butyl styrene.

But other vinyl monomer of copolymerization can exemplify ethene, propylene, divinyl, vinyl compounds such as isoprene, vinyl cyanide, vinyl cyanide compounds such as methacrylonitrile, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, the vinylformic acid pentyl ester, Ethyl acrylate, Octyl acrylate, 2-EHA, cyclohexyl acrylate, vinylformic acid dodecane ester, vinylformic acid octadecane ester, phenyl acrylate, alkyl acrylates such as vinylformic acid benzene methyl, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, the methacrylic acid pentyl ester, N-Hexyl methacrylate, Octyl methacrylate, methacrylic acid 2-ethylhexyl, cyclohexyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, phenyl methacrylate, alkyl methacrylates such as methacrylic acid benzene methyl, maleimide, N-methyl maleimide, the N-ethyl maleimide, the N-butyl maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, maleimide compounds such as N-(to bromophenyl) maleimide etc.

As the object lesson of composition of the present invention (C), can exemplify polystyrene, vinyl cyanide-styrol copolymer, methyl methacrylate-styrol copolymer, alpha-methyl styrene-styrol copolymer, n-butyl acrylate-styrol copolymer, (A) composition phenylethylene resin series such as vinylbenzene-butadiene block copolymer in addition of general polystyrene, modified rubber.From considering, be preferably the random copolymers, n-butyl acrylate-styrol copolymer, vinylbenzene-styrene butadiene random copolymer-styrene block copolymer of polystyrene, vinylbenzene and (methyl) acrylate of general polystyrene, modified rubber etc. with the intermiscibility of composition (A) and composition (B).

Composition (C) also can adopt a kind that is selected from above-mentioned phenylethylene resin series, or the phenylethylene resin series more than 2 kinds uses together.

(C) describes to good especially composition.

General polystyrene is very good with the intermiscibility as the syndiotactic structure polystyrene of composition (B), and is also better with the intermiscibility as the segmented copolymer of the aromatic ethenyl compound of composition (A) and conjugated diene copolymer.Therefore, by adopting this general polystyrene, can obtain good transparency by the degree of crystallinity of control syndiotactic structure polystyrene.

By in forming outermost layer, adding high-impact polystyrene especially, can carry out reinforcement to film, and prevent bonding (blocking) between film.Even high-impact polystyrene also preferably forms rubber particles the unit cell shape and disperses, its volume average particle size is preferably 0.1～2 μ m, more preferably 0.2～1.0 μ m.If be lower than 0.1 μ m, then reinforcing effect is not good, if surpass 2 μ m, the tendency of transparency deteriorates is arranged then.Proportional quantity is preferably 0.1～10 quality %.If less than 0.1%, prevent that then bonding effect is insufficient, if surpass 10 quality %, then transparency obviously descends.

When using n-butyl acrylate-styrol copolymer, can mix, the second-order transition temperature of hard phase is descended, the heat-shrinkable under the low temperature is increased with the hard of composition (A) as composition (C).

When adopting the styrene block-styrene butadiene random block do not have the micro phase separation structure that soft phase and hard form mutually-styrene block copolymer as composition (C), can mix with the hard of composition (A), the second-order transition temperature of hard phase is descended, the heat-shrinkable under the low temperature is increased.

The vinylbenzene chain length that is preferably aromatic ethenyl content and is 60～95 quality %, two ends is the above polymkeric substance of 0.5 whole quality %.

At this moment, the loss tangent value that is obtained by dynamic viscoelastic is preferably in more than 65 ℃ less than having maximum value in 100 ℃ the scope.

The mass ratio (adding up to 100) that constitutes each composition of the present invention (A)/(B)/(C) is 50～90/5～50/0～45, is preferably 50～80/10～45/1～40, more preferably 50～70/10～40/1～40.

Composition (A) if ratio less than value of the present invention, then the shock-resistance of film and stretchiness descend.

Composition (B) is if surpass 50 quality % of the present invention, and then the heat shrink rate of heat-schrinkable film descends, and natural shrinking percentage is excessive, and transparency descends, and flexibility descends, and is uneconomical in addition.Composition (B) is if less than 5 quality % of the present invention, and the thermotolerance that then causes heat-schrinkable film descends, and resistance descends, degradation under the rigidity.

Among the present invention, can under the prerequisite that does not influence the object of the invention, mix composition (A), (B) and (C) in addition thermoplastic resin, thermoplastic elastomer and phase solvent etc. as required.Thermoplastic resin can be selected straight chain shape high density polyethylene(HDPE) arbitrarily for use, straight chain shape new LDPE (film grade), the high-pressure process new LDPE (film grade), isotatic polypropylene, syndiotactic polypropylene, block polypropylene, Atactic Polypropelene, polybutene, 1, the 2-polyhutadiene, poly-4-methylpentene, it is the polyolefin-based resins of representative that cyclic polyolefin reaches with these multipolymers, with polycarbonate, polyethylene terephthalate, polybutylene terephthalate is the polyester based resin of representative, with polyamide 6, polyamide 6,6 for the polyamide-based resin of representative, polyphenylene oxide, known resin such as PPS.These thermoplastic resins can a kind be used singly or two or more kinds in combination.

The object lesson that can be used for the thermoplastic elastomer of polymkeric substance of the present invention can exemplify natural rubber, polyhutadiene, polyisoprene, polyisobutene, sovprene, thiorubber, mercaptan rubber, acrylic elastomer, urethanes, silicon rubber, epichloro hydrin rubber, vinylbenzene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), vinylbenzene-divinyl-styrene block copolymer (SBS), hydrogenated styrene-divinyl-styrene block copolymer (SEBS), vinylbenzene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), vinylbenzene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer vinyl benzene rubbers such as (SEPS), ethylene propylene rubber (EPM), propylene diene rubber (EPDM), ethylene series rubber such as straight chain shape new LDPE (film grade) based elastomers, perhaps divinyl-vinyl cyanide-vinylbenzene-core shell rubber (ABS), methyl methacrylate-divinyl-vinylbenzene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-vinylbenzene-core shell rubber (MAS), Octyl acrylate-divinyl-vinylbenzene-core shell rubber (MABS), alkyl acrylate-divinyl-vinyl cyanide-vinylbenzene-core shell rubber (AABS), divinyl-vinylbenzene-core shell rubber (SBR), with methyl methacrylate-butyl acrylate-siloxanes is the core-shell-type particle shape elastomericss such as core shell rubber that contain siloxanes of representative, perhaps with rubber after their modifications etc.These elastomericss can a kind use separately or are used in combination more than 2 kinds.

Under the prerequisite that does not influence effect of the present invention, can and be used for each (be total to) polymkeric substance of the present invention at resin combination of the present invention and mix stablizer, lubricant, processing aid, crystallization nucleating agent, anti-adhesive agent, anti-live agent, prevent additives such as turbid dose, weather resisting agent, softening agent, tackiness agent, tinting material, anti-live agent, mineral oil, fire retardant, filler.

By composition (D) the acrylate based compound shown in the general formula below in heat-schrinkable film of the present invention, adding, the original characteristic of composition that not only can keep composition (A), (B) and (C) form, the thermostability of the mechanical characteristics of the composition in the time of also can improving thermoforming and outward appearance tone.In addition, by and be that oxidation inhibitor and phenol are oxidation inhibitor (except the composition (D)) with phosphorus, can obtain better thermostable effect.

In the formula, R ₁The alkyl of expression hydrogen or carbonatoms 1～3, R ₂And R ₃The alkyl of representing carbonatoms 1～9 respectively independently, R ₄Expression hydrogen or methyl.

