CN100515764C - Heat shrink film - Google Patents
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- CN100515764C CN100515764C CNB2004800371218A CN200480037121A CN100515764C CN 100515764 C CN100515764 C CN 100515764C CN B2004800371218 A CNB2004800371218 A CN B2004800371218A CN 200480037121 A CN200480037121 A CN 200480037121A CN 100515764 C CN100515764 C CN 100515764C
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Abstract
There is provided a heat shrink polyester film characterized in that (A) at least one major surface thereof is overlaid with 0.002 to 0.5 g/m<2>, in terms of solid content coating amount, of a silicone containing easily sliding layer, (B) the easily sliding layer having an inter-easily sliding layer frictional coefficient mud <= 0.27, and that (C) the heat shrink polyester film exhibits a heat shrinkage factor, as measured in the direction of maximum shrinkage after immersion in 95 1/2 C water for 10 sec, of 50% or greater. Thus, there is provided the heat shrink film that when used as a label of beverage container, enhances the smoothness of external surface side to thereby prevent merchandise jamming in an automatic vending machine of beverage and that is fully satisfactory in solvent bonding capability and excels in processability.
Description
Technical field
The present invention relates to a kind of heat-schrinkable film, more particularly, its purpose is to provide a kind of heat-shrinkable polyester film and heat-shrinkable polystyrene type film, when these films are used as the label of beverage-container, owing to improved the lubricity of outside one side, prevented the obstruction of commodity in the Drink dispenser, and the suitable property of its processing is good.
Background technology
In recent years, with the external packing that is used to improve the package outward appearance, avoid packing that content directly is hit, the label packing of the function that has cover glass bottle or plastic bottle and expression commodity concurrently etc. is purpose, heat shrinkable plastic film has obtained extensive use.As being the plastic raw materials that purpose is used with these, oriented films such as polyvinyl chloride film, polystyrene type film, polyester film are used in the various containers such as PETG (PET) container, polyethylene can, glass container with the form of label and lid sealing or integral packaging.
But though polyvinyl chloride film shrinkage character is good, hear resistance is low, also has the problems such as reason that produce hydrogen chloride gas when burning, become the generation bioxin.In addition, if the shrink label of heat-shrinkable polyvinyl chloride resin film as pet container etc. used, then when recycling container, existing must separation tags and the problem of container.
On the other hand, the polystyrene type film can separate because of proportion is different with the PET bottle container, shrink finishing quality also good (as Patent Document 1).In addition, the solvent resistance of polyester film is good, does not produce black smoke and stench during burning, also is good aspect environment.But, if these films use with label as the PET bottle, then when selling end article with automatic vending machine, because the lubricity deficiency of label surface,, cause obstruction sometimes to the automatic vending machine input or when automatic vending machine is discharged, particularly commodity do not pass through path, do not arrive outlet, cause commodity, thereby necessity of improvement is arranged by the problem of multiple discharge.
Patent Document 1: the spy opens 2002-108217 number
When heat-schrinkable film is used for the covering of actual container, can implement as required to be processed to label (tubular label) and forms such as tube, bag after the printing.After this film processed dress is affixed on container, under the state that is stated from conveyer etc., inside by steam channel (blowing out the constricted channel mode that steam makes the type of its thermal contraction) and hot-air channel (blowing out the constricted channel mode that hot blast makes the type of its thermal contraction) makes its thermal contraction, is attached on the container.
The steam channel heat transfer efficiency is than hot blast passage height, and heat shrink is compared the good processing outward appearance of easier acquisition with hot-air channel more equably.Yet, in steam channel, in constituting the resin of film, for giving under the situation that lubricity adds the wax composition, can remove the wax composition of film surface for carrying out steam that thermal contraction blows out, cause the problem of shrink label lubricity variation.
In addition.As the means of improving lubricity, the someone has adopted the method (as Patent Document 2) at the good layer of the stacked lubricity of film surface.
Yet,,, also exist friction to produce degradation problem under wearing and tearing, the productivity owing to manufacturing procedure central roll etc. and laminate surface except the problem of cost aspect because need the back processing of film.In addition, if for giving before the printing or film surface after the printing imposes easy glide coating with lubricity, then solvent welding can variation, and because the decline of solvent welding, bonding portion is peeled off sometimes when thermal contraction, can not realize solvent welding under the opposite extreme situations.
