CN101160611A

CN101160611A - Shrink labels

Info

Publication number: CN101160611A
Application number: CNA2006800126696A
Authority: CN
Inventors: 丸市直之; 野崎孝典; 森川阳
Original assignee: Gunze Ltd
Current assignee: Gunze Ltd
Priority date: 2005-04-20
Filing date: 2006-02-16
Publication date: 2008-04-09
Anticipated expiration: 2026-02-16
Also published as: JP5075262B2; JP2011203741A; CN100526065C

Abstract

A shrink label comprising a multilayered film as a base film. It is excellent in low-temperature resistance, heat resistance, oil resistance, cuttability along perforations, and appearance and does not peel off after application. Also provided is a heat-shrinkable multilayered resin film which, when used in a shrink label for a container, can effectively prevent the contents of the container from being deteriorated by ultraviolet and which is excellent in cuttability along perforations and oil resistance. Furthermore provided is a shrink label comprising the heat-shrinkable multilayered resin film as a base film. The shrink labels each comprises as a base film a heat-shrinkable multilayered resin film comprising an interlayer made of a polystyrene resin and outer layers made of a polyester resin between which the interlayer is sandwiched, wherein the polystyrene resin constituting the interlayer is an aromatic vinyl hydrocarbon/conjugated diene copolymer and the interlayer is bonded to the outer layers through an adhesive layer comprising a product of the hydrogenation of an aromatic vinyl hydrocarbon/conjugated diene copolymer, the hydrogenated copolymer having in the molecule at least one kind of functional groups selected from the group consisting of carboxy, acid anhydride, amino, epoxy, and hydroxy groups.

Description

Shrink label

Technical field

The present invention relates to cutting, the outward appearance excellence at lower temperature resistance, thermotolerance, oil resistance, place, machine hole, and what can not peel off when installing is the shrink label of basement membrane with multilayer film, and when using as the shrink label of container, the content that can prevent container effectively is by UV degradation, and the multi-layer resinous film of heat-shrinkable of the cutting at place, machine hole and oil resistance excellence and be the shrink label of basement membrane with the multi-layer resinous film of this heat-shrinkable.

Background technology

In recent years, the shrink label of the basement membrane that comprises the heat-shrinkable resin film having been implemented printing etc. has been installed on containers such as many bottles or metal can.

As shrink label, the film that is made of polystyrene resins is a main flow because low temperature contractibility is excellent.Yet polystyrene based resin film is because thermotolerance is insufficient, so when for example heating in the well heater in the convenience store etc., shrink when also having bottle to fall down and the problem that label is out of shape or breaks takes place.In addition, polystyrene based resin film is because solvent resistance is insufficient, so adhere to the problem of shrinking or dissolving because of oil content when being used for the occasion of the article packing of oily sub and also having.

On the other hand, in order to replace polystyrene based resin film, also attempted using the polyester film of lower temperature resistance, thermotolerance or solvent resistance excellence as shrink label.Yet the low temperature contractibility of polyester film is poor, owing to shrink sharp the problem that is easy to generate wrinkle is arranged when event is installed on the container.In addition, on shrinkable film, for container often recycle the machine hole of peeling off usefulness is set so that easily the container after use peel off shrink label, but polyester film is poor at the cutting at place, machine hole, can not easily peel the problem of shrink label when also having from container.

To this, the bonding coat that is situated between and is made of olefine kind resin is disclosed, the outer coversheet that laminated polyester resin constitutes on the middle layer that polystyrene resins constitutes and the hard multi-layer shrink film that obtains in the patent documentation 1.In addition, disclose the outer coversheet that the polyester resin made in the laminated certain monomers in both sides in the middle layer that polystyrene resins constitutes constitutes in the patent documentation 2, had and do not utilize bonding coat between middle layer and the outer coversheet and the shrink label of laminated basement membrane.The shrink label that these are made of multilayer film, the middle layer that utilizes polystyrene resins to constitute, the cutting excellence at low temperature contractibility and machine hole place, and since this middle layer covered by the outer coversheet that polyester resin constitutes, so also excellence of solvent resistance, lower temperature resistance, thermotolerance.Yet, when in fact being installed in these shrink labels on the container, for the hard multi-layer shrink film described in the patent documentation 1, sometimes middle layer and outer coversheet generation is when mounted peeled off, for the shrink label described in the patent documentation 2, the occasion of film phase mutual friction or the occasion that scratched by people's nail or object in the transportation of goods after installation produce the problem of peeling off between internal surface layer and the outer coversheet when having.

In addition, in recent years, the basement membrane that the heat-shrinkable resin film is constituted is installed on the plastic containers such as bottle has been implemented the occasion of the shrink label of printing etc., compare with the preservation of using metal can, the ultraviolet ray deterioration that the content of having found container sends because of daylight or fluorescent light, the problem that keeping quality worsens.For example, the chlorophyll that contains in the edible wet goods decomposes under the wavelength below the 300nm and causes quality badness.In addition, the citral that uses as the spices of beverage etc. is subjected to the effect of 300～350nm light and becomes and have the composition that makes us unhappy fragrance.And amino acid such as the tryptophane that contains in the pure mellow wine, tyrosine are subjected to the light action of 320～380nm and variable color takes place.Therefore, in recent years for the content that prevents this container is subjected to flavor, local flavor reduction, variation or variable color that ultraviolet ray causes, fades, the shrinkable film with ultraviolet isolating is practicability.

As such shrink label, because low temperature contractibility excellence, main flow is the film that polystyrene resins constitutes, for example, disclose the polystyrene based resin film that is made of 3-tier architecture in the patent documentation 3, it is that the use level of ultraviolet light absorber in middle layer is than two outer UVA polystyrene resins heat-schrinkable films of Duoing.

Yet the heat-shrinkable polystyrene type film of Gou Chenging if do not add a large amount of ultraviolet light absorbers, has the problem of the following light of absorbing wavelength 400nm fully like this.And if add ultraviolet light absorber in large quantities, the problem that then has ultraviolet light absorber to separate out, or the cost aspect disadvantageous problem that becomes is arranged.In addition, the oil resistance of polystyrene type film is insufficient, and the occasion of label is installed on the container of the content of oily sub, also has because oil content adheres to the problem of shrinking or dissolving that produces.

In addition, also attempted the replacement polystyrene based resin film, make in the polyester film of lower temperature resistance or solvent resistance, oil resistance excellence and added the heat-shrinkable polyester film of ultraviolet light absorber as shrink label, for example, disclose in the patent documentation 4 and adopted method of in heat-shrinkable polyester film, adding ultraviolet light absorber or the method for adding ultraviolet light absorber, realized excellent ultraviolet isolating, the polyester resin film of heat-shrinkable at the internal layer of the laminated polyester film more than 2 layers.

Yet because the forming temperature height of polyester film, so carry out the occasion of extrusion molding, ultraviolet light absorber causes the deterioration of operating environment from die head distillation, volatilization, and the roller that draws the film of extruding from die head simultaneously is contaminated, so the production efficiency reduction.In addition, in order to prevent the heat ageing of ultraviolet light absorber, when reducing forming temperature, the production efficiency of film reduces significantly.In addition, the cutting at place, the also organic hole of polyester film is poor, can not easily peel off the problem of shrink label sometimes from container.

Therefore, need not cause the deterioration of operating environment or the reduction of production efficiency, have excellent ultraviolet isolating, the multi-layer resinous film of heat-shrinkable of machine hole cutting.

Patent documentation 1: the spy opens clear 61-41543 communique

Patent documentation 2: the spy opens the 2002-351332 communique

Patent documentation 3: the spy opens the 2002-326324 communique

Patent documentation 4: the spy opens the 2001-323082 communique

Summary of the invention

The problem that invention will solve

The present invention is in view of above-mentioned present situation, its purpose is to provide cutting, the outward appearance excellence at lower temperature resistance, thermotolerance, oil resistance, place, machine hole, and what can not peel off when installing is the shrink label of basement membrane with multilayer film, and the content that can prevent container effectively when using as the shrink label of container is by UV degradation, and the multi-layer resinous film of heat-shrinkable of the cutting at place, machine hole and oil resistance excellence and be the shrink label of basement membrane with the multi-layer resinous film of this heat-shrinkable.