In the aforementioned formula of expression acrylate based compound, R ₁Be the alkyl of hydrogen or carbonatoms 1～3, wherein, be preferably hydrogen and methyl, good especially is methyl.R ₂Be the alkyl of carbonatoms 1～9, wherein be preferably the alkyl of carbonatoms 4～8, good especially is by quaternary carbon and phenyl ring bonded alkyl, for example is more preferably the tertiary butyl, tert-pentyl and uncle's octyl group.R ₃Be the alkyl of carbonatoms 1～9, wherein be preferably the alkyl of carbonatoms 1～6, especially good is methyl, ethyl, the tertiary butyl and tert-pentyl.R ₄Be hydrogen or methyl, good especially is hydrogen.

The object lesson of acrylate based compound is as described below preferably.2-[1-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl acrylate, 2,4-di-t-butyl-6-[1-(3,5-di-t-butyl-2-hydroxy phenyl) ethyl] phenyl acrylate, 2,4-two tert-pentyls-6-[1-(3,5-two tert-pentyls-2-hydroxy phenyl) ethyl] phenyl acrylate, the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenmethyl)-4-aminomethyl phenyl methacrylic ester, 2,4-two tert-pentyls-6-[1-(3,5-two tert-pentyls-2-hydroxy phenyl) ethyl] the phenyl methyl acrylate.

Among the present invention, aforementioned acrylate based compound is corresponding to composition (A), (B) and the summation (C) of 100 mass parts, and its consumption is preferably 0.1～3 mass parts.If this proportional quantity is less than 0.1 mass parts, then the thermostability improved effect is insufficient, can produce a large amount of apertures when forming film, when printing, cause the printing error, if surpass 3 mass parts, then bleeding can appear, and cause surface property obviously to descend, the effect that can not obtain to match with it improves, and is unfavorable for cost control.

Among the present invention, can be that oxidation inhibitor and phenol are the also usefulness of oxidation inhibitor (except the composition (D)) also also, have the effect of improving thermostability exponentially with stablizer, particularly phosphorus beyond the above-mentioned acrylic ester compound.These stablizers exemplify as follows.

Phosphorus is that oxidation inhibitor can exemplify following compound.

Distearyl pentaerythritol diphosphite, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphite, four (2, the 4-di-tert-butyl-phenyl) two phosphonous acid 4,4 '-biphenyl ester, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphite, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) phosphorous acid monooctyl ester, four (tridecyls) 4, two (the 3-methyl-6-tert butyl phenyl) diphosphites of 4 '-butylidene, 2,2 '-ethylenebis (4, the 6-di-tert-butyl-phenyl) fluorophosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphite, trisnonyl phenyl phosphite.

Phosphorus is summation 100 mass parts of the proportional quantity of oxidation inhibitor corresponding to composition (A), (B), (C), is preferably 0～1 mass parts.If surpass 1 quality %, then bleeding can appear, and cause surface property to descend.

To phenol is that the kind of oxidation inhibitor (except the composition (D)) is not particularly limited, and object lesson exemplifies as follows.

3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane base ester, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic acid] triethyleneglycol ester, 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxybenzene methyl) benzene, three (the 4-tertiary butyls-3-hydroxyl-2,6-dimethyl benzene methyl) isocyanuric acid ester, 2, two (positive hot the sulfenyl)-6-(3,5-di-t-butyl-4-hydroxybenzene amido)-1 of 4-, 3, the 5-triazine, three (3,5-di-t-butyl-4-hydroxybenzene methyl) isocyanuric acid ester, 2,2 '-ethylenebis (2, the 4-DI-tert-butylphenol compounds), 2, the 6-di-tert-butyl-4-methy phenol, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2,2 '-ethylenebis (4-methyl-6-tert butyl phenol).

Phenol is summation 100 mass parts of the proportional quantity of oxidation inhibitor (except the composition (D)) corresponding to composition (A), (B), (C), is preferably 0～1 mass parts.If surpass 1 mass parts, then bleeding can take place, cause that surface property descends.

In addition, as lubricant, machining agent, anti-adhesive agent, anti-live agent, anti-turbid dose, can exemplify palmitinic acid, saturated fatty acids such as stearic acid docosoic, Wickenol 155, fatty acid esters such as octyl stearate, pentaerythritol fatty ester, erucicamide, oleylamide, fatty acid amides such as stearylamide, ethylenebisstearamide, glycerol mono fatty acid ester, dialycerides fat acid esters, and sorbitan monopalmitate, sorbitan-fatty acid esters such as sorbitan monostearate are with tetradecyl alcohol, cetyl alcohol, stearyl alcohol etc. are the higher alcohols of representative etc.

As the weathering resistance rising agent, can exemplify 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-benzotriazoles such as 5-chlorobenzotriazole system, 2,4-di-tert-butyl-phenyl-3, ' 5 '-di-t-butyl-4 '-salicylates such as hydroxy benzo manthanoate system, benzophenone series UV light absorber such as Octabenzone, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3, hindered amine type weathering resistance rising agents such as 4-butane tetracarboxylic acid esters.In addition, also can add light oil and silicone oil etc.

The consumption of these additives corresponding to resin combination 100 mass parts, better is in the scope below 5 mass parts.

Each composition of (A)～(C) and the blending means of additive are not particularly limited, for example can do and mix, can also use extrusion machine fusionization, granulating by ヘ Application シ ェ Le mixing tank, ribbon blender, V-Mixer etc.Perhaps, when the preparation of each polymkeric substance, polymerization begins in preceding, the polymerization process, the stages such as aftertreatment of polymkeric substance add.

When making heat-schrinkable film of the present invention, preferably the resin combination solid that the mixing postcooling of pre-fusion is obtained is conducted to the extrusion stretching operation once more.

Like this, raw-material mixing in advance by carrying out, the dispersiveness of each composition is become well, thereby obtain the balance of good heat endurance, heat shrink rate and anti-natural shrinkability etc.

Thermotolerance heat-schrinkable film of the present invention is to contain by (A): the ratio of aromatic ethenyl compound is 50～90 quality %, formed and had segmented copolymer 50～95 quality % of the soft micro phase separation structure that forms mutually with hard mutually with conjugated diolefine by aromatic ethenyl compound, (B): have styrene polymer 5～50 quality % of syndiotactic structure, (C): the layer that styrenic 0～45 quality % different with composition (A), (B) and the additive that adds as required form is as the multilayer film of one deck at least of top layer or central core etc.

To be used for multilayer film by composition (A), (B), (C) etc. the resinous principle of the layer beyond the layer of formation is not particularly limited, for example can exemplify aromatic ethenyl compound-conjugated diene block copolymer, the polymerization of aromatic vinyl thing, the multipolymer that aromatic ethenyl compound and (methyl) vinylformic acid form, the multipolymer that aromatic ethenyl compound and (methyl) acrylate form, the styrenic of modified rubber, good especially is aromatic ethenyl compound-conjugated diene block copolymer and as the combination of composition of main body etc.Can certainly be form the different compositions more than a kind or 2 kinds (A), (B), (C) wait the layer multi-layer that forms stacked and must film.

Layer structure is not particularly limited, is preferably 2 layers～7 layers structure, more preferably the structure of 2 layers or 3 layers.In addition, the bed thickness ratio is not particularly limited, when for example being 3-tier architecture, this ratio is 1～30: 98～40: 1～30 (adding up to 100), be preferably 3～30: 94～40: 3～30 (adding up to 100).If the bed thickness ratio in middle layer surpasses 98, then the characteristic on top layer is difficult to manifest, and the characteristic in middle layer can not be given full play to.

When being 2 layers of structure, the bed thickness ratio was 5～95: 95～5 (adding up to 100), was preferably 20～80: 80～20 (adding up to 100).If thickness proportion is outside above-mentioned scope, then the characteristic of the layer that thickness proportion is little is difficult to manifest, and is difficult to expectation and obtains the ideal effect.

Thickness to heat-schrinkable film of the present invention is not particularly limited, and is preferably 10～300 μ m.

Film of the present invention can adopt the whole bag of tricks manufacturing of in the past using.Used in the past method has methods such as extrusion process, calendering method.When making multilayer film, be preferably and carry out coextrusion method.