Patent Document 2: the spy opens 2002-196677 number
Summary of the invention
In view of the foregoing, the object of the present invention is to provide following heat-schrinkable film, the transparency of this film is good, and when using as the label of beverage-container, can prevent the obstruction of commodity in the Drink dispenser by the lubricity that improves outside one side, and can fully satisfy solvent welding, the suitable property of processing is good.More particularly, described film is heat-shrinkable polyester film and heat-shrinkable polystyrene type film.
The application's that can address the above problem the 1st invention is the good heat-shrinkable polyester film of lubricity, and described film satisfies above-mentioned condition (A)～(C).
(A) in the one side at least of polyester film, being formed with the solid constituent coating amount that contains the silicone composition is 0.002～0.5g/m
2The easy glide layer;
(B) coefficientoffriction d≤0.27 of easy glide interlayer;
(C) percent thermal shrinkage of the maximum collapse direction of dipping after 10 seconds is more than 50% in 95 ℃ hot water.
Satisfy under the situation of this scope, can be provided in the heat-shrinkable polyester film of the obstruction that can prevent when using in the automatic vending machine and the transparency, excellent processability as the label of container for drink.
In this case, coefficientoffriction d≤the 0.24th of easy glide interlayer, suitable.
Also have, in this case, silicone composition containing ratio is that 10～80 weight % and silicone component content are 0.001 to 0.4g/m in the easy glide layer solid constituent
2Be suitable.
In this case, it is suitable containing the mylar composition that has the styrene part in the molecule in the easy glide layer.
In addition, in this case, one side and another side can be bonding with organic solvent is suitable.
In addition, the application's that can address the above problem the 2nd invention is the good heat-shrinkable polystyrene type film of lubricity, and described film satisfies above-mentioned (a)～(c),
(a) coefficientoffriction d≤0.25 between the film single face at least;
(b) film was flooded 20 seconds in 80 ℃ hot water, simultaneously take out thermal contraction 10% back on main shrinkage direction, air dry after 24 hours in the atmosphere of 23 ℃ of relative humidity 65%, coefficientoffriction d≤0.28 between the film single face at least;
(c) dipping is after 10 seconds in 95 ℃ hot water, and the percent thermal shrinkage of maximum collapse direction is more than 50%.
Satisfy under the situation of this scope, can find that film has good heat shrinkability characteristic, simultaneously, after in steam channel, being covered in bottle container and shrinking, also have excellent lubrication with label-like.
In this case, preferred satisfied
(d) coefficientoffriction d≤0.20 between the film single face at least;
(e) film was flooded 20 seconds in 80 ℃ hot water, make its thermal contraction 10% on main shrinkage direction simultaneously, take out, air dry after 24 hours in the atmosphere of 23 ℃ of relative humidity 65%, coefficientoffriction d≤0.23 between the film single face at least;
At this moment, after in steam channel, being covered in bottle container with label-like and it is shunk, also can demonstrate excellent lubrication more.
Also have, in this case, the easy glide layer that contains the lubricant composition in the one side setting of single face at least of film is suitable as outermost layer.If the one side at least of this film be provided with contain the lubricant composition the easy glide layer as outermost layer, then can make the surface lubrication when making label good, thereby be preferred.If only make the outermost layer of film contain the lubricant composition, issuable shortcoming in the time of can avoiding making film all to contain the lubricant composition, as the transparency descend and painted, film strength under degradation, and, also be favourable on cost owing to the use amount that can reduce the lubricant composition.
Also have in addition, in this case, above-mentioned easy glide layer is suitable by the coating process setting.If use coating process, compare as the layered manner that utilizes coextrusion etc. with other method, can form thinner easy glide layer, also be favourable therefore embodying aspect the solvent welding described later.
In this case, one side can both be suitable with solvent welding with another side.If can use solvent welding, then be fit to use the usual method (central seal method) of general heat-schrinkable film being carried out solvent welding processing, can easily process.