Be used to solve the method for problem

The present invention 1 shrink label, be that the multi-layer resinous film of heat-shrinkable with the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping is the shrink label of basement membrane, the polystyrene resins that constitutes aforementioned middle layer is aromatic ethenyl hydrocarbon-conjugated diene copolymer, and the bonding coat that aforementioned middle layer and outer coversheet utilization contain the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule carries out bonding.

The present invention 2 shrink label, be that the multi-layer resinous film of heat-shrinkable with the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping is the shrink label of basement membrane, the polystyrene resins that constitutes aforementioned middle layer is the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, and aforementioned middle layer and outer coversheet utilization contain and have the carboxylic acid group of being selected from the molecule, anhydride group, amino, the bonding coat of the hydride of the aromatic ethenyl hydrocarbon-conjugated diene copolymer of at least a kind of functional group carries out bonding in epoxy radicals and the hydroxyl.

The multi-layer resinous film of heat-shrinkable of the present invention is the multi-layer resinous film of heat-shrinkable that comprises the outer coversheet that contains polyester resin in the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping, and ultraviolet light absorber is contained in aforementioned middle layer.

Below the present invention is described in detail.

The present invention 1 shrink label is that the multi-layer resinous film of heat-shrinkable with the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping is the shrink label of basement membrane, the polystyrene resins that constitutes aforementioned middle layer is aromatic ethenyl hydrocarbon-conjugated diene copolymer, and the bonding coat that aforementioned middle layer and outer coversheet utilization contain the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule carries out bonding.

The present inventor finds, be in the shrink label of basement membrane to comprise the multi-layer resinous film of heat-shrinkable that contains as the outer coversheet that contains polyester resin in the middle layer of the aromatic ethenyl hydrocarbon-conjugated diene copolymer of polystyrene resins and clamping middle layer, Jie by specific bonding coat with above-mentioned middle layer and outer coversheet when bonding, can not produce splitting and installation stably, thereby finish the present invention 1 shrink label.

As the method that shrink label is installed on the container, usually adopt between the end of using the solvent welding shrinkable film and after being processed into tubulose (central authorities' sealing processing) method that heating is shunk film under by the state of coated container.

When Fig. 1 represents to use the present invention 1 shrink label, near the synoptic diagram of state central sealing when near the synoptic diagram of the state central sealing in a series of installation procedure, Fig. 2 are represented to use with in the past multilayer film as the shrink label of basement membrane in the series installation operation.

The present inventor has investigated the result of the installation undesirable condition when having used with in the past multilayer film to the shrink label of basement membrane in minute detail, for the shrink label described in the patent documentation 2, shown in Fig. 2 (a) as can be known, after central authorities' sealing, after making its thermal shrinkage, after the thermal shrinkage in the transportation of goods the occasion of film phase mutual friction, or produced to peel off between internal surface layer 1 and outer coversheet 2 by the occasion that people's nail or object scratch and (should illustrate, in order to compare, in Fig. 2 (a), become the figure that peels off in the end of film, and the end of film in fact not only, central portion grades also can produce and peels off).In addition, for the shrink label described in the patent documentation 1, shown in Fig. 2 (b) as can be known, after the central authorities sealings, when making it thermal shrinkage, the outer coversheet 2 of central sealed sides and bonding coat 3 ' between produce and peel off.

For the shrink label described in the patent documentation 2, do not utilize bonding coat between internal surface layer 1 and the outer coversheet 2 and directly laminated, in the patent documentation 2, the outer coversheet that the polyester resin of being made by certain monomers by use constitutes, improved the affinity of internal surface layer 1 with outer coversheet 2, improved bond strength, and in fact the bond strength of interlayer is not high, thinks that interlayer in internal surface layer 1 and outer coversheet 2 has produced to peel off.

On the other hand, for the shrink label described in the patent documentation 1, because the bonding coat 3 that Jie is made of olefine kind resin ' internal surface layer 1 and outer coversheet 2 is laminated, so the bond strength of interlayer should be high.Central authorities' sealing means uses solvent bonding between the end of shrinkable film down.At this moment, make the solvent of the polyester resin dissolving of using in the outer coversheet, with the part dissolving of outer coversheet and fit as solvent.The olefine kind resin that uses as bonding coat in the patent documentation 1, high for the solvent solvent resistance that makes the polyester resin dissolving, do not dissolve basically or swelling not.Therefore, even the part dissolving of outer coversheet during central authorities' sealing, solvent also can not be penetrated into the inside of shrink label, and the bounding force of the bonding coat that the outer coversheet of dissolving is inboard with it reduces, think during stress application during thermal shrinkage outside surface layer 1 and bonding coat 3 ' between peel off.

And the present invention 1 shrink label, as shown in Figure 1, even central authorities sealing back does not produce splitting yet when making its thermal shrinkage.

The present invention 1 shrink label, owing to utilize the bonding coat 3 that contains the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule laminated internal surface layer 1 and outer coversheet 2, so the bond strength of interlayer is high.In addition, constitute the resin of this bonding coat 3, because for the dissolution with solvents or the swelling that make polyester resin dissolving, so when central authorities sealed, solvent was penetrated into the inside of shrink label, integrally carries out bonding.Therefore, because the bounding force of each interlayer further improves at central sealing, think not cause splitting.

The present invention 1 shrink label, with the multi-layer resinous film of heat-shrinkable of the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the above-mentioned middle layer of clamping as basement membrane.

The polystyrene resins that constitutes above-mentioned middle layer is aromatic ethenyl hydrocarbon-conjugated diene copolymer.Aromatic ethenyl hydrocarbon-conjugated diene copolymer is because the low temperature contractibility excellence, so the shrinkable film that makes can not produce wrinkle etc. and easily be installed on the container.And the cutting at place, machine hole is also excellent.

As above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer, there is not particular determination, for example, can enumerate styrene, o-methyl styrene, p-methylstyrene etc., can enumerate 1 as conjugated diolefine as the aromatic ethenyl hydrocarbon, 3-butadiene, 2-methyl isophthalic acid, 3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene etc.These can distinguish use separately, also can more than 2 kinds and use.Wherein, from low temperature contractibility or the excellent especially consideration of machine hole cutting, optimization styrene-butadiene-styrene copolymer (SBS resin).In addition, in order to make flake film still less, the preferred use utilized the 2-methyl isophthalic acid, and 3-butadiene (isoprene) is as the styrene-isoprene-styrene copolymer-(SIS resin) of conjugated diolefine or styrene-isoprene-butadiene-styrene copolymer (SIBS resin) etc.

When using SBS resin, SIS resin or SIBS resin, can use a kind of resin separately, also various kinds of resin can be used in combination as above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer.Use to do when multiple to mix and also can use the laminated resin that uses the extruder mixing granulator by certain specific composition.The such resin of independent or multiple use preferably becomes styrene-content 65～90 weight %, the composition of conjugated diolefine content 10～35 weight %.The cutting at the low temperature contractibility of the resin of this composition or place, machine hole is excellent especially.On the other hand, conjugated diolefine content is during less than 10 weight %, and fracture easily sometimes when film is applied tension force is suspected less than the ground film when using as the conversion of printing etc. or label sometimes and ruptured.When conjugated diolefine content surpasses 35 weight %, be easy to generate foreign matters such as gel during processing and forming sometimes.

The polyester resin that constitutes above-mentioned outer coversheet can make by making dicarboxylic acid and dibasic alcohol polycondensation.

Do not have particular determination as above-mentioned dicarboxylic acid, for example can enumerate the acid anhydrides of phthalic acid, terephthalic acid (TPA), m-phthalic acid, succinic acid, hexane diacid, decanedioic acid, azelaic acid, octyl group succinic acid, cyclohexane cyclohexanedimethanodibasic, naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, decamethylene carboxylic acid, these dicarboxylic acid and lower alkyl esters etc.