Coextrusion mode is not particularly limited, and can be in material mould (feed block) mode, the manifold mode any.By adopting coextrusion mode,, also can make the laminate film that interlaminar adhesion is good, transparency is higher without tackiness agent.

Method as beyond the aforesaid method also can make single thin film earlier respectively, and is with tackiness agent that they are stacked again.Mould can adopt coating suspension bracket mould, T mould, annulus mould etc.

By after fusion (being total to) extruding, then the flap (being total to) that obtains is stretched, can effectively make oriented film.As drawing process, can adopt methods such as stretch of drum method commonly used in the past, long gap stretching method, tenter machine stretching method, tubular type stretching method.For example, can adopt uniaxial extension, simultaneously biaxial stretch-formed, biaxial stretch-formed and with the multistage stretching method of their combinations one by one.Wherein, for the present invention, be preferably simultaneously or biaxial stretch-formed one by one method.

As the method for making oriented film, the good especially T mould that is to use carries out (being total to) extruding, carries out stretch of drum along the direction of extrusion again, carries out tenter machine then and stretches, and adopts biaxial stretch-formed one by one method.

Stretching ratio better is that the longitudinal stretching multiplying power is 1.0 times～2.0 times, and the cross directional stretch multiplying power is 2.0 times～10 times.If stretching ratio is outside above-mentioned value scope, then the value of heat shrink rate is not enough or excessive, and the anisotropy that occurs heat shrink sometimes is too high.

As the better method in the manufacture method of heat-schrinkable film of the present invention, promptly use the T mould to carry out (being total to) extruding, carry out stretch of drum along the direction of extrusion again, it is as described below to carry out tenter machine tensile condition then.

Extrusion temperature is preferably as the above temperature of the fusing point of the styrene polymer with syndiotactic structure of composition (B).If below fusing point, then not fusion of crystallization portion, mixing insufficient.Casting mold roller (cast roll) temperature is set at 30 ℃～100 ℃, is preferably 40 ℃～90 ℃.If the casting mold roll temperature is less than 30 ℃, because molten mass by chilling, so be prone to uneven film thickness, if surpass 100 ℃, does not then carry out enough chillings, degree of crystallinity improves before stretching process, and transparency descends.

Stretch of drum, the draft temperature when tenter machine stretches are 50～100 ℃, are preferably 60～90 ℃.If draft temperature is less than 50 ℃, the situations such as film fracture in then easily stretching are difficult to obtain enough stretching ratios, if above 100 ℃, then the shrinking percentage during heat shrink descends sometimes.

The heat setting temperature that stretches after finishing is 50～100 ℃, is preferably 60～90 ℃, and is preferably in below the draft temperature.If the heat setting temperature less than 50 ℃, then can not obtain enough heat setting effects, if surpass 100 ℃, then the shrinking percentage of heat-schrinkable film descends sometimes.

The present invention sneaks into the salvage material of heat-schrinkable film of the present invention in the novel material and the heat-schrinkable film that obtains, so also can form heat-shrinkable, anti-natural shrinkability, the good heat-schrinkable film of rigidity.

Blending ratio to salvage material is not particularly limited, considers from heat-shrinkable and rigidity aspect, and better be the salvage material of in novel material, sneaking into below the 50 quality %.

Among the present invention, for the surface property that makes the gained film good, can be at surface coated anti-live agent and lubricant etc.

In addition, also can make heat-shrinkable film foaming of the present invention.As the manufacture method of foamed thin sheet, consider from the productivity aspect, be preferably the composition that adopts above-mentioned (A), (B), (C) etc. to form, in being conducted to extrusion machine, whipping agent carries out the method for melt extruded.

Above-mentioned whipping agent can adopt thermolysis type whipping agent and the volatile foaming agent that is generally used for resin treatment.Thermolysis type whipping agent can adopt volatile salt, azodicarbonamide, dinitropentamethylenetetramine, volatile foaming agent can adopt lower paraffin hydrocarbonss such as propane, butane, Skellysolve A, iso-pentane, halohydrocarbon such as Refrigerant 12, Tetrafluoroethane, trichlorofluoromethane, methyl chloride, and carbonic acid gas and nitrogen.In addition, also can use bladder regulators such as frothing aids such as metal oxide and Calucium Silicate powder.

Below, the characteristic of heat-schrinkable film of the present invention (comprising multilayer heat-shrinkable film) is described.

Degree of crystallinity as the styrene polymer with syndiotactic structure of the composition (B) that forms heat-schrinkable film of the present invention is 3～80%, is preferably 5～60%, more preferably 10～50%.If degree of crystallinity is less than 3%, then the thermotolerance of heat-schrinkable film, intensity and resistance etc. are not ideal enough.

The crystallization of the styrene polymer with syndiotactic structure of formation heat-schrinkable film mainly generates small crystallization by the oriented crystallization in the stretching process and causes.

Cold junction crystallization temperature from the styrene polymer with syndiotactic structure of heat-schrinkable film of the present invention is preferably 120～170 ℃, more preferably 130～160 ℃.If the cold junction crystallization temperature is less than 120 ℃, then crystallization becomes big, has pair transparency to produce dysgenic tendency, if surpass 170 ℃, does not then carry out crystallization, may cause deficiencies such as thermotolerance.

Here during said cold junction crystallization temperature is meant that the DSC of heat-shrinkable film measures, the peak top temperature of the exothermic peak of the DSC in the temperature-rise period of 10 ℃/min.

Crystallization fusion from the styrene polymer with syndiotactic structure of heat-schrinkable film can be preferably 0.01～20J/g, more preferably 0.05～15J/g.If less than 0.01J/g, then thermotolerance is abundant inadequately, if surpass 20J/g, then transparency descends.

Here said crystallization is fused in the DSC mensuration that can be meant by heat-shrinkable film, the value of the peak area (A2) of the DSC endotherm(ic)peak in the temperature-fall period of area of the endotherm(ic)peak of the DSC in the temperature-rise period of 10 ℃/min (A1) and 10 ℃/min measuring thereafter, the value that derives by following formula.

Crystallization fusion energy=A2-A1

That is, A2 is regarded as the experiment crystallization of the resin combination that forms heat-shrinkable film and fuse energy, A1 is regarded as in the theoretical crystallization fusion of heat-shrinkable film can descend the not crystallization fusion energy of crystallising part.A2-A1 represents the crystallization fusion energy that heat-shrinkable film possesses.

90 ℃, 10 seconds heat shrink rate of heat-schrinkable film of the present invention better is more than 35% more than 30%, is more preferably more than 40%.If the heat shrink rate under this condition less than 30%, when for example being attached on the PET bottle as label, can not pasted the jail with the shape of bottle, but can occur loosening or the generation fold.

80 ℃, 10 seconds heat shrink rate better is more than 25% more than 20%, is more preferably more than 30%.If the heat shrink rate under this condition less than 20%, when for example being attached on the PET bottle as label, can not pasted the jail with the shape of bottle, but can occur loosening or the generation fold.

70 ℃, 10 seconds heat shrink rate better is more than 15% more than 10%, is more preferably more than 20%.If the heat shrink rate under this condition is less than 10%, for example in the beverage production line of the PET bottles of packing into such as aseptic filling, when being attached on the PET bottle as label, its low temperature contractibility deficiency can not pasted the jail with the shape of bottle, may occur loosening or the generation fold.

40 ℃, 7 days shrinking percentage (index of natural shrinking percentage) of heat-schrinkable film of the present invention is below 5%, more fortunately below 4%, better below 3%.If this shrinking percentage surpasses 5%, then hypersystole can appear in heat-shrinkable film in preservation, the shrinking percentage deficiency when occurring printing distortion and heat shrink sometimes.

Total turbidity value of heat-schrinkable film of the present invention better is below 60%, is preferably below 50%, more preferably below 40%.If total turbidity value surpasses 60%, then the transparency deficiency of film is difficult to see content.When using, be difficult to carry out the inner face printing as label.Because the outside turbidity value of film is bigger, thus whole total turbidity value raising, and the surperficial outside turbidity value of multilayer heat-shrinkable film of the present invention descends, and total turbidity value is descended.