Also have in this case, main shrinkage direction at film, at flexible pattern: frequency 50Hz ,-20 ℃ to 250 ℃ temperature range, programming rate: when measuring the film dynamic viscoelastic under 2 ℃/minute the condition, in the temperature range that instrumentation comes the α of self-polystyrene to disperse dispersion in addition, it is suitable measuring α dispersion dispersion in addition.Measure the polystyrene type film that α disperses dispersion in addition in this temperature range, when disperseing promptly to become the lax dispersion of cause of thermal contraction phenomenon, α can produce contraction producing, if shrinking near the end of a period time point, then can become the hear resistance after the contraction and the material of excellent size stability because generation crystallization or gel-like structure produce dispersion.In addition, syndiotactic polytyrene and copolymer thereof are more common in the dispersion beyond α disperses, and more are more common in the polystyrene resins composition that contains the crystallinity composition.
The effect of invention
Heat-schrinkable film of the present invention, its transparency is good, and when using, can prevent the obstruction of commodity in the Drink dispenser by the lubricity that improves outside one side as the label of beverage-container, and can fully satisfy solvent welding, the suitable property of processing is good.
The specific embodiment
Heat-shrinkable polyester film of the present invention contains the easy glide layer on the top layer of heat-shrinkable polyester film.
Heat-shrinkable polyester film of the present invention is meant that the ester units to be formed by known polybasic carboxylic acid composition and polyol component is the single copolyester of primary structure unit, or uses the resulting material of mixture of two or more polyester.
The shrinkage factor of the maximum collapse direction when heat-shrinkable polyester film of the present invention floods 10 seconds in 95 ℃ of hot water is more than 50%.If the percent thermal shrinkage of film is lower than 50%, the percent thermal shrinkage deficiency of film then is covered on the container and can not be attached to container when shrinking, and can produce bad order, thereby be not preferred.Preferred percent thermal shrinkage is more than 52%, especially to be preferably more than 55%.At this, " hot water shrinkages under 95 ℃ " are meant among the present invention, with heat-shrinkable polyester film (when being laminated with easy glide layer etc., refer to laminate film integral body) be cut into the heat-shrinkable polyester film of the square shape of 10cm * 10cm, dipping took out the value that the back is measured specimen sizes (vertical and horizontal) and calculated according to following formula in 10 seconds in 95 ℃ of hot water, with a side's big in the vertical and horizontal the value hot water shrinkage as the maximum collapse direction.
Size * 100 before shrinkage factor (%)=(size before the heating-heating back size)/heating
Below such heat-shrinkable polyester film is elaborated.
Dicarboxylic acids composition as polyester in the feedstock composition that is configured for heat-shrinkable polyester film of the present invention, except the terephthalic acid (TPA) that constitutes the ethylene glycol terephthalate unit, can also use any in aromatic dicarboxylic acid and the ester ring type dicarboxylic acids.
As aromatic dicarboxylic acid, can enumerate benzoic acids such as M-phthalic acid, phthalic acid, 5-tert-butyl M-phthalic acid, 5-sodium sulfonate M-phthalic acid; 2, naphthalene dicarboxylic acids classes such as 6-naphthalene dicarboxylic acids; 4,4-dicarboxyl hexichol, 2,2,6,6-tetramethyl biphenyl base-4,4 '-dicarboxylate biphenyl classes such as dicarboxylic acids; 1,1,3-trimethyl-3-phenylindan-4,5-dicarboxylic acids and substituted compound thereof, 1,2-biphenoxyl ethane-4,4 '-dicarboxylic acids and substituted compound thereof etc.
As fatty acid carboxylate, can enumerate ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, decanedioic acid, pimelic acid, suberic acid, 11 (alkane) acid, dodecanedicarboxylic acid, brazilic acid, tetradecane dicarboxylic acid, thapsic acid, nonadecane dicarboxylic acids, docosane dicarboxylic acids and their substituted compound, 4,4 '-dicarboxyl cyclohexane and substituted compound thereof etc.
As the glycol component of the polyester that is contained in feedstock composition, headed by the ethylene glycol that constitutes the PETG unit, other can use any in aliphatic dihydroxy alcohol, ester ring type dihydroxylic alcohols and the aromatic diol.
