CN101155689B - Heat shrinkable polyester film and heat shrinkable label - Google Patents
Heat shrinkable polyester film and heat shrinkable label Download PDFInfo
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- CN101155689B CN101155689B CN2006800112246A CN200680011224A CN101155689B CN 101155689 B CN101155689 B CN 101155689B CN 2006800112246 A CN2006800112246 A CN 2006800112246A CN 200680011224 A CN200680011224 A CN 200680011224A CN 101155689 B CN101155689 B CN 101155689B
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Abstract
To provide a heat-shrinkable polyester film which little causes printing omission in spite of its being produced by using a recycled material such as PET bottle and which satisfies the requirements of application of PET Bottle Recycling Recommendation Mark. [MEANS FOR SOLVING PROBLEMS] A heat-shrinkable polyester film produced either by laminating a substrate layer containing recycled PET bottle material with a layer free from recycled PET bottle material on at least one side and printing the layer free from recycled PET bottle material or by laminating a substrate layer containing 45 to 80 wt% of recycled PET bottle material with layers made mainly of a noncrystalline raw material on the both sides, in which when the film is dipped in water at 80 DEG C for 10 seconds and drawn up, the heat shrinkage in the main-shrinkage direction is 30% or above and the heat shrinkage in the direction perpendicular to the main-shrinkage direction is 10% or below and which is stretched at least uniaxially.
Description
Technical field
The present invention relates to apply flexibly the heat-contractable ployester series film of the recycling that is of value to the PETG bottle that adapts with environmental problem, resources effective.
Background technology
Lid shape sealing as the body label of PETG bottle container etc. or glass container etc. use heat-schrinkable film, the film that mainly uses polystyrene, polyester to be.Because heat-shrinkable polystyrene film compares with heat-contractable ployester series film, cheap and be easier to carry out shrink process, therefore use mainly as current version.On the other hand, because heat-contractable ployester series film compares with the polystyrene film, the gloss with excellent heat resistance, film is good, the characteristics such as fastening stress height after shrinking, and therefore is mainly used in the purposes that requires GOOD TASTE.
On the one hand, viewpoint such as apply flexibly from environmental problem or resources effective, the work of polyester regenerative raw materials such as recycling PETG bottle is carried out just actively, and heat-contractable ployester series film is film a kind of that can carry out recycling.For example, in patent documentation 1, put down in writing the invention of the heat-schrinkable film material that constitutes by PETG container made source resin and non-crystalline polyester.
But the PETG regenerative raw materials that is made of PETG bottle etc. is the raw material that is mixed with various containers.Except dissimilar polymers such as label or lid, also sneak in circulation or step for regeneration the sand that adheres to etc.Use the film of this regenerative raw materials to exist and become projection as karyomorphism, the problem such as bad of biting and brushing with described tramp material.In addition, departing from of rerum naturas such as monomer composition, degree of crystallinity is big, even make the heat-shrinkable film of 1 layer of structure, can not obtain the goods of stabilizing quality.In addition, estimate undercapacity, add man-hour printing to wait, the problem of cut-out takes place because of the decline film of the molecular weight in the step for regeneration.In addition, use the heat-contractable ployester series film of the more PETG raw material that comprises regenerative raw materials, also exist and to carry out bonding problem with solvents tetrahydrofurane commonly used.
Patent documentation 1: the spy opens 2004-196918
Summary of the invention
One of the present invention, brush few heat-contractable ployester series film even provide use PETG bottle regenerative raw materials such as (PET Bottle) also to bite, two, even regenerative raw materials such as using the PETG bottle is provided, do not cut off man-hour printing etc. to add, can carry out bondingly with oxolane, and be suitable for the heat-contractable ployester series film that sign (recycling recomenndation mark) applicable elements is recommended in the recycling of PETG bottle.
Can solve the application's of above-mentioned problem the 1st heat-contractable ployester series film of inventing, at the folded layer that does not contain PETG bottle regenerative raw materials of at least one surface layer of the basic unit of containing PETG bottle regenerative raw materials, the percent thermal shrinkage that floods the main shrinkage direction after picking up for 10 seconds in 80 ℃ warm water is more than 30%, the percent thermal shrinkage of the direction vertical with main shrinkage direction is below 10%, do not contain PETG bottle regenerative raw materials the layer as at least the one side side outermost layer.Satisfying under the situation of this scope, brushing few heat-contractable ployester series film even can provide regenerative raw materials such as using the PETG bottle also to bite.
This embodiment is with regard to above-mentioned film, become more than the preferred 4 μ m of thickness of layer of the regenerative raw materials that does not contain the PETG bottle of face of printing surface, the content of the PETG bottle regenerative raw materials of basic unit is the following embodiments of 40 weight %.