Do not have particular determination as above-mentioned dibasic alcohol, for example can enumerate ethylene glycol, 1, ammediol, 1,4-butylene glycol, diglycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3 butylene glycol, 2,3-butylene glycol, neopentyl glycol (2,2-dimethylpropane-1,3-glycol), 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl isophthalic acid, 3-pentanediol, 2-ethyl-1, aliphatic diol classes such as 3-hexanediol; 2, two (4-hydroxy-cyclohexyl) propane, 2 of 2-, the oxyalkylene addition product, 1 of two (4-hydroxy-cyclohexyl) propane of 2-, alicyclic di-alcoholss such as 4-cyclohexanediol, 1,4 cyclohexane dimethanol etc.

As above-mentioned polyester resin, wherein, preferably contain composition from terephthalic acid (TPA), and contain from the composition of ethylene glycol and 1,4 cyclohexane dimethanol resin as glycol component as the dicarboxylic acid composition.By using such polyester resin, can give extra high thermotolerance and solvent resistance to the present invention's 1 of making shrink label.

In addition, give the occasion of extra high thermotolerance and solvent resistance, preferred to use the content from the composition of ethylene glycol be 60～80 moles of %, is the resin of 10～40 moles of % from the content of the composition of 1,4 cyclohexane dimethanol.Such polyester resin can also contain 0～20 mole of % of composition from diglycol.

Polyester resin as constituting above-mentioned outer coversheet can use the polyester resin with above-mentioned composition separately, also can will have the polyester resin more than 2 kinds of above-mentioned composition and use.

As above-mentioned polyester resin, preferably use the resin of crystalline melt temperature below 240 ℃.In the manufacturing of shrinkable film, generally the cutting edge sheet of stretching bead or circulation film are reused as salvage material and make.Usually, such salvage material mixes with polystyrene resins as the raw material in middle layer, but because the different in kinds such as fusing point of polystyrene resins and polyester resin, so carry out the occasion of film forming under the temperature of the moulding that is suitable for polystyrene resins, polyester resin is extruded with the state of not fusion sometimes.But, lower or do not have the polyester resin of crystalline melt temperature by using crystalline melt temperature, can prevent from that the not fused mass of polyester resin becomes foreign matter in the film after moulding to produce.And crystalline melt temperature is when surpassing 240 ℃, and as the occasion that salvage material carries out moulding, it is residual that the not fused mass of polyester resin becomes foreign matter in the film, and it is not good to produce outward appearance sometimes, or printing ink disperses and produces problems such as printing is not good during printing.Be more preferably below 220 ℃.

In the multi-layer resinous film of above-mentioned heat-shrinkable, the bonding coat that above-mentioned middle layer and outer coversheet utilization contain the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule carries out bonding.Such bonding coat and the polystyrene resins that constitutes the middle layer, any affinity of polyester resin that constitutes outer coversheet are all high, and be can high strength ground that both are bonding.In addition, owing in dissolving constitutes the solvent of polyester resin of outer coversheet, dissolve or swelling,, can prevent generation splitting when thermal shrinkage thereafter so solvent can be penetrated into the inside of shrink label during central seal.In addition, because the coetrusion moulding can be adopted with outer coversheet in the middle layer, so production efficiency is also excellent.

As having the carboxylic acid group of being selected from the above-mentioned molecule, anhydride group, amino, the hydride of the aromatic ethenyl hydrocarbon-conjugated diene copolymer of at least a kind of functional group in epoxy radicals and the hydroxyl, there is not particular determination, for example, preferred maleic anhydride modified styrene-ethylene/butylene-styrene block copolymer (maleic anhydride modified SEBS resin), amine modified phenylethylene-ethylene/butylene-styrene block copolymer (amine modified SEBS resin), amine modified phenylethylene-butadiene/butylene-styrene segmented copolymer (amine modification SBBS resin) or carboxyl acid modified styrene-butadiene/butylene-styrene segmented copolymer (carboxyl acid modified SBBS resin) etc.

Above-mentioned SEBS resin, SBBS resin all can make by the SBS resin is carried out hydrogenation, also can pass through grafted maleic anhydride, thereby or make reaction such as amines, carboxylic acid compound portion's addition amine or carboxylic acid endways, can easily obtain modifier.

The preferred lower limit of content that has the aromatic ethenyl hydrocarbon composition in the hydride of the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the above-mentioned molecule is 20 weight %, and the preferred upper limit is 80 weight %.During less than 20 weight %, when being installed, shrink label is easy to generate splitting.During greater than 80 weight %, the cohesive of bonding coat reduces, and can not obtain sufficient bond strength sometimes.The preferred upper limit is 50 weight %.

The preferred lower limit of content that has the above-mentioned functional group in the hydride of the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the above-mentioned molecule is 0.05 weight %, and the preferred upper limit is 5.0 weight %.During less than 0.05 weight %, the cohesive with outer coversheet becomes insufficient especially sometimes, and during greater than 5.0 weight %, the hot deterioration of resin is easy to generate foreign matters such as gel sometimes during the above-mentioned functional group of addition.Preferred lower limit is 0.1 weight %, and the preferred upper limit is 3.0 weight %.

The preferred lower limit of the thickness in above-mentioned middle layer is 22 μ m, and the preferred upper limit is 37 μ m.During less than 22 μ m, the cutting at place, sufficient machine hole can not be obtained sometimes, during greater than 37 μ m, sufficient thermotolerance can not be obtained sometimes.Preferred lower limit is 26 μ m, and the preferred upper limit is 36 μ m.

The preferred lower limit of the thickness of above-mentioned outer coversheet is 3 μ m, and the preferred upper limit is 10 μ m.During less than 3 μ m, sufficient oil resistance or thermotolerance can not be obtained sometimes, during greater than 10 μ m, the cutting at place, sufficient machine hole can not be obtained sometimes.Preferred lower limit is 4 μ m, and the preferred upper limit is 8 μ m.

The preferred lower limit of the thickness of above-mentioned bonding coat is 0.7 μ m, and the preferred upper limit is 1.5 μ m.During less than 0.7 μ m, can not obtain sufficient bond strength sometimes, during greater than 1.5 μ m, heat shrinkability characteristic worsens sometimes.Preferred lower limit is 0.8 μ m, and the preferred upper limit is 1.3 μ m.

Method as the shrink label of making the present invention 1 does not have particular determination, but preferably adopts the method for each layer of coetrusion moulding simultaneously.For example, when adopting the coextrusion of T font die head, can be feed tank mode, branch manifold mode as laminated method, or any with the method for these modes and usefulness.Especially the later temperature of part of collaborating by the resin that makes each layer is preferably more than 230 ℃, more preferably more than 240 ℃, can obtain the good multilayer film of cohesive of each layer.

The present invention 1 shrink label can add adjuvants such as antioxidant, thermal stabilizer, lubricant, antistatic agent, antiblocking agent as required.Especially by adding the generation that thermal stabilizer or antioxidant can suppress gel.

The present invention 1 shrink label is a basement membrane with the multi-layer resinous film of above-mentioned heat-shrinkable, as required other layers such as laminated printed layers.

The present invention 2 shrinkable film is that the multi-layer resinous film of heat-shrinkable with the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping is the shrink label of basement membrane, the polystyrene resins that constitutes aforementioned middle layer is the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, and aforementioned middle layer and outer coversheet utilization contain and have the carboxylic acid group of being selected from the molecule, anhydride group, amino, the bonding coat of the hydride of the aromatic ethenyl hydrocarbon-conjugated diene copolymer of at least a kind of functional group is bonding in epoxy radicals and the hydroxyl.

The present inventor finds, be in the shrink label of basement membrane to comprise the multi-layer resinous film of heat-shrinkable that contains as the outer coversheet that contains polyester resin in the middle layer of the hybrid resin of the aromatic ethenyl hydrocarbon-conjugated diene copolymer of polystyrene resins and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer and clamping middle layer, Jie by specific bonding coat with above-mentioned middle layer and outer coversheet when bonding, can not produce splitting and installation stably, thereby finish the present invention 2 shrink label.