As aliphatic dihydroxy alcohol, diethylene glycol (DEG), propane diols, butanediol, 1 are arranged, 6-hexylene glycol, 1,10-decanediol, neopentyl glycol, 2-methyl-2-ethyl-1, ammediol, 2-diethyl-1, ammediol, 2-ethyl-2-n-butyl-1, ammediol etc.As the ester ring type dihydroxylic alcohols, have 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol etc.As aromatic diol, have 2, the ethylene oxy additives of PVC ス ゲ ノ-Le compounds such as 2-two (4 '-beta-hydroxy ethoxyl phenenyl) sulfone, benzene dimethanol etc.In addition, PAG such as polyethylene glycol and polypropylene glycol also can be used as the dihydroxylic alcohols use.
The contained polyester of above-mentioned raw materials composition is the material that is made of above-mentioned sour composition and glycol component, if will adjust polyester, improvement is as the characteristic of heat-schrinkable film, then preferred compositions is used more than one sour composition or glycol component, and the kind of the monomer component of combination and content can suitably be selected according to required film characteristics, economy etc.The polyester that can contain in addition, one or more in the feedstock composition.Contained polyester is under a kind of situation, to be made as the copolyester that contains the ethylene glycol terephthalate unit.Mix under the situation of two or more polyester, be made as the copolyester of required composition and the mixture of homopolymerization polyester.It is general because the copolyester melting point is low, operate problems such as difficulty when having drying, therefore preferred the mixing used homopolymerization polyester (PETG, poly-to (ethylene naphthalate), poly-(terephthalic acid (TPA) 1,4-cyclohexene two ethyls) etc.) and copolyester.Wherein, during as heat-shrinkable polyester film, 1～2 mole of whole % of preferred polyester is the aliphatic dicarboxylic acid unit.By being adjusted to this scope, the beginning temperature of thermal contraction can be controlled at desirable scope.
Polyester in the above-mentioned raw materials composition, any can be with in the past method manufacturing, for example can use dicarboxylic acids and dihydroxylic alcohols directly the ester-interchange method of direct esterification method, dicarboxylic acids dimethyl esters and the diol reaction of reaction wait and adjust polyester.Adjustment can be carried out with any method of batch (-type) and continous way.
In the feedstock composition, except above-mentioned polyester, can also add various known additives as required, as additive, can enumerate lubricants such as titanium dioxide, finely particulate silica, kaolin, calcium carbonate, antistatic agent, age resistor, ultra-violet absorber, colouring agent (dyestuff etc.).
The above-mentioned raw materials composition is configured as the film shape with known method (for example extrusion molding, rolling process etc.).Film be shaped as plane or tubular, there is no particular limitation.As drawing process, can adopt as known methods such as roller pulling method, long gap pulling method, tentering device pulling method, blowing pulling methods.Any of these methods can carry out biaxial tension one by one, biaxial tension simultaneously, simple tension and combination stretching thereof.In the above-mentioned biaxial tension, the stretching of direction can be carried out simultaneously in length and breadth, also can carry out either party stretching earlier.Stretching ratio can be set arbitrarily 1.0 times to 7.0 times scope, and the multiplying power of a direction of preferred regulation is more than 3.5 times.
In the stretching process, preferably more than the glass transition temperature (Tg) of the polymer that constitutes film and in the temperature below Tg+80 ℃, carry out preheating.Heat-set treatment during stretching is recommended as after stretching about 1～30 second of heating region by 30～150 ℃.In addition also can be behind film stretching, the amplitude with regulation before or after the heat-set treatment stretches.Also have, can add the operation of cooling off when under the state that keeps elongation or stretch, giving membrane stress after the above-mentioned stretching, perhaps be right after the operation of cooling off behind this processings releasing extended state.The thickness of gained film is preferably the scope of 6～250 μ m.
Constitute the composition of the polystyrene resins of heat-shrinkable polystyrene type film involved in the present invention, as long as can embody the heat shrinkability characteristic of defined, just there is no particular limitation.