Can solve the application's of above-mentioned problem the 2nd heat-contractable ployester series film of inventing, it is characterized in that, contain the above PETG bottle regenerative raw materials of 25 weight % in the film, in 80 ℃ warm water, flood the percent thermal shrinkage of the main shrinkage direction after picking up for 10 seconds more than 30%, and the percent thermal shrinkage of the direction vertical with main shrinkage direction is below 10%, with film 30 ℃ of temperature, keeping was carried out tension test after 28 days in the atmosphere of relative humidity 85% on the direction vertical with main shrinkage direction, and the ratio of the total relatively test piece number of the test piece number that ruptures under the situation of elongation below 5% is below 25%.
Heat-contractable ployester series film of the present invention, the regenerative raw materials that no matter uses the PETG bottle whether, all have good printing or mechanical strength, in addition, can carry out bonding in common solvent, also be suitable for the recycling of PETG bottle and recommend the sign applicable elements, also useful from the angle that environmental problem or resources effective are applied flexibly.
The specific embodiment
The heat-contractable ployester series film of the application's the 1st invention, it is at least one single face in the basic unit that comprises PETG bottle regenerative raw materials, the stacked heat-contractable ployester series film that does not comprise the layer of PETG bottle regenerative raw materials.With regard to PETG bottle regenerative raw materials, though in its operation, carry out raw-material differentiation of xenogenesis or washing, can sneak into lid or printed label, perhaps sneak into attached to the sand on the PETG bottle etc.When using this regenerative raw materials to make film, these impurity become nuclear and form the projection of 0.1～a few μ m on films., around projection perk taking place and the China ink of this part is not shifted when this film copying and printing China ink by intaglio printing etc., causes becoming the brush of biting.
But, in the application's the 1st invention, with heat-contractable ployester series film as multi-ply construction, be different from the layer that comprises PETG bottle regenerative raw materials, by at least on printing surface stacked do not comprise PETG bottle regenerative raw materials the layer and can improve bite the brush film.Become above-mentioned film printing surface do not comprise PETG bottle regenerative raw materials the layer the preferred 4 μ m of thickness more than.At this moment because if this layer thickness is thin than 4 μ m, the effect that then hides the projection that the PETG bottle regenerative raw materials by basic unit causes reduces and the brush of biting becomes cause how.The thickness of layer that does not comprise PETG bottle regenerative raw materials is more preferably more than the 6 μ m, further more than the preferred 10 μ m.Under the situation of implementing two-face printing, the layer that does not comprise PETG bottle regenerative raw materials more than the 4 μ m need be set on table back of the body two sides.
In the application's the 1st invention, below the preferred 40 weight % of addition of the PETG bottle regenerative raw materials of basic unit.More preferably below the 30 weight %.Because PETG bottle regenerative raw materials is except having the problem that impurity such as xenogenesis raw material or sand are sneaked into, still by the material that melt viscosity, molecular weight, molecular weight distribution, monomer are formed, different various PETG bottles such as the kind of degree of crystallinity, polymerization catalyst or addition constitute, so there be very wide departing from these rerum naturas on every production lot of regenerative raw materials.The film that adds regenerative raw materials such more than the 40 weight % exists departing from of quality big, can not obtain the percent thermal shrinkage of needs or the situation of mechanical strength as heat-shrinkable label.With regard to regard to the lower limit of the adding rate of the PETG bottle regenerative raw materials of basic unit, have no particular limits, but more than the preferred 10 weight %, more preferably more than the 15 weight %.
But, in the application's the 1st invention, by with heat-shrinkable film as multi-ply construction, the addition of restriction PETG bottle regenerative raw materials, and the mode of the layer that does not comprise PETG bottle regenerative raw materials is set, guarantees percent thermal shrinkage or mechanical strength.The addition of PETG bottle regenerative raw materials is more preferably below all 25 weight % of film, can by adjust basic unit and do not add PETG bottle regenerative raw materials layer ratio realize.Preferred 40: 60～95: 5 of layer ratio.Below all 20 weight % of the further preferred film of addition of PETG bottle regenerative raw materials.
With regard to the lower limit of addition, have no particular limits, but more than the preferred 5 weight %, more preferably more than the 10 weight %.The usage rate of regenerative raw materials is high more, and the recycling efficient of PETG bottle is just high more, and is from the viewpoint that environmental problem, resources effective are applied flexibly, preferred.
The heat-contractable ployester series film of the application's the 2nd invention, in film, contain more than the 25 weight %, the PETG bottle regenerative raw materials of preferred 25～45 weight %, the main component that more preferably constitutes film is an ethylene glycol terephthalate, the less important constituent that comprises more than one, contain neopentyl glycol or 1 as maximum less important constituents, any one of 4-cyclohexanedimethanol.The heat-contractable ployester series film that further preferably has the multi-ply construction more than 2 layers of the layer (A layer) that comprises 45～80 weight % PETG bottle regenerative raw materials and other layers (B layer), wherein, the B layer with ethylene glycol terephthalate as the main composition composition, and contain more than one the less important constituent that constitutes by polybasic carboxylic acid composition and/or polyol component, when with the total amount of polybasic carboxylic acid composition as 100 moles of %, the total amount of polyalcohol alcohol composition is during as 100 moles of %, and the content that becomes the polybasic carboxylic acid composition of the maximum less important constituents in the B layer or polyol component is at 20 moles more than the %.With regard to this film, even the adding rate of the PETG by improving basic unit and the low recycling raw material of operating characteristic viscosity also can be guaranteed the mechanical strength of practical level, become amorphous less important constituent and guarantee essential shrinkage factor by containing, and can carry out bonding with the common solvent oxolane as shrink label at the table backing layer.Also have in the present invention, can carry out solvent welding and just be meant that solvent welding intensity is more than the 3N/15mm in the evaluation method of embodiment described later.