The present invention 2 shrink label is a basement membrane with the multi-layer resinous film of heat-shrinkable of the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the above-mentioned middle layer of clamping.

The polystyrene resins that constitutes above-mentioned middle layer is the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer.The film that such hybrid resin constitutes, because the low-temperature extension excellence, so the shrinkable film that makes becomes the lower temperature resistance height, the shrinkable film that the cutting at place, machine hole is also excellent.

As above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer, can use the multipolymer same with the present invention 1 shrink label.

In addition, when using SBS resin, SIS resin or SIBS resin as above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer, preferably using styrene-content is 65～85 weight %, and conjugated diolefine content is the resin of 15～35 weight %.The resin of this composition, the cutting at low temperature contractibility or place, machine hole is excellent especially.

As above-mentioned aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, there is not particular determination, for example, can enumerate styrene, o-methyl styrene, p-methylstyrene etc. as the aromatic ethenyl hydrocarbon, as esters of unsaturated carboxylic acids, can enumerate methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate etc.These can distinguish use separately, also can more than 2 kinds and use.

As above-mentioned aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, when using the styrene-propene butyl acrylate copolymer, preferably using styrene-content is 60～90 weight %, and butyl acrylate content is the multipolymer of 10～40 weight %.By the aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer that uses this composition, can make the shrink label of lower temperature resistance or machine hole place cutting excellence.

The preferred lower limit of complex that constitutes the above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer in the hybrid resin in above-mentioned middle layer is 20 weight %, and the preferred upper limit is 80 weight %.Low-temperature extension reduces during less than 20 weight %, and when error fell during stored refrigerated, shrinkable film broke sometimes, during greater than 80 weight %, and the contraction when shrinkable film is preserved sometimes, the so-called contraction naturally increases.Preferred lower limit is 30 weight %, and the preferred upper limit is 70 weight %.

Among the present invention 2, constitute the polyester resin of above-mentioned outer coversheet, can make by making dicarboxylic acid and dibasic alcohol polycondensation.

In addition, above-mentioned middle layer and the outer coversheet utilization bonding coat that contains the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule carries out bonding.

The present invention 2 shrink label is because above-mentioned middle layer and outer coversheet Jie are laminated so the bond strength of interlayer is high by above-mentioned bonding coat.In addition, be that the resinoid solvent of dissolved polyester is dissolved or the resin of swelling owing to constitute the resin of above-mentioned bonding coat, so solvent is penetrated into the inside of shrink label when central authorities seal, integral body is carried out bonding.Therefore, because the bounding force of each interlayer further improves at central sealing, think not cause splitting.

Moreover, in the present invention 2 the shrink label, the hydride and the adjuvant of the aromatic ethenyl hydrocarbon-conjugated diene copolymer that uses in the polyester resin that uses in the relevant above-mentioned outer coversheet, the above-mentioned bonding coat, since identical with the present invention 1 shrink label, its detailed explanation of Therefore, omited.

Among the present invention 2, the preferred lower limit of the thickness in above-mentioned middle layer is 22 μ m, and the preferred upper limit is 37 μ m.During less than 22 μ m, can not obtain sufficient low temperature contractibility sometimes, perhaps can not obtain the cutting at place, machine hole, during greater than 37 μ m, can not obtain sufficient lower temperature resistance.Preferred lower limit is 26 μ m, and the preferred upper limit is 36 μ m.

The preferred lower limit of the thickness of above-mentioned outer coversheet is 3 μ m, and the preferred upper limit is 10 μ m.During less than 3 μ m, sufficient oil resistance or lower temperature resistance can not be obtained sometimes, during greater than 10 μ m, the cutting at place, sufficient machine hole can not be obtained sometimes.Preferred lower limit is 4 μ m, and the preferred upper limit is 8 μ m,

Method as the shrink label of making the present invention 2 does not have particular determination, but preferably adopts the method for each layer of coetrusion moulding simultaneously.When for example using the coextrusion of T font die head, can be material feeding box mode, branch manifold mode or any with the method for these and usefulness as laminated method.Especially be preferably more than 230 ℃ by the later temperature of part that makes each layer resin interflow, more preferably more than 240 ℃, can make the good multilayer film of cohesive of each layer.

The multi-layer resinous film of heat-shrinkable of the present invention is the multi-layer resinous film of heat-shrinkable that comprises the outer coversheet that contains polyester resin in the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping, and aforementioned middle layer is the layer that contains ultraviolet light absorber.

The result that the present inventor studies with great concentration, discovery is by adding ultraviolet light absorber in the middle layer of the multi-layer resinous film of heat-shrinkable of the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and clamping middle layer, ultraviolet light absorber is not separated out, do not produce heat ageing, can have excellent UVA effect and machine hole place cutting concurrently, can solve the problem when in the heat-shrinkable multilayered film that has used polyester resin or polystyrene resins separately, adding ultraviolet light absorber, thereby finish the multi-layer resinous film of heat-shrinkable of the present invention.

The multi-layer resinous film of heat-shrinkable of the present invention comprises the middle layer of containing polystyrene resins and the outer coversheet that contains polyester resin in the above-mentioned middle layer of clamping.

As the polystyrene resins that constitutes above-mentioned middle layer, for example, can enumerate the hybrid resin etc. of aromatic ethenyl hydrocarbon-conjugated diene copolymer, aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer.

Above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer, because the low temperature contractibility excellence, so the shrinkable film that makes wrinkle etc. does not take place and can easily be installed on the container, the cutting that becomes place, machine hole simultaneously is the shrinkable film of excellence also.

In addition, the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, because low-temperature extension excellence when forming film, so the shrinkable film that makes becomes the lower temperature resistance height, the shrinkable film that the cutting at place, machine hole is also excellent.

In addition, above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer can use to have the aromatic ethenyl hydrocarbon-conjugated diene copolymer of isoprene as the conjugated diolefine composition.When especially using many aromatic ethenyl hydrocarbon of the ratio of butadiene-conjugated diene copolymer, that carries out easily during moulding that the butadiene composition causes is crosslinked, produces flake in the film that the result makes, or the problem of printing deterioration etc. takes place to produce.And use when having isoprene as the aromatic ethenyl hydrocarbon of conjugated diolefine composition-conjugated diene copolymer, because crosslinked when suppressing moulding, so can prevent production of foreign matters such as gel.

This is considered to because the butadiene composition of above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer, because the heating during moulding, generation is imbued with reactive free radical, make other compound dehydrogenations, thereby or add to be easy to generate on two keys chain crosslinked, and the isoprene composition produces the reactive free radical of shortage, suppresses crosslinked carrying out thereby mutually combine.

In addition, the aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer that uses in the relevant multi-layer resinous film of heat-shrinkable of the present invention since with its detailed description of the identical Therefore, omited of shrink label of the present invention 2.

As above-mentioned middle layer, when using the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer, the preferred lower limit of use level of the above-mentioned aromatic ethenyl hydrocarbon-conjugated diene copolymer in the hybrid resin is 20 weight %, and the preferred upper limit is 80 weight %.During less than 20 weight %, low-temperature extension reduces sometimes, and shrinkable film broke when error fell during stored refrigerated, and during greater than 80 weight %, increase is promptly shunk in the contraction when shrinkable film is preserved sometimes naturally.Preferred lower limit is 30 weight %, and the preferred upper limit is 70 weight %.

In the multi-layer resinous film of heat-shrinkable of the present invention, ultraviolet light absorber is contained in above-mentioned middle layer.

By adding ultraviolet light absorber in this wise, can give ultraviolet isolating, the multi-layer resinous film of heat-shrinkable of the present invention, because the barrier of the ultraviolet ray (wavelength 380nm is following) that daylight or fluorescent light are sent is excellent especially, so can prevent the content deterioration of container, can improve keeping quality.

In addition, contain ultraviolet light absorber, can solve problems such as heat ageing when in polyester resin, having added ultraviolet light absorber or roller pollution by only making in the middle layer of containing polystyrene resins.In addition, even the poor occasion of ultraviolet light absorber, owing to also can realize desired ultraviolet isolating, so it is favourable also to become aspect cost.