The shrinkage factor of the maximum collapse direction when heat-shrinkable polystyrene type film of the present invention floods 10 seconds in 95 ℃ of hot water is more than 50%.If the percent thermal shrinkage of film is lower than 50%, the percent thermal shrinkage deficiency of film then, covering container also can not be attached to container when shrinking, and can produce bad order, thereby be not preferred.Preferred percent thermal shrinkage is more than 52%, especially to be preferably more than 55%.
Below such polystyrene type film is described in detail.
Polystyrene resins among the present invention is preferably the resin that contains the polystyrene with syndiotactic structure, in fact, as polystyrene, more preferably uses the polystyrene resins that in fact only contains syndiotactic structure.If use the polystyrene resins of syndiotactic structure, obtain the better film of mechanical strength and hear resistance easily.Just density is not low for such polystyrene resins, help the separation in the circulating process, and hear resistance, the excellent heat resistance when particularly heating is preserved etc., by film shaped back produce through the time shrink the print gap (pich) that brings and change also little, improved printing precision, thereby be preferred as label.Durability to the contained solvent of printing-ink is also good in addition, can obtain the good film of printing.
Polystyrene resins with above-mentioned syndiotactic structure, with regard to its steric regularity of using nuclear magnetic resonance standard measure side chain phenyl and/or substituted-phenyl, two unit group (diad, construction unit is 2) be preferably more than 75%, more preferably more than 85%, in addition, five unit group (pentad, construction unit is 5) be preferably more than 30%, more preferably more than 50%.
As the polystyrene composition that is configured for polystyrene resins of the present invention, can enumerate polystyrene, poly-(p-, m-, or o-methyl styrene), poly-(2,4-, 2,5-, 3,4-, or 3, the 5-dimethyl styrene), poly-(ring-alkylated styrenes) such as poly-(p-t-butyl styrene), poly-(p-, m-, or o-chlorostyrene), poly-(p-, m-, or o-bromostyrene), poly-(p-, m-, or o-fluorostyrene), poly-(halogenated styrenes) such as poly-(o-methyl-p-fluorostyrene), poly-(p-, m-, or o-1-chloro-4-methyl-benzene) etc. poly-(halogenation substituted alkyl styrene), poly-(p-, m-, or o-methoxy styrene), poly-(p-, m-, or o-ethoxybenzene ethene) etc. poly-(alkoxystyrene), poly-(p-, m-, or o-carboxymethyl styrene) etc. poly-(carboxyalkyl styrene), poly-(alkyl ether styrene) such as poly-(p-vinyl benzyl propyl ether), poly-(alkyl silicyl styrene) such as poly-(p-trimethyl silyl styrene), especially poly-(vinyl benzyl dimethoxy phosphide) etc.
Preferred characteristic as heat-shrinkable polystyrene type film of the present invention, at flexible pattern: frequency 50Hz ,-20 ℃ to 250 ℃ temperature range, programming rate: when measuring the dynamic viscoelastic of film master shrinkage direction under 2 ℃/minute the condition, preferably the temperature range of the dispersion beyond the α that instrumentation derives from polystyrene disperses measures the dispersion of α beyond disperseing.
By the way, according to the 44th (1996) 169～172 pages of rheology discussion summary collection (two-story valley, hillside plot etc.), α disperses, promptly becomes the lax dispersion of thermal contraction phenomenon reason, is more common in syndiotactic polytyrene and copolymer thereof and the polystyrene resins composition that contains the crystallinity composition.
The heat-shrinkable polystyrene type film of the present invention that possesses this specific character, can obtain by the following thin slice that do not stretch that stretches, the described thin slice that do not stretch is, at flexible pattern: frequency 50Hz ,-20 ℃ to 250 ℃ temperature range, programming rate: during the dynamic viscoelastic of the thin slice that do not stretch before measuring the stretching when obtaining this film under 2 ℃/minute the condition, in instrumentation derives from the temperature range that the α of polystyrene disperses, measured the not stretching thin slice of the dispersion beyond α disperses.In addition, such thin slice that do not stretch can be by after being melt extruded material resin under 250 ℃ the temperature by the T die head, through about 20～50 ℃ chill roll cooling curing and obtaining rapidly.