The content of PETG bottle regenerative raw materials in the heat-contractable ployester series film of the application's the 2nd invention more than 25 weight %, preferred 25～45 weight %.If be lower than 25 weight %, then from being not suitable for the PETG bottle recycling recommendation sign that the recycling of PETG bottle advances consultation to assert, the recycling efficient of PETG bottle is low, the viewpoint that environmental problem, resources effective are applied flexibly is set out, and need carry out improved cause.On the other hand, if be higher than 45 matter weight %, then because essential shrinkage factor deficiency, therefore not sorrow choosing.
In the application's the 2nd invention, preferred implementation is the heat-contractable ployester series film with multi-ply construction more than 2 layers of the layer (A layer) that comprises the above PETG bottle regenerative raw materials of 45 weight % and other layers (B layer), more than the preferred 45 weight % of adding rate of the PETG bottle regenerative raw materials of A layer below the 80 weight %.If it is above less than 45 weight % that this adding rate is 25 weight %, mechanical undercapacity then takes place easily, add the cut problem of film in man-hour printing etc.If be lower than 25 weight %, then the recycling efficient from the PETG bottle is low, and the viewpoint that environmental problem, resources effective are applied flexibly is set out, and needs to improve.On the other hand, if be higher than 80 weight %, then essential shrinkage factor is with deficiency.To the addition of the PETG bottle regenerative raw materials of A layer more preferably more than the 45 weight % below the 70 weight %, further below the above 65 weight % of preferred 50 weight %.
Lit-par-lit structure with the present invention during as multi-ply construction, the 2 kinds 3 layers structure, 2 kinds that can adopt 2 kinds 2 layers structure, the B/A/B of A/B more than 4 layers structure and increased the 3rd layer B/C/A/C/B or any one of 3 kinds of structures more than 3 layers such as C/B/A/B/C etc., particularly from using the angle of tetrahydrofuran solvent stable adhesion, 2 kinds of 3 layers of formations of preferred B/A/B.The 3rd layer of C layer can be that the middle of A layer, B layer formed, and also can be the layer that comprises colouring agent or ultra-violet absorber.In addition, when being used for outermost layer,, therefore also can be used as the layer that does not comprise regenerative raw materials owing to worry the problem of regenerative raw materials, promptly contain contaminant.Also have, when as multi-ply construction, can adjust by addition and each layer ratio with respect to the PETG bottle regenerative raw materials of each layer with respect to all addition of the film of PETG bottle regenerative raw materials.Preferred layer ratio, for example the preferred layer ratio of A layer and B layer is 30: 70～70: 30 in 2 kinds of 3 layers of structures of B/A/B.
In 2 kinds of 3 layers of structures of described B/A/B, preferably introduce the noncrystalline composition to table backing layer (B layer), guarantee essential shrinkage factor, and guarantee bonding with the common solvent oxolane, preferred 20 moles more than the % of the content of maximum less important constituents (noncrystalline composition) as shrink label.As said noncrystalline composition here, preferred neopentyl glycol composition and/or 1, the 4-cyclohexanedimethanol, if act concrete example, then use PETG and neopentyl glycol and/or 1, the 4-cyclohexanedimethanol is as the copolymer of main body, and this copolymerization ratio is preferably in the scope of 20～40 moles of %.When copolymerization ratio is during less than 20 moles of %, be difficult to carry out bonding with oxolane, can not obtain essential shrinkage factor in addition.On the other hand,, then be difficult to improve the degree of polymerization if copolymerization ratio is higher than 40 moles of %, in addition in system predrying before the film, the baking temperature etc. that can not raise for the adhesion between the powder, thus production efficiency descends.More than the preferred 65 weight % of the addition to the B layer of this copolymer.Also have, preferred below 35% to the addition of the PETG bottle regenerative raw materials of B layer, more preferably below 20%.
The percent thermal shrinkage of the main shrinkage direction of heat-contractable ployester series film of the present invention in 80 ℃ warm water is more than 30%.If this shrinkage factor is less than 30%, when then being contracted on the container such as bottle when lining, having and be not bonded in the part on the container and become bad as label.The percent thermal shrinkage of main shrinkage direction is more preferably more than 40%, and is further preferred more than 50%.
In addition, the percent thermal shrinkage of the direction vertical with main shrinkage direction is below 10%.If this shrinkage factor is greater than 10%, when then lining is shunk on container vertical contraction of label big, appearance poor not only thus, and the position of label is also unstable.The percent thermal shrinkage of the direction vertical with main shrinkage direction is more preferably below 8%, and is further preferred below 6%.