In addition, inner turbidity value below 30%, is more preferably below 20% more fortunately, and good especially is below 10%.If this turbidity value surpasses 30%, then the transparency deficiency of film is difficult to see content, when using as label, is difficult to carry out the inner face printing.The film that turbidity value is high can be used as the label that carries out surface printing and uses.

When foamed thin sheet uses as heat-schrinkable film, the layer of foaming as internal layer, outer is adopted aforementioned outer agent etc., can make film have surface smoothing.By carrying out surface printing, can use as label.

Heat-schrinkable film of the present invention contacted on 120 ℃ hot plate left standstill 120 seconds, confirm not form the above perforation of 1mm.If confirm porose appearance on 120 ℃ hot plate; when then using as the label of PET bottle; under the situation that is placed in incubation chamber such as well heater; the temperature of the hot plate portion of placement container is sometimes above 120 ℃ in the heating of the paste container of paying is preserved; if container upset in well heater, then heat-schrinkable film can be crimped on the hot plate surface, because too high temperature and pressure condition; the defective of film can be extended, obviously diminishes the due functions of label such as demonstration, protection sometimes.

The ratio of the cross directional stretch direction of the film of heat-shrinkable film of the present invention and the mitigation stress of direction rectangular with it is preferably 1.2～10, and more preferably 1.5～8.If this ratio is less than 1.2, then the anisotropy of film is less, be attached to bottle and can produce fold when first-class, if greater than 10, then be attached to bottle when last only a side contraction become big, still can be attached to generation fold when bottle first-class.

As the purposes of heat-schrinkable film of the present invention, good especially is packaging label, heat-schrinkable film lids etc. such as heat-shrinkable label, also can be used for packaging film etc. in addition.

Embodiment

Below, exemplify embodiment the present invention is further detailed, but the present invention is not limited in these examples.φ among the embodiment represents diameter.

[raw material]

The manufacture method of segmented copolymer (composition) etc. that is used for embodiment is as described below as a reference example.

The vinylbenzene-styrene butadiene random copolymer-styrene block copolymer that does not have the micro phase separation structure that soft phase and hard form mutually as composition (C) is synthetic according to reference example 1, synthesizes according to reference example 2～8 as the soft segmented copolymer that constitutes mutually with hard mutually and have a micro phase separation structure that is formed by aromatic ethenyl compound and conjugated diolefine of composition (A).

Reference example 1

(1) in reactor, packs into as the hexanaphthene 511kg and the styrene monomer 1.9kg of polymer solvent, temperature is remained on 30 ℃.Thereafter embodiment, the polymer solvent in the comparative example all are to adopt hexanaphthene.

(2) add the 10 quality % cyclohexane solutions of 960mL therein, carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.Thereafter embodiment, the polymerization catalyst solution in the comparative example all adopt 10 quality % cyclohexane solutions of n-Butyl Lithium.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 162.2kg simultaneously with certain interpolation speed of 81.5kg/h, 11.6kg/h respectively is the divinyl of 23.1kg, after interpolation finishes this state is kept 5 minutes.

(4) styrene monomer that adds 1.9kg again finishes polymerization.

(5) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight (GPC polystyrene conversion, down with) be 230000, comprise the polystyrene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 2

(1) pack in reactor polymer solvent 490kg and styrene monomer 8.4kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 2390mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 119.7kg simultaneously with certain interpolation speed of 119.7kg/h, 9.9kg/h respectively is the divinyl of 9.9kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 63.6kg, reaction is proceeded.

(5) styrene monomer that adds 8.4kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 120000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 3

(1) pack in reactor polymer solvent 490kg and styrene monomer 8.4kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 2940mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 122.0kg simultaneously with certain interpolation speed of 122.0kg/h, 7.6kg/h respectively is the divinyl of 7.6kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 63.6kg, reaction is proceeded.

(5) styrene monomer that adds 8.4kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 110000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 4

(1) pack in reactor polymer solvent 490kg and styrene monomer 8.4kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 1430mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 120.3kg simultaneously with certain interpolation speed of 96.7kg/h, 7.4kg/h respectively is the divinyl of 9.2kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 19.5kg, reaction is proceeded.

(5) styrene monomer that adds 52.5kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 170000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 5

(1) pack in reactor polymer solvent 500kg and styrene monomer 80kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 1200mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 38.0kg simultaneously with certain interpolation speed of 76.0kg/h, 26.8kg/h respectively is the divinyl of 13.4kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 18.6kg, reaction is proceeded.

(5) styrene monomer that adds 50.0kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 200000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 6

(1) pack in reactor polymer solvent 500kg and styrene monomer 8.0kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 1230mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 110.0kg simultaneously with certain interpolation speed of 87.8kg/h, 10.7kg/h respectively is the divinyl of 13.4kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 18.6kg, reaction is proceeded.

(5) styrene monomer that adds 50.0kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 190000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 7

(1) pack in reactor polymer solvent 500kg and styrene monomer 8.0kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 1720mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 114.4kg simultaneously with certain interpolation speed of 76.5kg/h, 9.9kg/h respectively is the divinyl of 14.8kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 54.8kg, reaction is proceeded.

(5) styrene monomer that adds 8.0kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 160000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

Reference example 8

(1) pack in reactor polymer solvent 500kg and styrene monomer 2.0kg remain on 30 ℃ with temperature.

(2) add the 10 quality % cyclohexane solutions of 1750mL therein, make styrene monomer carry out anionoid polymerization as the n-Butyl Lithium of polymerization catalyst solution.

(3) after the percent polymerization of styrene monomer surpasses 99%, interior temperature in reaction system remains in 80 ℃, adding styrene monomer and the total amount that total amount is 94.0kg simultaneously with certain interpolation speed of 94.0kg/h, 15.0kg/h respectively is the divinyl of 15.0kg, after interpolation finishes this state is kept 5 minutes.

(4) remain in 80 ℃ in the temperature that will react system, once add the divinyl of 52.0kg, reaction is proceeded.

(5) styrene monomer that adds 36.0kg is again finished polymerization.

(6) last, make the terminal inactivation of all polymerization activities by water, to obtain weight-average molecular weight be 150000, comprise polystyrene block part, polybutadiene block part and have the polymer fluid of polymkeric substance of the random structure of vinylbenzene and divinyl.

After each polymkeric substance of the reference example 1～8 of solution state makes the polymer solvent pre-concentration respectively,, form particulate state, be used for test described later with the processing that outgases of ventilated type extrusion machine.

(1) under 260 ℃ condition each polymer beads is added hot extrusion, forming thickness is the flap of 0.3mm.

(2) cut out the test film of suitable size from this flap, after 23 ℃, the indoor preservation of 50%RH carried out maturation process more than 24 hours, with following device, when changing temperature, the polymkeric substance inherent storage spring rate and the loss resilience rate that form test film are measured, calculated its loss tangent value.The results are shown in table 1.

Device: レ オ メ ト リ Network ス corporate system solid determination of viscoelasticity device RSA3

Design temperature scope: 0～130 ℃

Set heat-up rate: 4 ℃/minute

Measure frequency: 1Hz

The SBS resin of the composition (A) as a reference example is the system Network リ ア レ of Deuki Kagaku Kogyo Co., Ltd Application 730L, and it is directly used in thereafter test.

The styrene polymer with syndiotactic structure as composition (B) is the following vinylbenzene and the multipolymer of p-methylstyrene, and they are directly used in thereafter test.

The system XAREC201AE (multipolymer) of Idemitsu Petrochemical Co., Ltd.

The system XAREC145AE (multipolymer) of Idemitsu Petrochemical Co., Ltd.

As composition (C) be following resin with (A), styrenic that (B) is different, they are used for test described later.