In addition, also can in the middle layer of the shrink label of the

present invention

1 or 2, add above-mentioned ultraviolet light absorber.

As above-mentioned ultraviolet light absorber, for example, can enumerate 2,4-dihydroxy benaophenonel, 2,2 ', 4,4 '-benzophenone ultraviolet light absorber such as tetrahydroxybenzophenone, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid, Octabenzone; 2-(2 '-hydroxyl-4 '-the n-octyloxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-positive methoxyphenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '; 5 "-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-[2 '-hydroxyl-3 '-(3 "; 4 ", 6 " tetrahydric phthalimide methyl)-5 5 " '-aminomethyl phenyl] benzotriazole ultraviolet light absorber such as benzotriazole; 2,4-di-tert-butyl-phenyl-3, benzoates ultraviolet light absorbers such as 5-di-tert-butyl-4-hydroxybenzoic acid ester; To salicylate class ultraviolet light absorbers such as tert-butyl-phenyl salicylates; Ethyl-2-cyano group-3,3-diphenylacrylate ester, octyl group-2-cyano group-3, cyanoacrylate ultraviolet light absorbers such as 3-diphenylacrylate ester etc.

Wherein, consider from ultraviolet-absorbing and stable on heating balance are excellent, preferred 2-(2 '-hydroxyl-5 '-positive methoxyphenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole.

The content of above-mentioned ultraviolet light absorber, with respect to material 100 weight portions in formation middle layers such as base resin or recycled material, preferred lower limit is 1 weight portion, the preferred upper limit is 10 weight portions.During less than 1 weight portion, it is insufficient that ultraviolet isolating becomes, the occasion of using as the shrink label of container, sometimes can not prevent the deterioration of content, during greater than 10 weight portions, the physical strength of the multi-layer resinous film of heat-shrinkable reduces, and the occasion as the printing and dyeing processing or the shrink label of printing etc. uses ruptures sometimes.The preferred lower limit of the content of above-mentioned ultraviolet light absorber is 2 weight portions, and the preferred upper limit is 8 weight portions.

The multi-layer resinous film of heat-shrinkable of the present invention has the outer coversheet that contains polyester resin in the above-mentioned middle layer of clamping.

In addition, the multi-layer resinous film of heat-shrinkable of the present invention, between middle layer and outer coversheet, has the bonding coat that contains the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a kind of functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule.

The multi-layer resinous film of heat-shrinkable of the present invention is because above-mentioned middle layer and outer coversheet Jie are laminated by above-mentioned bonding coat, so the bond strength of interlayer is high.In addition, be that the resinoid solvent of dissolved polyester is dissolved or the resin of swelling owing to constitute the resin of above-mentioned bonding coat, so when central authorities sealed, solvent was penetrated into inside, integrally carries out bonding.Therefore, because the bounding force of each interlayer further improves at central sealing, so think and do not cause splitting.

In addition, the formation of relevant above-mentioned outer coversheet and bonding coat, since identical with the present invention 1 shrink label, its detailed explanation of Therefore, omited.

The preferred lower limit of thickness of the multi-layer resinous film of heat-shrinkable of the present invention is 30 μ m, and the preferred upper limit is 60 μ m.During less than 30 μ m, fracture easily during greater than 60 μ m, has the cutting at place, hole on opportunity to reduce.

The preferred lower limit of the thickness in above-mentioned middle layer is 50% of the multi-layer resinous overall film thickness of heat-shrinkable, and the preferred upper limit is 85%.Less than 50% o'clock, can not obtain the cutting at place, machine hole sometimes, greater than 85% o'clock, film surface scratched easily sometimes, and ultraviolet light absorber is separated out from scuffing.

The preferred lower limit of the thickness of above-mentioned outer coversheet is 5% of the multi-layer resinous overall film thickness of heat-shrinkable, and the preferred upper limit is 24%.Less than 5% o'clock, can not obtain sufficient oil resistance or lower temperature resistance sometimes, greater than 24% o'clock, can not obtain the cutting at place, sufficient machine hole sometimes.

Do not have particular determination as the method for making the multi-layer resinous film of heat-shrinkable of the present invention, but preferably adopt the method for each layer of coetrusion moulding simultaneously.For example, when adopting the coextrusion of T font die head,, can be method any of feed tank mode, branch manifold mode or these modes and usefulness as laminated method.Especially the later temperature of part of collaborating by the resin that makes each layer is preferably more than 230 ℃, more preferably more than 240 ℃, can make the good multilayer film of cohesive of each layer.

In addition, do not have particular determination, for example, can enumerate ultraviolet light absorber is directly dropped into method in the extruder as the adding method of above-mentioned ultraviolet light absorber; With ultraviolet light absorber and above-mentioned polystyrene resins is mixing make masterbatch after, cooperate mother material that the masterbatch make dilutes etc.

In the multi-layer resinous film of heat-shrinkable of the present invention, also can add adjuvants such as antioxidant, thermal stabilizer, lubricant, antistatic agent, antiblocking agent as required.Especially by adding the generation that thermal stabilizer or antioxidant can suppress gel.

By the multi-layer resinous film of heat-shrinkable of the present invention is used as basement membrane, can make shrink label.Such shrink label also is one of the present invention.

Shrink label of the present invention can be a basement membrane with the multi-layer resinous film of above-mentioned heat-shrinkable, as required other layers such as laminated printed layers.

The invention effect

According to the present invention, cutting, the outward appearance excellence at lower temperature resistance, thermotolerance, oil resistance, place, machine hole can be provided, and can not produce what peel off when installing is the shrink label of basement membrane with multilayer film, and the content that can prevent container effectively when using as the shrink label of container is by UV degradation, and the multi-layer resinous film of heat-shrinkable of the cutting at place, machine hole and oil resistance excellence and be the shrink label of basement membrane with the multi-layer resinous film of this heat-shrinkable.

Description of drawings

Fig. 1 is near expression synoptic diagram of the state central sealing in the series installation operation when using shrink label of the present invention.

Fig. 2 is near expression synoptic diagram of the state central sealing in the series installation operation when using with in the past multilayer film to the shrink label of basement membrane.

Symbol description

1 middle layer

2 outer coversheet

3,3 ' bonding coat

Embodiment

Below enumerate embodiment and illustrate in greater detail the present invention, but the present invention has more than and is defined in these embodiment.

(embodiment 1)

As outer coversheet, use as the dicarboxylic acid composition and use terephthalic acid (TPA), as glycol component contain 67 moles of % of composition from ethylene glycol, from the polyester resin of 33 moles of % of composition of 1,4 cyclohexane dimethanol.Moreover this polyester resin is the resin that does not observe fusing point.

As the middle layer, use s-B-S multipolymer (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch).

As bonding coat, use maleic anhydride modified styrene-ethylene/butylene-styrene block copolymer (styrene-content 30 weight %, maleic anhydride addition amount 1.0 weight %, MFR 4.0g/10 branch, proportion 0.92).

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m)/middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.In addition, the later temperature of the part of each laminated stream is 230 ℃.

(embodiment 2)

As outer coversheet, use is used terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 70 moles of % of composition from ethylene glycol, from 10 moles of % of composition of diglycol, from the polyester resin of 20 moles of % of composition of 1,4 cyclohexane dimethanol.In addition, this polyester resin is the resin that does not observe fusing point.

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m)/middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 230 ℃.

(embodiment 3)

As outer coversheet, use as the dicarboxylic acid composition and use terephthalic acid (TPA), as glycol component contain 67 moles of % of composition from ethylene glycol, from the polyester resin of 33 moles of % of composition of 1,4 cyclohexane dimethanol.

As the middle layer, use s-B-S multipolymer (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR5.6g/10 branch).

As bonding coat, use maleic anhydride modified styrene-ethylene/butylene-styrene block copolymer (styrene-content 30 weight %, maleic anhydride addition amount 0.5 weight %, MFR 4.0g/10 branch, proportion 0.91).

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m)/middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 240 ℃.