PETG bottle regenerative raw materials among the present invention is meant the regenerative raw materials of PETG containers such as PETG bottle, though material regeneration raw material, chemical regeneration raw material are arranged, its any kind can be used.Can only use a kind of or the mixing use.
More than the preferred 0.61dl/g of the inherent viscosity of film of the present invention.Owing to more than 0.61dl/g, improves the mechanical strength or the anti-breaking property of film, process or solvent welding adds and can reduce unfavorable conditions such as fracture man-hour printing by the inherent viscosity that makes film.For the inherent viscosity that makes film more than 0.61dl/g, for example can realize by the mode of in employed polyester, adding the raw material of HMW.In the present invention, though exist in basic unit's situation different with the printed layers inherent viscosity, all as film, if inherent viscosity is then harmless more than 0.61dl/g.Also have, the more preferably inherent viscosity of film is more than 0.63dl/g.
Also have, in the application's the 1st invention, with regard to mechanical strength, with film in the atmosphere of 30 ℃ of temperature, relative humidity 85% keeping 28 days after, carry out the tension test of the direction vertical with main shrinkage direction, the ratio (initial stage fracture rate) of the total relatively test piece number of the test piece number that ruptures under the situation of elongation 5% is preferred below 70%, below 25%, is below 25% in the application's the 2nd invention more preferably.By making this initial stage fracture rate in prescribed limit, behind long-time keeping film, also can guarantee good suitable processability.In order to be controlled in the prescribed limit by the initial stage fracture rate, preferably control described PETG bottle regenerative raw materials combined amount, lit-par-lit structure, film inherent viscosity and with film-forming method combination described later.
Heat-contractable ployester series film of the present invention will be had as the main composition unit by the ester units that polybasic carboxylic acid composition and polyol component form.If consider the anti-breaking property, intensity, hear resistance of film etc., among then preferred 100 moles of % in formation unit that select to make heat-contractable ployester series film the above ethylene glycol terephthalate unit of 50 moles of % is arranged.Thereby preferably in 100 moles of % of polybasic carboxylic acid composition, terephthalic acid (TPA) composition (composition that is made of terephthalic acid (TPA) or its ester) is 50 moles more than the %, and in 100 moles of % of polyol component, glycol component is 50 moles more than the %.Preferred ethylene glycol terephthalate unit is 55 moles more than the %, further preferred 60 moles more than the %.
Conduct is used to form the multivalence alcohols of multivalence alcohol composition in ester units, except above-mentioned ethylene glycol and neopentyl glycol, can also be also with 1, ammediol, triethylene glycol, 1,4-butanediol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1, ammediol, 1,9-nonanediol, 1, the alkylene oxide additives of aliphatic diols such as 10-decanediol, trimethylolpropane, glycerine, pentaerythrite, diethylene glycol (DEG), two poly-dihydric alcohols, polyoxy tetramethyl glycol, bisphenol compound or derivatives thereof etc.
In addition, as the polybasic carboxylic acid class that is used to form the polybasic carboxylic acid composition, except above-mentioned terephthalic acid (TPA) and ester thereof, the derivative that can utilize aromatic dicarboxylic acid, form by their ester, aliphatic dicarboxylic acid etc.As aromatic dicarboxylic acid, can enumerate for example M-phthalic acid, naphthalene-1,4-or-2,6-dicarboxylic acids, 5-sulfoisophthalic acid sodium etc.In addition, as the ester derivant of these aromatic dicarboxylic acids or terephthalic acid (TPA), can enumerate derivatives such as dialkyl, diaryl ester.As aliphatic dicarboxylic acid, can enumerate glutaric acid, adipic acid, decanedioic acid, azelaic acid, oxalic acid, butanedioic acid etc. or be commonly referred to the aliphatic dicarboxylic acid of dimeric dibasic acid.In addition, can also be as required also with polybasic carboxylic acids such as hydroxycarboxylic acid, trimellitic anhydride, pyromellitic acid dianhydride such as p-hydroxybenzoic acids.
Outside, though be not polyalcohol, polybasic carboxylic acid class, also can use a part with the lactone of 6-caprolactone as representative.Can think that lactone is the material that is made of the unit that has ester bond after the open loop at two ends, 1 lactone to come source unit be the carboxylic acid composition and be pure composition.Thereby, when using lactone, the amount of adding the source quantity of units of lactone in the amount of polyol component is calculated 1, the amount of 4-cyclohexanedimethanol composition or the amount of other polyol components as 100 moles of %.In addition, when calculating the amount of each polybasic carboxylic acid composition, will become the amount of the source quantity of units of adding lactone in the component at polybasic carboxylic acid as 100 moles of %.