Japan vinylbenzene Co., Ltd. system: HRM10 random polystyrene

Japan vinylbenzene Co., Ltd. system: the polystyrene of E640N modified rubber

Acrylate based compound as composition (D) is as described below, uses it for test described later.

Sumitomo Chemical Co's system: SumilizerGS 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl-]-4,6-di-tert-pentyl-phenyl acrylate

Other additive is as described below, and they are used for test described later.

The different chemical company system of vapour Bart: Irganox 1076 octadecyls-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester

Rising sun electrification Co., Ltd. system: ア デ カ ス Block 2112RG three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester

The oriented film that is used for the mensuration of the heat-shrinkable of heat-schrinkable film of the present invention, natural shrinkability, degree of crystallinity, crystallized temperature, transparency etc. makes according to following steps.

(1) to each polymkeric substance of supplying with embodiment, comparative example according to the proportioning shown in table 2 and the table 3, with 30mm φ double-shafted extruder, carry out melting mixing with 250 ℃ mould temperature, form particle.Use 25mm φ double-shafted extruder (the wide T mould of Japan system ラ ボ プ ラ ス attached 25cm of ト ミ Le of smart machine Co., Ltd.) again, with the mould temperature shown in table 2 and the table 3 this particle is pushed, cool off with the casting mold roll temperature shown in table 2 and the table 3 again, making thickness is the not tensile extruding plate of 0.3mm, then, cut out the square small pieces of 9cm along direction of extrusion axle from this flap.The MD direction will be called along the direction of extrusion axis, the TD direction will be called with the direction that the MD direction intersects vertically.

(2) adopt the biaxial stretch-formed device of the smart machine Co., Ltd.'s system of Japan, when flap being heated with the regulation draft temperature shown in table 2 and the table 3, according to the multiplying power shown in table 2 and the table 3, stretch according to the multiplying power shown in table 2 and the table 3, make heat-shrinkable film in the TD direction in the MD direction.The heat setting temperature is 23 ℃.

Adopt material mould multilayer tablet extrusion machine, the layer structure of the particle fusion stratification regulation of embodiment, comparative example will be supplied with, push with the T mould again, after acquisition thickness is the multilayer tablet of 0.3mm, according to the same step of the oriented film of individual layer this multilayer tablet that stretches, make heat-shrinkable multilayered film.The layer ratio, mould temperature, casting mold roll temperature etc. that are used for composition, the ectonexine of skin, internal layer are shown in table 4.Used extrusion machine is that internal layer adopts Na カ ニ machinery system 60m/m φ single shaft extrusion machine, the outer Na カ ニ machinery system 40m/m φ single shaft extrusion machine that adopts.

[mensuration of dynamic viscoelastic]

Adopt the loss tangent value of each polymkeric substance (composition) of the method mensuration embodiment same, comparative example with reference example.

[DSC mensuration]

(1) accurate weighing sample 10mg of difference and Alpha-alumina 10mg as a reference in aluminum dish, with the system differential scanning calorimeter DSC6200R of Seiko instrument Co., Ltd., from 30 ℃ of initial stage temperature, be warming up to 300 ℃ with 10 ℃/minute of heat-up rates, 300 ℃ were kept 5 minutes, be cooled to 30 ℃ with 10 ℃/minute then, measure.

[cold junction crystallization temperature]

The peak top temperature of the exothermic peak that DSC heat up is measured is as the cold junction crystallization temperature.

[crystallized temperature]

The peak top temperature of the endotherm(ic)peak that DSC cooling is measured is as crystallized temperature.

[degree of crystallinity]

Obtain the area (A2) of the endotherm(ic)peak of the area (A1) of the endotherm(ic)peak that DSC heat up to measure and DSC cooling mensuration, obtain degree of crystallinity according to following formula.

Degree of crystallinity (%)=(A2-A1)/A2 * 100

[crystallization fusion energy]

Calculate the crystallization fusion energy of heat-shrinkable film according to following formula.

The crystallization fusion can (J/g)=A2-A1

That is, A2 is regarded as the theoretical crystallization fusion energy of the resin combination that forms heat-shrinkable film, A1 is regarded as in the experiment crystallization fusion of heat-shrinkable film can descend the not crystallization fusion energy of crystallising part.A2-A1 represents the crystallization fusion energy that heat-shrinkable film possesses.

[mensuration of percent thermal shrinkage]

(1) cutting out the MD direction from the oriented film of thick 60 μ m is that 20mm, TD direction are the test film of 120mm.

(2) stick 100.0mm graticule at interval in the TD of this test film direction.

(3) this test film is flooded in the warm water of specified temperature (70 ℃, 80 ℃, 90 ℃) after 10 seconds and to take out, wipe the moisture that adheres to after, measure distance between graticule with vernier callipers with the unit of 0.1mm, its measurement result is represented with L1.

(4) calculate percent thermal shrinkage according to following formula.Percent thermal shrinkage is more than 10% at 70 ℃, and 80 ℃ is more than 20%, and 90 ℃ is more than 30%, reaches practical standard.

Percent thermal shrinkage (%)=(100.0-L1)/100.0} * 100

[mensuration of natural shrinking percentage]

(1) cutting out the MD direction from the oriented film of thick 60 μ m is that 20mm, TD direction are the test film of 120mm.

(2) stick 100.0mm graticule at interval in the TD of this test film direction.

(3) this test film was left standstill in 40 ℃ thermostat layer 7 days, with the distance between the unit mensuration graticule of 0.1mm, its measurement result is represented with L2 with vernier callipers.

(4) calculate the nature shrinking percentage according to following formula.The nature shrinking percentage reaches practical standard below 5%.

Nature shrinking percentage (%)=(100.0-L2)/100.0) * 100

[stable on heating evaluation]

(1) cutting out the MD direction from the oriented film of thick 60 μ m is that 20mm, TD direction are the test film of 120mm.

(2) with adhesive tape fixing subsides the in the two ends of this test film paid in the drum surface of φ 50mm, weight 300g, make between film and cylinder seamless.

(3) as shown in Figure 1, the stainless steel that the cylinder that posts film is statically placed in temperature adjustment to 120 in advance ℃ heats on the plate, and film is contacted with hot plate.

(4) after film contacts 120 seconds with hot plate, film is taken off the variation of visual valuation film from hot plate together with cylinder.

Zero: the hole that no φ 1mm is above

*: the above hole of φ 1mm is arranged or occur damaged

[mensuration of transparency]

Employing is the turbidity that benchmark is measured oriented film with lower device with ASTM D1003.

Utilize total turbidity (haze) that the Japanese electric look system NDH2000 of Industrial Co., Ltd measures film (H1).In the cuvette of optical path length 1cm, fill light oil (エ Network ソ Application モ-PVC Le corporate system Network リ ス ト-Le J-352) in advance, measure turbidity (H2), film is immersed in this cuvette, measure turbidity (H3), calculate inner turbidity by following formula.

Inner turbidity=H3-H2

As embodiment 1～25 and comparative example 1～9, the evaluation result of afore-mentioned test is shown in table 2～table 7.

As embodiment 26, corresponding to the used resin combination 99 quality % of embodiment 7, Yonghe County of sneaking into as whipping agent changes into the system セ of Industrial Co., Ltd Le ボ Application SC-K 1%, carries out each test similarly to Example 1.Consequently expansion ratio is 1.6 times, and the percent thermal shrinkage in the time of 70,80,90,100 ℃ is respectively 11%, 34%, 55%, 60%.In addition, natural shrinking percentage is 2%, and thermotolerance is good.

As embodiment 27, the resin combination that embodiment 21 is used is respectively as internal layer and skin, as extrusion machine, internal layer adopts Na カ ニ machinery system 60m/m φ single shaft extrusion machine, the outer Na カ ニ machinery system 40m/m φ single shaft extrusion machine that adopts, adopt 250 ℃ material mould fusion stacked, utilize 250 ℃ T mould to squeeze out 3 layers of flap again, then carry out 1.1 times longitudinal stretching then with 80 ℃ roller with 40 ℃ casting mold roller, then carry out 5 times cross directional stretch, obtain the thermal contraction multilayer film of 50 μ m with holt machinery Co., Ltd. system tenter machine.At this moment, the linear velocity of tenter machine is 5m/min, and the temperature of the preheating oven of tenter machine, stretching furnace, heat setting stove is respectively 110 ℃, 90 ℃, 70 ℃.