(embodiment 4)

As the middle layer, use s-B-S multipolymer (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 part).

As bonding coat, use amine modified phenylethylene-ethylene/butylene-styrene block copolymer (styrene-content 30 weight %, MFR 4.0g/10 branch, proportion 0.91, end are amino).

(embodiment 5)

As the middle layer, use s-B-S multipolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points, MFR 7.8g/10 branch).

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m) middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.In addition, the later temperature of the part of each laminated stream is 230 ℃.

(embodiment 6)

As outer coversheet, use as the dicarboxylic acid composition and use terephthalic acid (TPA), contain from from 67 moles of % of composition of ethylene glycol, from the polyester resin of 33 moles of % of composition of 1,4 cyclohexane dimethanol as glycol component.

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (9 μ m)/bonding coat (1 μ m)/middle layer (25 μ m)/bonding coat (1 μ m)/outer coversheet (9 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 230 ℃.

(embodiment 7)

As the middle layer, use styrene-isoprene-butadiene-styrene copolymer (styrene 75 weight %, isoprene 10 weight %, butadiene 15 weight %, 82 ℃ of Vicat softening points, MFR 8.0g/10 branch).

(embodiment 8)

As the middle layer, use mixes styrene-isoprene-butadiene-styrene copolymer with the s-B-S multipolymer hybrid resin A (styrene 84.5 weight %, isoprene 1.5 weight %, butadiene 14 weight %, 70 ℃ of Vicat softening points, MFR 9.0g/10 branch).

(embodiment 9)

As outer coversheet, use is used terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 70 moles of % of composition from ethylene glycol, from 10 moles of % of composition of diglycol, from the polyester resin of 20 moles of % of composition of 1,4 cyclohexane dimethanol.

As the middle layer, use is by hybrid resin A (styrene 84.5 weight, isoprene 1.5 weight %, butadiene 14 weight %, 70 ℃ of Vicat softening points, MFR 9.0g/10 branch) 70 weight %, with s-B-S multipolymer (styrene 77 weight %, butadiene 23 weight %, 82 ℃ of Vicat softening points, MFR 6.0g/10 branch) resin that constitutes of 30 weight %.

(embodiment 10)

As outer coversheet, use is by using 94 moles of % of terephthalic acid (TPA), 6 moles of % of hexane diacid as the dicarboxylic acid composition, as glycol component contain 88 moles of % of composition from ethylene glycol, from 1, the polyester resin of 12 moles of % of composition of 4-cyclohexanedimethanol (211 ℃ of fusing points), 70 weight % with use terephthalic acid (TPA) as the dicarboxylic acid composition, the resin that contains 67 moles of % of composition, constitutes from the polyester resin 30 weight % of 33 moles of % of composition of 1,4 cyclohexane dimethanol as glycol component from ethylene glycol.

As the middle layer, use hybrid resin A (styrene 84.5 weight %, isoprene 1.5 weight %, butadiene 14 weight %, 70 ℃ of Vicat softening points, MFR 9.0g/10 branch) 70 weight % and s-B-S multipolymer (styrene 77 weight %, butadiene 23 weight %, 82 ℃ of Vicat softening points, MFR 6.0g/10 branch) resin that constitutes of 30 weight %.

As bonding coat, use polymer ends to introduce amino amine modified phenylethylene-ethylene/butylene-styrene block copolymer (styrene-content 30 weight %, MFR 4.0g/10 branch, proportion 0.91).

(embodiment 11)

As outer coversheet, use is by using 83 moles of % of terephthalic acid (TPA), 11 moles of % of m-phthalic acid, 6 moles of % of hexane diacid as the dicarboxylic acid composition, used polyester resin (216 ℃ of fusing points) the 50 weight % of ethylene glycol and used terephthalic acid (TPA) as glycol component as the dicarboxylic acid composition, the resin that contains 70 moles of % of composition, constitutes as glycol component from 10 moles of % of composition of diglycol, from the polyester resin 50 weight % of 20 moles of % of composition of 1,4 cyclohexane dimethanol from ethylene glycol.

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (8 μ m)/bonding coat (1 μ m)/middle layer (29 μ m)/bonding coat (1 μ m)/outer coversheet (8 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 230 ℃.

(embodiment 12)

As outer coversheet, use is by using terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 70 moles of % of composition from ethylene glycol, from 10 moles of % of composition of diglycol, from 1, the polyester resin 80 weight % of 20 moles of % of composition of 4-cyclohexanedimethanol with use terephthalic acid (TPA) as the dicarboxylic acid composition, used 1 as glycol component, the resin that the polyester resin of 4-butylene glycol (227 ℃ of fusing points) 20 weight % constitute.

(embodiment 13)

As the middle layer, use is by the hybrid resin B that is mixed with the s-B-S multipolymer (styrene 85 weight %, butadiene 15 weight %, 70 ℃ of Vicat softening points, the MFR8.0g/10 branch) 70 weight % and s-B-S multipolymer (styrene 77 weight %, butadiene 23 weight %; 82 ℃ of Vicat softening points, MFR 6.0g/10 branch) resin that constitutes of 30 weight %.

Use maleic anhydride modified styrene-ethylene/butylene-styrene block copolymer (styrene-content 30 weight %, maleic anhydride addition amount 1.0 weight %, MFR 4.0g/10 branch, proportion 0.92) as bonding coat.

(comparative example 1)

Use is used terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 67 moles of % of composition from ethylene glycol, from 1, the polyester resin of 33 moles of % of composition of 4-cyclohexanedimethanol adopts extrusion molding to extrude the film of thickness 45 μ m, with it as shrink label.

(comparative example 2)

Use s-B-S multipolymer (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch), adopt extrusion molding to extrude the film of thickness 45 μ m, with it as shrink label.

(comparative example 3)

As bonding coat, use maleic anhydride modified straight chain shape low density polyethylene (LLDPE).

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m)/middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 250 ℃.

(comparative example 4)

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by this 3-tier architecture of outer coversheet (6 μ m)/middle layer (33 μ m)/outer coversheet (6 μ m), with its film as shrink label.Moreover the later temperature of the part of each laminated stream is 250 ℃.

(evaluation)

Adopt following method that the shrink label of making in embodiment 1～13 and the comparative example 1～4 is estimated.The results are shown in table 1.

(1) installation property, outward appearance

Effect 1,3-two oxa-s penta encircle the two ends of the bonding shrink label of mixed solvent of 100 weight portions and cyclohexane 50 weight portions, are processed into the tubular of internal diameter 6.5cm.The shrink label of the tubular that obtains is overlayed on the bottle of diameter 6.5cm, the hot blast that blows 85 ℃ makes it to shrink installation.Moreover the machine hole is gone up in processing in advance on each shrink label.

After respectively 100 bottles being installed, after scraping with nail again, be the installment state of center visualization shrink label integral body, by following standard evaluation installation property, outward appearance with central sealing.

Zero: do not find splitting or wrinkle fully.

*: have at least 1 to find splitting or wrinkle.

(2) thermotolerance

30 of the bottles (can not having the bottle that splitting or wrinkle ground are installed) that shrink label is installed are being incubated after leaving standstill 15 minutes on 130 ℃ the hot plate, and the state of visualization shrink label is by following standard evaluation thermotolerance.

Zero: do not find wrinkle on the shrink label fully or break.

*: have at least 1 shrink label to find wrinkle or break.

(3) cutting at place, machine hole

To 30 of bottles that shrink label is installed (can not having the bottle that splitting or wrinkle ground are installed), locate to scratch to take off shrink label with hand slave hole.Observe the state of this moment, by the cutting at following place, standard evaluation machine hole.

Zero: take off shrink label thereby can easily scratch the machine hole.

*: the shrink label that useful hand is difficult to take off.

(4) oil resistance

After coating edible oil on the shrink label that 30 of the bottles of shrink label (can not having the bottle that splitting or wrinkle ground are installed) are installed, the state of visualization shrink label is by following standard evaluation oil resistance.

Zero: do not find wrinkle on the shrink label fully or break.