As the preferred component that constitutes the unit beyond the ethylene glycol terephthalate unit, preferably can reduce the material of guaranteeing low temperature heat-shrinkable or solvent welding based on the high crystalline of ethylene glycol terephthalate unit.As the crystalline composition of such reduction, in the polybasic carboxylic acid composition, can enumerate M-phthalic acid, naphthalene-1 as preferred substance, 4-or-2, the 6-dicarboxylic acids can be enumerated neopentyl glycol, 1 as preferred substance in polyol component, 4-cyclohexanedimethanol, 1,4-butanediol, 1, ammediol.By and reduce crystalline composition with these, can balancedly improve heat shrinkability characteristic and the anti-breaking property and the solvent welding of film.Particularly, preferably becoming the layer of superficial layer at least, using the polyester that comprises by at least a unit that constitutes of these preferred components as part of raw materials from the viewpoint of solvent welding.In the 100 moles of % in the formation unit of raw material polyester, comprise these unit that reduce crystalline composition preferably at 10 moles more than the %, more preferably 12 moles more than the %, further preferred 15 moles more than the %.Particularly preferred embodiment is, with the total amount of polybasic carboxylic acid composition as 100 moles of %, the total amount of polyol component is during as 100 moles of %, the neopentyl glycol and/or 1 that contains 10～30 moles of %, the 4-cyclohexanedimethanol, and contain 1 of 5～30 moles of %, 4-butanediol and/or 1, ammediol.
The polyester that constitutes heat-contractable ployester series film can be made by carrying out melt polymerization according to common method, but can enumerate, carry out directly polymerization polycondensation, so-called with making omega-dicarboxylic acids and glycols directly react resulting oligomer, make the dimethyl ester body of dicarboxylic acids and glycol carry out carrying out after the ester exchange reaction polycondensation, so-called ester-interchange method etc., can be suitable for autofrettage arbitrarily.In addition, also can be the polyester that obtains by other polymerization.As polymerization catalyst, can use various catalyst commonly used, can enumerate, for example Titanium series catalyst (four titanium butoxide etc.), antimony-based catalyst (antimony trioxide etc.), germanium series catalysts (germanium dioxide), cobalt series catalyst (cobalt acetate etc.) etc.
In addition,, also can add inorganic lubricants such as titanium dioxide, finely particulate silica, kaolin, calcium carbonate for example, organic lubricant such as long-chain fatty acid ester for example in addition in order to improve easy the to be sliding property of heat-schrinkable film.In addition, as required, can also add additives such as stabilizing agent, colouring agent, antioxidant, antistatic agent, ultra-violet absorber.
Make heat-contractable ployester series film of the present invention, preferred following method.At first, use sheet PETG (PET) bottle recycling raw material and the polyester raw material beyond these, it is used drying machines such as box drier, vane type drying machine, or vacuum drier carries out drying.Afterwards, suit to mix, under 200～300 ℃ temperature, extrude with the film shape from extruder.Perhaps, removing the moisture limit with undried at clino-axis type extruder inner edge extrudes with the film shape.Make the method for the laminate film of multi-ply construction, can use coextrusion.PETG bottle recycling raw material can use the sheet-shaped material that washs, pulverizes with well-known method.
Can use any one of original methods such as T modulus method, tubular method when extruding.Extrude the back and obtain non-stretched film with casting (casting) roller quenching.Also have, " non-stretched film " also comprises the film that has acted on the required tension force of the film feeding in the manufacturing process.Between above-mentioned extruder and casting roll, set electrode, electrostatic by applied voltage between electrode and casting roll again film is bonded on the roller, from the viewpoint of the thickness spot that suppresses film, preferred.
Carry out stretch processing with regard to above-mentioned non-stretched film.With regard to stretch processing, both can carry out continuously after the cooling by above-mentioned casting roll etc., can also cool off the back in case curl and being the roller shape, carry out again afterwards.Also have and since the maximum collapse direction be film horizontal stroke (width) to, on production efficiency, have practicality, therefore represent the example of maximum collapse direction below as the pulling method of horizontal situation.With the maximum collapse direction as film vertical (length) to situation under, also can stretch according to the bearing of trend in the following method is changed 90 ° of common operations such as grade.
When heat-contractable ployester series film being carried out cross directional stretch with stenter, before stretching process, film is heated to surface temperature and becomes uniform temperature in the Tg+0 ℃～Tg+60 ℃ scope, under the set point of temperature in Tg-20 ℃～Tg+40 ℃ scope, be stretched to 2.3～7.3 times, preferred 2.5～6.0 times.Afterwards, under the set point of temperature in 50 ℃～110 ℃ scopes, heat-treat when carrying out the mitigation of 0～15% stretching or 0～15%, carry out further heat treatment under the set point of temperature in 40 ℃～100 ℃ scopes as required, thereby obtain heat-contractable ployester series film.
As the method that stretches, not only can implement horizontal uniaxial tension, but also can implement 1.0 times longitudinally～4.0 times, preferred 1.1 times～2.0 times stretching with stenter.Under the situation of carrying out 2 such stretchings, can use one by one any one of 2 stretchings, 2 stretchings simultaneously, as required, can also stretch again.In addition, in 2 stretchings one by one, as the order that stretches, can be in length and breadth, horizontal vertical, longitudinal and transverse any one that waits in length and breadth in length and breadth.