The percent thermal shrinkage of layer when being 10/80/10,70,80,90,100 ℃ of this heat-shrinkable film is respectively 13%, 37%, 56%, 63%.In addition, natural shrinking percentage is 3%, and total turbidity of film is 3%.

As embodiment 28, composition 100 mass parts corresponding to the resin combination of the used internal layer cladding material of embodiment 21, add the Sumitomo Chemical Company Ltd system ス ミ ラ イ ザ-GS of 0.5 mass parts as (D) composition, add 0.4 mass parts rising sun electrification system ア デ カ ス Block 2112RG of Co., Ltd. and the different chemical company system Irganox 1076 of 0.2 mass parts vapour Bart again, this resin combination is pushed with aforementioned extrusion machine, form internal layer and skin respectively.As extrusion machine, internal layer adopts Na カ ニ machinery system 60m/m φ single shaft extrusion machine, the outer Na カ ニ machinery system 40m/m φ single shaft extrusion machine that adopts, adopt 250 ℃ material mould fusion stacked, utilize 250 ℃ T mould to squeeze out 3 layers of flap again, then carry out 1.1 times longitudinal stretching then with 40 ℃ casting mold roller, then carry out 5 times cross directional stretch, obtain the thermal contraction multilayer film of 50 μ m with holt machinery Co., Ltd. system tenter machine with 80 ℃ roller.At this moment, the linear velocity of tenter machine is 5m/min, and the temperature of the preheating oven of tenter machine, stretching furnace, heat setting stove is respectively 110 ℃, 90 ℃, 70 ℃.

The percent thermal shrinkage of layer when being 10/80/10,70,80,90,100 ℃ of this heat-shrinkable film is respectively 12%, 38%, 57%, 62%.In addition, natural shrinking percentage is 2%, and total turbidity of film is 3%.

Measure as aperture, cut out 5 films of wide 10cm * long 50cm, the number of the aperture more than the 0.5mm in the film that visual observation cuts out from oriented film.The mean value of count results less than 30 be qualified.The aperture count results of the film of embodiment 27 is 55, and the aperture count results of the film of embodiment 28 is 7.

The possibility of utilizing on the industry

Heat-schrinkable film of the present invention is to comprise specific aromatic ethenyl compound and conjugated diolefine segmented copolymer that forms and the heat-schrinkable film with styrene polymer of syndiotactic structure, it is to diminish heat-shrinkable in the past, natural shrinkability, transparency, and thermotolerance has obtained the heat-schrinkable film of obvious improvement.Therefore, the present invention is applicable to the protective film of heated heat-shrinkable label, heat-schrinkable film lid and bottle etc.

In the specification sheets of the present invention, Japanese patent application 2002-294392 number and the full content of Japanese patent application 2003-101477 specification sheets have been quoted, with this announcement as invention as the application's the basis that requires right of priority.

Table 1

Segmented copolymer	Reference example 1	Reference example 2	Reference example 3	Reference example 4	Reference example 5	Reference example 6	Reference example 7	Reference example 8
									The temperature of loss tangent value acquisition maximum value: T (℃)	73	84	91	93	98	82	73	70
Loss tangent value during temperature T ℃: X	2.64	2.41	2.51	2.69	1.53	2.26	2.23	1.86
									Loss tangent value during temperature (T-10) ℃: Y	0.52	0.59	0.64	0.61	0.38	0.51	0.31	0.61
Loss tangent value during temperature (T-30) ℃: Z	0.09	0.07	0.13	0.11	0.14	0.09	0.07	0.07
									Loss tangent value in the time of 30 ℃: Q	0.06	0.04	0.04	0.04	0.06	0.04	0.04	0.05
Y/X×100(％)	19.8	24.5	25.3	22.5	24.7	22.5	13.9	32.5
									Z/X×100(％)	3.5	2.9	5.3	4.0	9.2	4.0	3.0	4.0
Micro phase separation structure	Do not have	Have	Have	Have	Have	Have	Have	Have

Table 2

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
						Proportioning
(A) composition	Reference example 2	26	27	25
						Reference example 3				27
	Reference example 4				53
						Reference example 5		27	25
	Reference example 6	54	26	25
						(B) composition	201AE	20	20	25	20
Processing conditions
						The mould temperature (℃)		250	250	250	250
The roller temperature (℃)		50	50	50	50
						MD direction stretching ratio (doubly)		5	5	5	5
TD direction stretching ratio (doubly)		1.1	1.1	1.1	1.1
						Draft temperature (℃)		80	80	80	90

Table 2 is continuous

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
						Thermotolerance		○	○	○	○
Shrinkage determination	70 ℃/10 seconds (%)	20	15	14	12
						80 ℃/10 seconds (%)	44	40	30	22
	90 ℃/10 seconds (%)	71	70	55	56
						100 ℃/10 seconds (%)	75	73	61	59
	40 ℃/7 days (%)	4	3	3	2
						Transparency is measured	Total turbidity (%)	30	20	21	33
Inner turbidity (%)	2	2	2	1
					Measurement of Dynamic Viscoelasticity		Temperature when the loss tangent value obtains maximum value: T (℃)	82	88	89	90
Loss tangent value during temperature T ℃: X	1.93	1.63	1.92	2.20
						Loss tangent value during temperature (T-10) ℃: Y	0.57	0.63	0.69	0.62
Loss tangent value during temperature (T-30) ℃: Z	0.11	0.15	0.15	0.11
						Y/X×100(％)	29	39	36	28
Z/X×100(％)	5	9	8	5
						Loss tangent value during 30 ℃ of temperature: Q	0.04	0.03	0.04	0.03
DSC measures	The cold junction crystallization temperature (℃)	139	138	138							138
					Crystallized temperature (℃)	212	212	212	212
	Degree of crystallinity (%)	41％	47％	52％						44％
					Crystal energy (J/g)	3.9	4.3	5.3	4.1

Table 3

		Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10
								Proportioning
(A) composition	Reference example 7	72	72	64	64		64
								Reference example 8					64
	(B) composition	142AE		10		20	20
201AE								10		20			20
		(C) composition	Reference example 1	18	18	16	16							16	16
Processing conditions
		The mould temperature (℃)		250	250	250	260							260	250
The roller temperature (℃)								50	50	50	50	50	50
		MD direction stretching ratio (doubly)		5	5	5	5							5	5
TD direction stretching ratio (doubly)								1.1	1.1	1.1	1.1	1.1	1.1
		Draft temperature (℃)		80	80	80	80							80	70

Table 3 is continuous

		Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10
								Thermotolerance		○	○	○	○	○	○
Shrinkage determination	70 ℃/10 seconds (%)	15	13	12	11	14	20
								80 ℃/10 seconds (%)	50	51	36	39	36	56
	90 ℃/10 seconds (%)	67	65	57	57	48	69
								100 ℃/10 seconds (%)	70	71	60	65	55	72
	40 ℃/7 days (%)	2	2	2	3	3	5
								Transparency is measured	Total turbidity (%)	28	36	48	55	58	27
Inner turbidity (%)	1	2	3	5	8	2
							Measurement of Dynamic Viscoelasticity		Temperature when the loss tangent value obtains maximum value: T (℃)	75	74	76	76	71	76
Loss tangent value during temperature T ℃: X	1.80	1.70	1.75	1.59	1.59	1.75
								Loss tangent value during temperature (T-10) ℃: Y	0.52	0.53	0.48	0.41	0.43	0.48
Loss tangent value during temperature (T-30) ℃: Z	0.10	0.10	0.08	0.05	0.05	0.08
								Y/X×100(％)	29	31	28	26	27	28
Z/X×100(％)	5	6	4	3	3	4
								Loss tangent value during 30 ℃ of temperature: Q	0.04	0.04	0.04	0.03	0.03	0.04
DSC measures	The cold junction crystallization temperature (℃)	148	142	142	140	142									142
							Crystallized temperature (℃)	210	216	211	216	217	211
	Degree of crystallinity (%)	11％	11％	41％	35％	13％								49％
							Crystal energy (J/g)	2.2	2.5	4.3	3.3	3.2	4.0