*: finding at least 1 shrink label has wrinkle or breaks.

(5) interlaminar strength

With contain outer coversheet the layer as peel ply, with contain the middle layer the layer as being stripped from layer.Measure these layers by wide 10mm, along the intensity of 180 degree directions when peeling off.

[table 1]

	Installation property, outward appearance	Thermotolerance	Cutting	Oil resistance	Interlaminar strength (N/mm)
	Installation property, outward appearance	Thermotolerance	Cutting	Oil resistance	Interlaminar strength (N/mm)	Embodiment 1	○	○	○	○	1.2
Embodiment 2	○	○	○	○	1.3	Embodiment 1	○	○	○	○	1.2
Embodiment 2	○	○	○	○	1.3	Embodiment 3	○	○	○	○	1.1
Embodiment 4	○	○	○	○	1.1	Embodiment 3	○	○	○	○	1.1
Embodiment 4	○	○	○	○	1.1	Embodiment 5	○	○	○	○	1.3
Embodiment 6	○	○	○	○	1.2	Embodiment 5	○	○	○	○	1.3
Embodiment 6	○	○	○	○	1.2	Embodiment 7	○	○	○	○	1.3
Embodiment 8	○	○	○	○	1.1	Embodiment 7	○	○	○	○	1.3
Embodiment 8	○	○	○	○	1.1	Embodiment 9	○	○	○	○	1.2
Embodiment 10	○	○	○	○	1.2	Embodiment 9	○	○	○	○	1.2
Embodiment 10	○	○	○	○	1.2	Embodiment 11	○	○	○	○	1.2
Embodiment 12	○	○	○	○	1.1	Embodiment 11	○	○	○	○	1.2
Embodiment 12	○	○	○	○	1.1	Embodiment 13	○	○	○	○	1.3
Comparative example 1	×	○	×	○	-	Embodiment 13	○	○	○	○	1.3
Comparative example 1	×	○	×	○	-	Comparative example 2	○	×	○	×	-
Comparative example 3	×	○	○	○	0.7	Comparative example 2	○	×	○	×	-
Comparative example 3	×	○	○	○	0.7	Comparative example 4	×	○	○	○	0.2

(embodiment 14)

As the middle layer, use styrene-butadiene block copolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points, MFR 6.0g/10 branch) 50 weight %, styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) hybrid resin of 50 weight %.

(embodiment 15)

As outer coversheet, use is used terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 70 moles of % of composition from ethylene glycol, from 10 moles of % of composition of diglycol, from the polyester resin of 20 moles of % of composition of 1,4 cyclohexane dimethanol.Moreover this polyester resin is the resin that does not observe fusing point.

(embodiment 16)

As the middle layer, use is by s-B-S multipolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points, MFR 6.0g/10 branch) 50 weight % and styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) hybrid resin that constitutes of 50 weight %.

(embodiment 17)

(embodiment 18)

As the middle layer, use styrene-butadiene block copolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points, MFR 6.0g/10 branch) 30 weight %, styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) hybrid resin of 70 weight %.

(embodiment 19)

(embodiment 20)

As the middle layer, use is by styrene-isoprene-butadiene-styrene copolymer (styrene 75 weight %, isoprene 10 weight %, butadiene 15 weight %, 82 ℃ of Vicat softening points, MFR 8.0g/10 branch) 50 weight %, styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) hybrid resin that constitutes of 50 weight %.

(embodiment 21)

As outer coversheet, use is by using 94 moles of % of terephthalic acid (TPA) as the dicarboxylic acid composition, 6 moles of % of hexane diacid, as glycol component contain 88 moles of % of composition from ethylene glycol, from 1, the polyester resin of 12 moles of % of composition of 4-cyclohexanedimethanol (211 ℃ of fusing points), 70 weight % with use terephthalic acid (TPA) as the dicarboxylic acid composition, the hybrid resin that contains 67 moles of % of composition, constitutes from the polyester resin 30 weight % of 33 moles of % of composition of 1,4 cyclohexane dimethanol as dicarboxylic acid component from ethylene glycol.

As the middle layer, use is by styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) 70 weight %, styrene-isoprene-butadiene-styrene copolymer (styrene 70 weight %, isoprene 15 weight %, butadiene 15 weight %, 65 ℃ of Vicat softening points, MFR 10g/10 branch) hybrid resin that constitutes of 30 weight %.

(comparative example 5)

Use styrene-butadiene block copolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points, MFR 6.0g/10 branch) 50 weight %, styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points, MFR 4.0g/10 branch) hybrid resin of 50 weight %, adopt extrusion molding to extrude the film of thickness 45 μ m, with it as shrink label.

(comparative example 6)

As the middle layer, use styrene-butadiene block copolymer (styrene 75 weight %, butadiene 25 weight %, 83 ℃ of Vicat softening points) 50 weight %, styrene-propene butyl acrylate copolymer (styrene 85 weight %, butyl acrylate 15 weight %, 70 ℃ of Vicat softening points) hybrid resin of 50 weight %.

Use maleic anhydride modified straight chain shape low density polyethylene (LLDPE) as bonding coat.

(comparative example 7)

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by this 3-tier architecture of outer coversheet (6 μ m)/middle layer (33 μ m)/outer coversheet (6 μ m), with it as shrink label.Moreover the later temperature of the part of each laminated stream is 250 ℃.

(evaluation)

Shrink label to making in embodiment 14～21 and the comparative example 1,5～7 adopts method same as the above-mentioned method, each evaluation of installation property, outward appearance, place, machine hole cutting, oil resistance, interlaminar strength.In addition, adopt following method to estimate lower temperature resistance.The results are shown in table 2.

(lower temperature resistance)

Make 30 bottles that shrink label is installed (can not having the bottle that splitting or wrinkle ground are installed), be incubated after falling from the height of 70cm under 4 ℃ the state, the state of visualization shrink label is by following standard evaluation lower temperature resistance.

Zero: do not find breaking of place, slave hole fully.

*: at least 1 discovery has breaking of place, slave hole.

[table 2]

	Installation property, outward appearance	Lower temperature resistance	Cutting	Oil resistance	Interlaminar strength (N/mm)
	Installation property, outward appearance	Lower temperature resistance	Cutting	Oil resistance	Interlaminar strength (N/mm)	Embodiment 14	○	○	○	○	1.2
Embodiment 15	○	○	○	○	1.2	Embodiment 14	○	○	○	○	1.2
Embodiment 15	○	○	○	○	1.2	Embodiment 16	○	○	○	○	1.1
Embodiment 17	○	○	○	○	1.1	Embodiment 16	○	○	○	○	1.1
Embodiment 17	○	○	○	○	1.1	Embodiment 18	○	○	○	○	1.1
Embodiment 19	○	○	○	○	1.2	Embodiment 18	○	○	○	○	1.1
Embodiment 19	○	○	○	○	1.2	Embodiment 20	○	○	○	○	1.2
Embodiment 21	○	○	○	○	1.1	Embodiment 20	○	○	○	○	1.2

Comparative example 1	×	○	×	○	-
Comparative example 1	×	○	×	○	-	Comparative example 5	○	×	○	×	-
Comparative example 6	×	○	○	○	0.7	Comparative example 5	○	×	○	×	-
Comparative example 6	×	○	○	○	0.7	Comparative example 7	×	○	○	○	0.2

(embodiment 22)

As the middle layer, use is with respect to Styrene-Butadiene (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch) 100 weight %, added 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-composition of 5-chlorobenzotriazole 2.5 weight portions.

As bonding coat, use the maleic anhydride adduct (styrene-content 30 weight %, maleic anhydride addition amount 0.5 weight %, MFR 4.0g/10 branch, proportion 0.91) of hydrogenation of styrene-butadieno copolymer thing.

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by these 5 layers of structures of outer coversheet (6 μ m)/bonding coat (1 μ m)/middle layer (31 μ m)/bonding coat (1 μ m)/outer coversheet (6 μ m), with it as shrink label.