With regard to the thickness of heat-contractable ployester series film of the present invention, there is no particular limitation, and for example, as the label heat-contractable ployester series film, recommending total thickness is more than the 20 μ m, more than the preferred 25 μ m, and below the 300 μ m, the film that preferred 200 μ m are following.
For above-mentioned heat-contractable ployester series film is made heat-shrinkable label, inboard a little at the ora terminalis of the single face of film one end with the bonding solvent of using of Rack coating, immediately film is rounded the back overlapped ends and carry out bondingly, be processed as tubulose with the shaping of well-known tubulose with device again.This pipe can be blocked with specific length and as heat-shrinkable label of the present invention.
With regard to film bonding, though can adopt a part that makes film to carry out the melting adhered method of fusion, the viewpoint of the change of the heat shrinkability characteristic that suppresses label of not associating etc. is set out, and preferably uses solvent to carry out.As spendable solvent, can enumerate, for example, aromatic hydrocarbons such as benzene,toluene,xylene, trimethylbenzene; Halogenated hydrocarbons such as carrene, chloroform; Phenol such as phenol; Furans such as oxolane; 1,3-oxa-penta ring waits the tetrahydrofuran class, waits organic solvent.Wherein, preferred 1 from safe viewpoint, 3-oxa-penta ring or oxolane.After this heat-shrinkable label being contained on the containers such as PETG bottle, can making its thermal contraction and be covered with well-known thermal contraction device (hot-flow flue or steam air channel etc.).
Below, further describe the present invention according to embodiment, but following embodiment is not limited to the present invention, in the scope that does not exceed aim of the present invention, change the situation of enforcement, be contained in the present invention.In addition, the assay method of the rerum natura of the film that obtains from embodiment and comparative example is as follows.
(1) percent thermal shrinkage
Film is blocked square into 10cm * 10cm, in 95 ℃ ± 0.5 ℃ warm water, flooded for 10 seconds and carry out thermal contraction with no load condition, be immersed in immediately afterwards in 25 ℃ ± 0.5 ℃ the warm water, measure the length of the vertical and transverse direction of sample afterwards, according to following formula evaluation.With the direction of shrinkage factor maximum as the maximum collapse direction.
Percent thermal shrinkage (%)=(length after perisystolic length-contraction) ÷ (perisystolic length) * 100
(2) printing
Use the eastern paddy ironworker system PAS of society of institute type printing machine, Japan's China ink is made the gravure roll of the China ink (shrinking the EX grass green) of society's system with 150 lines * 30 μ m * 20%, speed with 100m/ minute is printed on film, amplify printing surface with magnifying glass (15 times), the black hole count that number is corresponding per 1 square centimeter is estimated with following judgment standard again.
Zero: 0～10
△: 11～50
*: more than 51
(3) mechanical strength
To carry out tension test (distance: 20mm, draw speed: 200mm/ minute, temperature between test piece width: 15mm, test piece length: 120mm, chuck: 23 ℃, sample number: 20) on the direction vertical after 28 days in keeping under the atmosphere of 30 ℃ * relative humidity 85% with the maximum collapse direction, the test piece number that ruptures under the situation of elongation below 5% is counted, estimated with following judgment standard again.Also have, the ratio (%) of the total relatively test piece number of the test piece number that ruptures under the situation of elongation below 5% is as the initial stage fracture rate.
Zero: 0～5 (initial stage fracture rate 0～25%)
△: 6～14 (initial stage fracture rate 30～70%)
*: 15～20 bars (initial stage fracture rate 75～100%)
(4) inherent viscosity
The smart 0.1g sample (sheet or film) that claims, be dissolved in the mixed solvent of phenol/tetrachloroethanes=3/2 (mass ratio) of 25ml after, measure under 30 ± 0.1 ℃ with oersted Wa Erteshi viscosimeter.Inherent viscosity [η] is tried to achieve according to following formula (Huggins formula).
[several 1] η
Sp/ c=[η]+k[η]
2c
K is so-called Huggins constant, is the interactional yardstick of hydrodynamics between solute molecule.
From the viscosimetric analysis of the different solution of a plurality of concentration, with η
Sp/ c is that [η] tried to achieve in c → 0 with respect to the c trace with resulting linear extrapolation.
η
SpInherent viscosity when concentration is c.
(5) solution cementability
At the single face of film with coating amount 3g/m
2, width 5mm continuously coating oxolane (THF), immediately film is bondd to each other, film is engaged is processed as tubulose.After placing 24 hours under the environment of 25 ℃ of temperature, relative humidity 65%, this Guan Zaiyu is added passing through on the vertical direction of direction to cut off with width 15mm and taking a sample of man-hour, the disbonded test of T type is carried out with regard to above-mentioned direction in the bonding part according to JIS K 6854.
The test piece number as 20, carrying out under the condition apart from 20mm, test piece width 15mm, 23 ℃ of temperature, draw speed 200mm/ minute between test piece length 60mm, chuck, is estimated according to following judgment standard.