Table 4

			Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17
										Proportioning
(A) composition		Reference example 7	60	60	56	56	56	56	56
										?730L							10
		(B) composition		?142AE														30
?201AE	25									25	30	20	10		20
				(C) composition		Reference example 1	15	15	14							14	14	14	14
?HRM10										10	20
						Processing conditions
The mould temperature (℃)			250	250	250					250	250	250	250
						The roller temperature (℃)			50					50	50	50	50	50	50
MD direction stretching ratio (doubly)			5	5	5					5	5	5	5
						TD direction stretching ratio (doubly)			1.1					1.1	1.1	1.1	1.1	1.1	1.1
Draft temperature (℃)			80	70	80					80	80	80	80

Table 4 is continuous

		Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17
									Thermotolerance		○	○	○	○	○	○	○
Shrinkage determination	70 ℃/10 seconds (%)	10	21	11	12	13	11	11
									80 ℃/10 seconds (%)	28	52	22	23	21	24	31
	90 ℃/10 seconds (%)	43	65	32	43	48	38	55
									100 ℃/10 seconds (%)	53	73	50	51	53	53	66
	40 ℃/7 days (%)	2	5	2	2	3	1	3
									Transparency is measured	Total turbidity (%)	56	44	54	51	48	57	41
Inner turbidity (%)	9	3	9	8	7	8	3
								Measurement of Dynamic Viscoelasticity		Temperature when the loss tangent value obtains maximum value: T (℃)	76	76	76	76	76	76	76
Loss tangent value during temperature T ℃: X	1.62	1.62	1.52	1.55	1.53	1.56	1.61
									Loss tangent value during temperature (T-10) ℃: Y	0.39	0.39	0.27	0.29	0.25	0.31	0.28
Loss tangent value during temperature (T-30) ℃: Z	0.07	0.07	0.05	0.06	0.05	0.07	0.06
									Y/X×100(％)	24	24	18	19	16	20	17
Z/X×100(％)	4	4	3	4	3	4	4
									Loss tangent value during 30 ℃ of temperature: Q	0.04	0.04	0.03	0.04	0.04	0.04	0.04
DSC measures	The cold junction crystallization temperature (℃)	143	143	140	150	148	137										144
								Crystallized temperature (℃)	211	212	212	209	208	217	211
	Degree of crystallinity (%)	35％	40％	60％	50％	12％	43％									47％
								Crystal energy (J/g)	5.2	5.4	6.7	4.6	2.7	5.5	4.3

Table 5

		Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7
									Proportioning
(A) composition	Reference example 2	33	34
									Reference example 3			34
	Reference example 4			66
									Reference example 5		33
	Reference example 6	67	33
									Reference example 7				64	56		20
	??730L						100
									(B) composition	??201AE							80
(C) composition	Reference example 1				16	14
									??HRM10				20	30
	Processing conditions
The mould temperature (℃)									250	250	250	250	250	250	250
		The roller temperature (℃)		50	50	50	50	50								50	50
MD direction stretching ratio (doubly)									5	5	5	5	5	5	2.3
		TD direction stretching ratio (doubly)		1.1	1.1	1.1	1.1	1.1								1.1	1.1
Draft temperature (℃)									80	80	80	80	80	95	100

Table 5 is continuous

		Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7
									Thermotolerance		×	×	×	×	×	×	○
Shrinkage determination	70 ℃/10 seconds (%)	25	19	11	12	10	8	2
									80 ℃/10 seconds (%)	60	57	42	32	30	20	7
	90 ℃/10 seconds (%)	75	74	70	54	43	42	10
									100 ℃/10 seconds (%)	79	78	79	66	54	57	15
	40 ℃/7 days (%)	3	3	1	2	4	6	0
									Transparency is measured	Total turbidity (%)	10	12	15	56	51	6	48
Inner turbidity (%)	2	2	2	8	9	2	7
								Measurement of Dynamic Viscoelasticity		Temperature when the loss tangent value obtains maximum value: T (℃)	82	87	95	76	75	107	1
Loss tangent value during temperature T ℃: X	2.47	1.73	1.70	1.55	1.61	1.50	2.11
									Loss tangent value during temperature (T-10) ℃: Y	0.69	0.48	0.61	0.38	0.31	0.59	0.42
Loss tangent value during temperature (T-30) ℃: Z	0.09	0.14	0.14	0.05	0.05	0.19	0.03
									Y/X×100(％)	28	28	36	25	20	39	20
Z/X×100(％)	4	8	8	3	3	13	1
									Loss tangent value during 30 ℃ of temperature: Q	0.04	0.06	0.03	0.03	0.03	0.08	0.05
DSC measures	The cold junction crystallization temperature (℃)	-	-	-	-	-	-										143
								Crystallized temperature (℃)	-	-	-	-	-	-	212
	Degree of crystallinity (%)	-	-	-	-	-	-									84
								Crystal energy (J/g)	-	-	-	-	-	-	8.6

Peak crystallization is not seen in-expression

Table 6

		Embodiment 18	Embodiment 19	Embodiment 20	Embodiment 21	Embodiment 22
							The SMIS material mixture ratio	Embodiment	3	100	100
Embodiment 7			100	100	100
						The cladding material proportioning		730L	99	99	99	99	99
E64N	1	1	1	1	1
							Processing conditions	The mould temperature (℃)	250	250	250	250	250
The roller temperature (℃)	50	50	50	50	50
						MD direction stretching ratio (doubly)		5	5	5	5	5
TD direction stretching ratio (doubly)	1.1	1.1	1.1	1.1	1.1
						Draft temperature (℃)		80	80	80	80	70
Layer ratio	Skin/internal layer/skin	10/80/10	10/90/0	5/90/5	10/80/10								10/80/10

Table 6 is continuous

		Embodiment 18	Embodiment 19	Embodiment 20	Embodiment 21	Embodiment 22
							Thermotolerance		○	○	○	○	○
Shrinkage determination	70 ℃/10 seconds (%)	8	7	12	10	11
							80 ℃/10 seconds (%)	28	30	38	36	48
	90 ℃/10 seconds (%)	52	55	56	54	59
							100 ℃/10 seconds (%)	55	61	61	59	64
	40 ℃/7 days (%)	3	5	2	2	5
							Transparency is measured	Total turbidity (%)	7	12	8	7	9
Inner turbidity (%)	2	2	4	6	5

Table 7

		Embodiment 23	Embodiment 24	Embodiment 25	Comparative example 8	Comparative example 9
							The SMIS material mixture ratio	Embodiment 7	100
Embodiment 11		100
						Embodiment 17				100
Comparative example 4				100
						Comparative example 5						100
The cladding material proportioning	Embodiment	1	99
						730L		99	99	99	99
	E64N	1	1	1	1							1
						Processing conditions	The mould temperature (℃)	250	250	250	250		250
The roller temperature (℃)	50	50	50	50	50
							MD direction stretching ratio (doubly)	5	5	5	5	5
TD direction stretching ratio (doubly)	1.1	1.1	1.1	1.1	1.1
							Draft temperature (℃)	80	80	80	80	80
Layer ratio	Skin/internal layer/skin	10/80/10	10/80/10	10/80/10	10/80/10								10/80/10

Table 7 is continuous

		Embodiment 23	Embodiment 24	Embodiment 25	Comparative example 8	Comparative example 9
							Thermotolerance		○	○	?○	×	×
Shrinkage determination	70 ℃/10 seconds (%)	15	10	14	8	5
							80 ℃/10 seconds (%)	52	28	31	31	27
	90 ℃/10 seconds (%)	61	43	51	49	40
							100 ℃/10 seconds (%)	67	53	62	63	51
	40 ℃/7 days (%)	2	2	3	2	3
							Transparency is measured	Total turbidity (%)	20	13	5	17	15
Inner turbidity (%)	5	7	2	9	8

Claims (29)

1. heat-schrinkable film, it is characterized in that, by following composition (A), (B) reaching the resin combination that (C) forms constitutes, at least stretch and get along the single shaft direction, 80 ℃, 10 seconds heat shrink rate is more than 20%, (A): the ratio of aromatic ethenyl compound is 50～90 quality %, form by aromatic ethenyl compound and conjugated diolefine, and segmented copolymer 50～95 quality % with micro phase separation structure that soft phase and hard form mutually, (B): have styrenic 5～50 quality % of syndiotactic structure, (C): with composition (A), (B) different styrenic 0～45 quality %.