(embodiment 23)

As the middle layer, use is at styrene-propene butyl acrylate copolymer (styrene 82 weight %, butyl acrylate 18 weight %, 62 ℃ of Vicat softening points, MFR 5.5g/10 branch) 50 weight portions and Styrene-Butadiene (styrene 77 weight %, butadiene 23 weight %, 82 ℃ of Vicat softening points, MFR 6.0g/10 branch) in the hybrid resin of 50 weight portions, added 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-composition of 5-chlorobenzotriazole 3.0 weight portions.

As bonding coat, use the maleic anhydride adduct (styrene-content 30 weight %, maleic anhydride addition amount 1.0 weight %, MFR 4.0g/10 branch, proportion 0.92) of hydrogenation of styrene-butadieno copolymer thing.

(embodiment 24)

As the middle layer, use is with respect to Styrene-Butadiene (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch) 100 weight portions, added 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-composition of 5-chlorobenzotriazole 7.5 weight portions.

(comparative example 8)

Except do not add 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-the 5-chlorobenzotriazole, make shrink label similarly to Example 1.

(comparative example 9)

As outer coversheet, use the polystyrene resins that constitutes by Styrene-Butadiene (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch).

As the middle layer, use is with respect to Styrene-Butadiene (styrene 78 weight %, butadiene 22 weight %, 72 ℃ of Vicat softening points, MFR 5.6g/10 branch) 100 weight portions, added 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-composition of 5-chlorobenzotriazole 2.5 weight portions.

Use these resins, adopt coetrusion, extrude the multi-layer resinous film of heat-shrinkable that constitutes by this 3-tier architecture of outer coversheet (7 μ m)/middle layer (31 μ m)/outer coversheet (7 μ m), with it as shrink label.

(comparative example 10)

(comparative example 11)

As the middle layer, use is with respect to using terephthalic acid (TPA) as the dicarboxylic acid composition, as glycol component contain 67 moles of % of composition from ethylene glycol, from 1, polyester resin 100 weight portions of 33 moles of % of composition of 4-cyclohexanedimethanol, added 2-as ultraviolet light absorber (2 '-hydroxyl-3 '-tert-butyl group-5 '-aminomethyl phenyl)-composition of 5-chlorobenzotriazole 2.5 weight portions.

(evaluation)

To the shrink label of making in embodiment 22～24 and the comparative example 8～11, adopt following method to estimate.The results are shown in table 3.

(1) ultraviolet ray transmissivity

To the shrink label that makes, adopt spectrophotometer (U-3410, Hitachi society system), measure ultraviolet ray (wavelength: 200～380nm) transmitance.Sweep velocity is the 120nm/ branch.Moreover, if ultraviolet ray transmissivity in the gamut of 200～380nm less than 1%, then think to have sufficient ultraviolet isolating.In addition, put down in writing the maximal value of the ultraviolet ray transmissivity under 200～380nm in the table 1.

(2) have or not and separate out

For the shrink label that makes, under the ambiance of 23 ℃ of temperature, humidity 55% from behind the firm system film after preserve a week, by with finger wiping film surface, have or not by following standard evaluation and to separate out.

Zero: not attached to the material on the finger.

*: pulverous material is attached on the finger.

(3) pollution of roller

After coextrusion finishes, the dirt of the chill roll of visualization traction engine, whether observation ultraviolet light absorber occurs is separated out cause fuzzy.

Zero: do not find fuzzy fully.

*: find to have fuzzy

(4) cutting at place, machine hole

Zero: scratch the machine hole easily, can take off shrink label.

*: be difficult to take off with hand sometimes.

(5) oil resistance

After coating edible oil on the shrink label of 30 containers that shrink label is installed, the state of visualization shrink label is by following standard evaluation oil resistance.

Zero: do not find wrinkle on the shrink label fully or break.

*: finding on the shrink label has wrinkle or breaks.

[table 3]

	Ultraviolet ray transmissivity (%) (showing peaked wavelength among 200～380nm)	Have or not and separate out	The pollution of roller	Machine hole cutting	Oil resistance
		Have or not and separate out	The pollution of roller	Machine hole cutting	Oil resistance	Embodiment 22	0.3(380nm)	○	○	○	○
Embodiment 23	0.7(380nm)	○	○	○	○	Embodiment 22	0.3(380nm)	○	○	○	○
Embodiment 23	0.7(380nm)	○	○	○	○	Embodiment 24	0	○	○	○	○
Comparative example 8	62(380nm)	○	○	○	○	Embodiment 24	0	○	○	○	○
Comparative example 8	62(380nm)	○	○	○	○	Comparative example 9	2.3(280nm)	○	○	○	×
Comparative example 10	0	×	○	○	×	Comparative example 9	2.3(280nm)	○	○	○	×
Comparative example 10	0	×	○	○	×	Comparative example 11	1.3(380nm)	○	×	×	○

Utilize possibility on the industry

According to the present invention, cutting, the outward appearance excellence at lower temperature resistance, heat resistance, oil resistivity, place, machine hole can be provided, and can not produce the shrink label take plural layers as basement membrane of peeling off when installing, and can prevent effectively that the content of container is deteriorated by ultraviolet ray when using as the shrink label of container, and the multi-layer resinous film of heat-shrinkable of the cutting at place, machine hole and oil resistivity excellence and the shrink label take the multi-layer resinous film of this heat-shrinkable as basement membrane.

Claims

1. shrink label is characterized in that,

Be that the multi-layer resinous film of heat-shrinkable with the outer coversheet that contains polyester resin that comprises the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping is the shrink label of basement membrane,

The polystyrene resins that constitutes aforementioned middle layer is aromatic ethenyl hydrocarbon-conjugated diene copolymer,

It is bonding that aforementioned middle layer and outer coversheet utilization contain the bonding coat of the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule.

2. shrink label is characterized in that,

The polystyrene resins that constitutes aforementioned middle layer is the hybrid resin of aromatic ethenyl hydrocarbon-conjugated diene copolymer and aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer,

The bonding coat that aforementioned middle layer and outer coversheet utilization contain the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule carries out bonding.

3. claim 1 or 2 described shrink labels, it is characterized in that the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule of formation bonding coat is maleic anhydride modified styrene-ethylene/butylene-styrene block copolymer, amine modified phenylethylene-ethylene/butylene-styrene block copolymer, amine modified phenylethylene-butadiene/butylene-styrene segmented copolymer or carboxyl acid modified styrene-butadiene/butylene-styrene segmented copolymer.

4. claim 1 or 3 described shrink labels is characterized in that, the aromatic ethenyl hydrocarbon-conjugated diene copolymer that constitutes the middle layer is s-B-S multipolymer and/or styrene-isoprene-butadiene-styrene copolymer.

5. claim 2 or 3 described shrink labels, it is characterized in that, the use level of the aromatic ethenyl hydrocarbon-conjugated diene copolymer in the hybrid resin in formation middle layer is 20～80 weight %, and the use level of aromatic ethenyl hydrocarbon-aliphatics unsaturated carboxylic acid ester copolymer is 20～80 weight %.

6. claim 1,2,3,4 or 5 described shrink labels, it is characterized in that, the polyester resin that constitutes outer coversheet contains composition from terephthalic acid (TPA) as the dicarboxylic acid composition, and contains composition from ethylene glycol and 1,4 cyclohexane dimethanol as glycol component.

7. the multi-layer resinous film of heat-shrinkable is characterized in that, is the multi-layer resinous film of heat-shrinkable that comprises the outer coversheet that contains polyester resin in the middle layer of containing polystyrene resins and the aforementioned middle layer of clamping, and ultraviolet light absorber is contained in aforementioned middle layer.

8. the multi-layer resinous film of the described heat-shrinkable of claim 7, it is characterized in that between middle layer and outer coversheet, having the bonding coat that contains the hydride that has the aromatic ethenyl hydrocarbon-conjugated diene copolymer that is selected from least a functional group in carboxylic acid group, anhydride group, amino, epoxy radicals and the hydroxyl in the molecule.

9. shrink label is characterized in that, uses claim 7 or the multi-layer resinous film of 8 described heat-shrinkables and forms.