Zero: more than the 3N/15mm
*: less than 3N/15mm
Experiment 1
Basic unit uses the polyester based resin that polyester A:10 weight %, polyester B:55 weight %, polyester C:10 weight %, polyester D:25 weight % are mixed, with regard to the table back of the body is outer, respectively with the polyester based resin of mixed polyester A:35 weight %, polyester B:55 weight %, polyester C:10 weight %, according to separately single shaft extruder after dissolving under 270 ℃, carry out coextrusion from the T mould, cool off with chill roller again, thereby obtained the non-stretched film (thickness: 200 μ m) of 3 layers of structure.With this non-stretched film after 88 ℃ of 10 seconds of following preheating, under 80 ℃, be stretched to 3.9 times with stenter to transverse direction, then carry out the heat treatment in 10 seconds under 78 ℃, (basic unit: 25 μ m/ show backing layer: heat-contractable ployester series film each 12 μ m) thereby obtain thickness 50 μ m.With the composition of employed polyester based resin and content representation in table 1.In table 1, TPA means that terephthalic acid (TPA), EG mean that ethylene glycol, BD mean 1, and 4-butanediol, NPG mean that neopentyl glycol, CHDM mean 1, the 4-cyclohexanedimethanol.In addition, the property list with film is shown in the table 2.
Experiment 2～4
Except the thickness that changes the table backing layer,, obtained the heat-contractable ployester series film of thickness 50 μ m by the method identical with embodiment 1.The property list of film is shown in the table 2.
Experiment 5
Basic unit uses the polyester based resin that polyester B:40 weight %, polyester C:10 weight %, polyester D:50 weight % are mixed, the table backing layer uses the polyester based resin with mixed polyester A:35 weight %, polyester B:55 weight %, polyester C:10 weight %, except showing backing layer respectively as the 4 μ m, by the method identical, obtained the heat-contractable ployester series film of thickness 50 μ m with embodiment 1.The property list of film is shown in the table 2.
Experiment 6～8
To carry out after raw materials mixed carries out drying with the raw material fit rate shown in the table 2 respectively, according to separately single shaft extruder after dissolving under 270 ℃, carry out coextrusion from the T mould, cool off with chill roller again, thereby obtained the non-stretched film (thickness: 160 μ m) of 3 layers of structure.With this non-stretched film after 85 ℃ of 10 seconds of following preheating, with stenter under 80 ℃ to 4 times of horizontal stretchings, then carry out the heat treatment in 10 seconds under 78 ℃, (basic unit: 20 μ m/ show backing layer: heat-contractable ployester series film each 10 μ m) thereby obtain thickness 40 μ m.With the composition of employed polyester based resin and content representation in table 1.The ployester series film that in experiment 6～8, makes, as shown in table 3, as seen have sufficient shrinkage factor and mechanical strength as heat-schrinkable film, can carry out bonding with the common solvent oxolane.
Experiment 9～10
Except as shown in the table 3 the raw material fit rate, by the methods identical, obtained the heat-contractable ployester series film of thickness 40 μ m with experiment 6～8.As shown in table 3, as seen a little less than the mechanical strength of basic unit's film identical (experiment 9) with the addition of the recycling raw material of table (skin) layer (table backing layer), little to basic unit with the shrinkage factor of the film (experiment 10) of high concentration interpolation recycling raw material, there is not sufficient shrinkage as film.
[table 1]
[table 2]
[table 3]
Utilize possibility on the industry
Although heat-shrinkable polyester film of the present invention uses PETG bottle regenerative raw materials owing to have the quality identical with in the past film, therefore as the heat-shrinkable label of close environment with film and useful.
Claims (10)
1. heat-contractable ployester series film, simple tension at least is characterized in that, the folded layer that does not contain PETG bottle regenerative raw materials of its at least one surface layer in the basic unit of containing PETG bottle regenerative raw materials,
For described do not contain PETG bottle regenerative raw materials the layer for, in 100 moles of % of polyol component of the raw material polyester that constitutes this layer that does not contain PETG bottle regenerative raw materials, the neopentyl glycol and/or 1 that contains 10～30 moles of %, the 4-cyclohexanedimethanol, and contain 1 of 5～30 moles of %, 4-butanediol and/or 1, ammediol.
And the percent thermal shrinkage that floods the main shrinkage direction after picking up for 10 seconds in 80 ℃ warm water is more than 30%, the percent thermal shrinkage of the direction vertical with main shrinkage direction is below 10%, do not contain PETG bottle regenerative raw materials the layer as at least the one side side outermost layer.
2. heat-contractable ployester series film according to claim 1 is characterized in that,
Do not contain PETG bottle regenerative raw materials the layer as at least the one side side outermost layer, the thickness of this layer is more than the 4 μ m.
3. heat-contractable ployester series film according to claim 1 and 2 is characterized in that,
The content of the PETG bottle regenerative raw materials in the basic unit is below the 40 weight %.