2. heat-schrinkable film as claimed in claim 1, its feature also are to have the block of random copolymer part of aromatic ethenyl compound and conjugated diolefine in the structure of the segmented copolymer of composition (A).

3. heat-schrinkable film as claimed in claim 1 or 2, its feature are that also composition (A) has following characteristic,

(1): the loss tangent value in the dynamic viscoelastic spectrum (tan δ) is in the maximum value that has at least in less than 100 ℃ temperature range more than 65 ℃ more than 1;

(2): the maximum value of the maximum value of (1) more than 1.5 less than 4.0 scope in;

(3): in the maximum value of (1), the loss tangent value that is lower than under the temperature of 10 ℃ of temperature that obtain maximum maximum value is maximum below 40% of maximum value;

(4): in the maximum value of (1), the loss tangent value that is lower than under the temperature of 30 ℃ of temperature that obtain maximum maximum value is maximum below 10% of maximum value;

(5): 30 ℃ loss tangent value more than 0.01 less than 0.4 scope in.

4. as each described heat-schrinkable film in the claim 1～3, its feature is that also the resin combination that constitutes heat-schrinkable film has following characteristic,

(1): the loss tangent value in the dynamic viscoelastic spectrum (tan δ) is in the maximum value that has at least in less than 100 ℃ temperature range more than 65 ℃ more than 1;

(2): the maximum value of the maximum value of (1) more than 1.5 less than 4.0 scope in;

(3): in the maximum value of (1), the loss tangent value that is lower than under the temperature of 10 ℃ of temperature that obtain maximum maximum value is maximum below 40% of maximum value;

(4): in the maximum value of (1), the loss tangent value that is lower than under the temperature of 30 ℃ of temperature that obtain maximum maximum value is maximum below 10% of maximum value;

(5): 30 ℃ loss tangent value more than 0.01 less than 0.4 scope in.

5. as each described heat-schrinkable film in the claim 1～4, its feature also is, the natural shrinking percentage in 40 ℃, 7 days is below 5%.

6. as each described heat-schrinkable film in the claim 1～5, its feature also is, as the styrenic of composition (C), comprise the styrenic of the block of random copolymer part that has aromatic ethenyl compound and conjugated diolefine in the structure.

7. as each described heat-schrinkable film in the claim 1～6, its feature also is, as the styrenic of composition (C), comprises the rubber modified polystyrene that contains the following dispersion rubber particle of volume average particle size 2 μ m.

8. as each described heat-schrinkable film in the claim 1～7, its feature also is, as the styrenic of composition (C), comprises the styrenic of the random copolymer structure that has vinylbenzene and (methyl) acrylate in the structure.

9. as each described heat-schrinkable film in the claim 1～8, its feature is that also the crystalline melt point of the styrenic with syndiotactic structure of composition (B) is in 160 ℃～260 ℃ scope, and its crystallization fusion can be more than 1J/g.

10. as each described heat-schrinkable film in the claim 1～9, its feature also is, is 3～80% from the degree of crystallinity of the composition (B) of heat-schrinkable film, and the cold junction crystallization temperature is 120～170 ℃.

11. as each described heat-schrinkable film in the claim 1～10, its feature is that also the inside turbidity value of heat-schrinkable film is below 30%.

12. as each described heat-schrinkable film in the claim 1～11, its feature is that also the ratio of the mitigation stress of the draw direction of film and its right angle orientation is 1.2～10.

13. as each described heat-schrinkable film in the claim 1～12, its feature also is, this film is contacted on 120 ℃ of hot plates left standstill 120 seconds, confirms not have the above perforation of 1mm to occur.

14. as each described heat-schrinkable film in the claim 1～13, its feature is that also the styrenic with syndiotactic structure of composition (B) has formed a domain structure in resin combination.

15. as each described heat-schrinkable film in the claim 1～14, its feature also is, corresponding to summation 100 mass parts of composition (A), (B), (C), contain the acrylate based compound that the following general formula of the conduct (D) of 0.1～3 mass parts is represented

In the formula, R ₁The alkyl of expression hydrogen or carbonatoms 1～3, R ₂And R ₃The alkyl of representing carbonatoms 1～9 respectively independently, R ₄Expression hydrogen or methyl.

16. as each described heat-schrinkable film in the claim 1～15, its feature is that also corresponding to summation 100 mass parts of composition (A), (B), (C), the phosphorus that contains 0.1～1 mass parts is stablizer.

17. as each described heat-schrinkable film in the claim 1～16, its feature is that also corresponding to summation 100 mass parts of composition (A), (B), (C), the phenol that contains 0.1～1 mass parts is stablizer (except the composition (D)).

18. heat-schrinkable film is characterized in that, each described heat-schrinkable film is a foam in the claim 1～17.

19. the heat-schrinkable film of multilayered structure is characterized in that, has each described heat-schrinkable film in 1 layer of claim 1～18 at least.

20. the heat-schrinkable film of multilayered structure as claimed in claim 19, its feature also is, at least 1 layer is formed by the resin combination that comprises the a kind of multipolymer that is selected from styrene-butadiene block copolymer, styrene-isoprene block copolymer, vinylbenzene-(methyl) acrylate based copolymer at least in the outermost layer.

21. as the heat-schrinkable film of claim 19 or 20 described multilayered structures, its feature also is, at least 1 layer of rubber modified polystyrene that contains the following dispersion rubber particle of volume average particle size 2 μ m that comprises 0.1～10 quality % in the outermost layer.

22. heat-schrinkable film as each described multilayered structure in the claim 19～21, its feature also is, multilayered structure constitutes by 3 layers, the middle layer is each described heat-schrinkable film in the claim 1～18, and this thickness proportion of 3 layers is 1～30: 98～40: 1～30 (adding up to 100).

23. heat-schrinkable film as each described multilayered structure in the claim 19～21, its feature also is, multilayered structure constitutes by 2 layers, and 1 layer is each described heat-schrinkable film in the claim 1～18, and the thickness proportion of these layers was 5～95: 95～5 (adding up to 100).

24. the manufacture method of each described heat-schrinkable film is characterized in that in the claim 1～23, in the drawing process, the casting mold roll surface temperature is 30～100 ℃.

25. the manufacture method of heat-schrinkable film as claimed in claim 24, its feature are that also in the drawing process, draft temperature is 50～100 ℃.

26. the manufacture method of heat-schrinkable film as claimed in claim 25, its feature are that also the heat setting temperature that stretches after finishing is 50～100 ℃, and below draft temperature.

27. the manufacture method of heat-schrinkable film as claimed in claim 26, its feature are that also in while or the biaxial stretch-formed one by one process, stretching ratio vertically is 1.05～2.0 times, laterally is 2.1～10 times.

28. the packaging label is characterized in that, is formed by each described heat-schrinkable film in the claim 1～23.

29. container is characterized in that, the described packaging label packing of each described heat-schrinkable film or claim 28 in claim 1～23.

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