4. a heat-contractable ployester series film is characterized in that,
Be to have the layer that contains PETG bottle regenerative raw materials and the heat-contractable ployester series film of the multi-ply construction more than 2 layers of other layer in the film, contain the above PETG bottle regenerative raw materials of 45 weight % in the wherein said layer that contains PETG bottle regenerative raw materials
Described other layer with ethylene glycol terephthalate as the main composition composition and contain 20 moles more than the % with neopentyl glycol or 1, the 4-cyclohexanedimethanol is as the less important constituent of polyol component,
The percent thermal shrinkage that described film is flooded the main shrinkage direction after picking up for 10 seconds in 80 ℃ warm water is more than 30%, and the percent thermal shrinkage of the direction vertical with main shrinkage direction is below 10%, pulling test on the direction vertical with main shrinkage direction is carried out in film keeping in the atmosphere of 30 ℃ of temperature, relative humidity 85% after 28 days, and the test piece number that ruptures under the situation of the elongation 5% below relatively always ratio of test piece number is below 25%.
5. heat-contractable ployester series film according to claim 4 is characterized in that,
The main composition composition that constitutes film is an ethylene glycol terephthalate, and the content of the PETG bottle regenerative raw materials in the film is 25～45 weight %.
6. according to claim 4 or 5 described heat-contractable ployester series films, it is characterized in that,
Film can carry out bonding with tetrahydrofuran solvent.
7. according to any described heat-contractable ployester series film in the claim 1,2,4,5, it is characterized in that,
The inherent viscosity of film is more than the 0.61dl/g.
8. heat-contractable ployester series film according to claim 1 and 2 is characterized in that,
To not contain the layer of PETG bottle regenerative raw materials as printing surface.
9. according to claim 4 or 5 described heat-contractable ployester series films, it is characterized in that,
Described heat-contractable ployester series film is to have the layer (A layer) that contains 45～80 weight % PETG bottle regenerative raw materials and the multi-ply construction more than 2 layers of other layers (B layer), the B layer with ethylene glycol terephthalate as the main composition composition, and contain with neopentyl glycol or 1, the 4-cyclohexanedimethanol is as the less important constituent of polyol component, when with the total amount of polyol component during as 100 moles of %, neopentyl glycol or 1 in the B layer, the content of 4-cyclohexanedimethanol composition are at 20 moles more than the %.
10. heat-shrinkable label, wherein,
It is made by any described heat-contractable ployester series film in the described claim 1,2,4,5.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005112176A JP5011651B2 (en) | 2005-04-08 | 2005-04-08 | Heat-shrinkable polyester film and heat-shrinkable label |
| JP112176/2005 | 2005-04-08 | ||
| JP180623/2005 | 2005-06-21 | ||
| JP2005180623A JP4894176B2 (en) | 2005-06-21 | 2005-06-21 | Heat-shrinkable polyester film and label using recycled PET bottle materials |
| PCT/JP2006/307313 WO2006109662A1 (en) | 2005-04-08 | 2006-04-06 | Heat-shrinkable polyester film and heat-shrinkable labels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101155689A CN101155689A (en) | 2008-04-02 |
| CN101155689B true CN101155689B (en) | 2011-05-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800112246A Expired - Fee Related CN101155689B (en) | 2005-04-08 | 2006-04-06 | Heat shrinkable polyester film and heat shrinkable label |
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| Country | Link |
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| JP (1) | JP5011651B2 (en) |
| CN (1) | CN101155689B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4524718B2 (en) * | 2008-08-08 | 2010-08-18 | 東洋紡績株式会社 | Heat-shrinkable polyester film |
| KR100964295B1 (en) | 2010-01-06 | 2010-06-16 | 에스케이씨 주식회사 | Heat shrinkable polyester film and preparation method thereof |
| CN111823680A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking low-density shrink film and preparation method thereof |
| CN111823679A (en) * | 2020-06-09 | 2020-10-27 | 山东圣和塑胶发展有限公司 | Light-blocking shrink film and preparation method thereof |
| JPWO2023013689A1 (en) * | 2021-08-05 | 2023-02-09 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004196918A (en) * | 2002-12-17 | 2004-07-15 | Fuji Seal Inc | Material for heat-shrinkable film, polyester heat-shrinkable film and polyester shrinkable label |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000141573A (en) * | 1998-11-17 | 2000-05-23 | Toray Ind Inc | Polyester biaxially stretched film |
| JP2001122988A (en) * | 1999-10-26 | 2001-05-08 | Toray Ind Inc | Polyester film for laminate |
| JP2002067210A (en) * | 2000-08-31 | 2002-03-05 | Toyobo Co Ltd | Laminated heat-shrinkable film and label for |
| JP2002103545A (en) * | 2000-10-03 | 2002-04-09 | Toyobo Co Ltd | Heat-shrinkable polyester-based film |
-
2005
- 2005-04-08 JP JP2005112176A patent/JP5011651B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004196918A (en) * | 2002-12-17 | 2004-07-15 | Fuji Seal Inc | Material for heat-shrinkable film, polyester heat-shrinkable film and polyester shrinkable label |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006289727A (en) | 2006-10-26 |
| CN101155689A (en) | 2008-04-02 |
| JP5011651B2 (en) | 2012-08-29 |
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