In heat-shrinkable polystyrene type film of the present invention, be used to reduce thermal contraction and begin temperature or the plasticizer of raising resistance to impact or the material of compatibilizing agent as constituting in the film polystyrene resins of one deck at least, preferably use when styrene polymerization or in the polystyrene base polymer, to have cooperated.
In heat-shrinkable polystyrene type film of the present invention, it also is effective cooperating other thermoplastic resin and/or rubber constituent again for polystyrene resins.As at this cooperated other thermoplastic resin, headed by the polystyrene resins such as the polystyrene of random to have (upright structure) structure, AS resin, ABS resin, can enumerate polyester resins such as PETG, PEN, polybutylene terephthalate (PBT); Polyamide-based resins such as nylon 6, nylon 66, nylon 12, nylon 4, polyhexamethylene adipamide; Polyolefin resins such as polyethylene, polypropylene, polybutene etc.
In addition,, be preferably and contain the rubbery copolymer of styrene compound, can enumerate random, block or the graft copolymer of from styrene and rubber constituent, selecting more than one and copolymerization respectively as its constituent as above-mentioned rubber constituent.Object lesson as such rubbery copolymer, can enumerate for example SB rubber, styrene-isoprene block copolymer rubber, in addition part or all rubber that is hydrogenated of butadiene part, methyl acrylate-BS rubber, acrylonitrile-butadiene-styrene copolymer rubber, acrylonitrile-alkyl acrylate-BS rubber, methyl methacrylate-alkyl acrylate-BS rubber etc. in these copolymer rubbers.
Contain the above-mentioned rubber-like polymer of styrene compound as its constituent, owing to contain styrene units in the molecule, thereby to the favorable dispersibility based on the polystyrene resins of syndiotactic structure, its result can bring into play the good rerum natura of p-poly-phenyl vinyl resins and improve effect.Particularly contain the rubbery copolymer of above-mentioned styrene compound, be fit to as the compatibility conditioning agent as its constituent.
As rubber constituent, except above-mentioned substance, can also use natural rubber, polybutadiene, polyisoprene, polyisobutene, chloroprene rubber, ethylene-propylene copolymer rubber, polyurethane rubber, silicon rubber, acrylic rubber, polyether ester rubber, polyester-ester rubber etc.
The weight average molecular weight that constitutes the polystyrene resins of heat-shrinkable polystyrene type film of the present invention is preferably more than 10,000, more preferably more than 50,000.Weight average molecular weight is lower than 10,000 material, and the tensile strength characteristics of film and hear resistance have deficiency easily slightly.Though the upper limit of weight average molecular weight has no particular limits,, more than 000,, thereby preferably be lower than 1,500,000 because the increase of tensile stress causes fracture easily if be 1,500.
In heat-shrinkable polystyrene type film of the present invention, except mentioned component, to improve electrostatic adherence, easy glide, draftability, the suitable property of processing, resistance to impact etc. is purpose, or be purpose with roughening, opacification, cavitation, lightweight etc., in the scope of not overslaugh performance required for the present invention, can suitably cooperate resin beyond above-mentioned and plasticizer, compatibility conditioning agent, inorganic particulate, organic filler, colouring agent, antioxidant, antistatic agent etc.
Heat-shrinkable polystyrene type film of the present invention, owing to use as the formation raw material of above-mentioned polystyrene resins as film, thereby heat shrinkability characteristic is good, when forming label and the cementability and the printing of printing ink also good, the film printing face also seldom produces pin hole etc.Also have, disposability is good, during burning disposal to the load of environment also seldom.
Aforesaid polystyrene resins can be with general extrusion molding that uses or rolling process etc. formed the film shape in the past.The shape of film is generally plane and tubular, and there is no particular limitation.Can unrestrictedly use the general in the past roller pulling method that adopts, long gap pulling method, tentering device pulling method, blowing pulling method etc. as pulling method, when adopting in these methods any method, all can adopt biaxial tension one by one, biaxial tension, simple tension simultaneously or make up these any method as stretching mode.When carrying out above-mentioned biaxial tension, direction can stretch simultaneously in length and breadth, but preferably either party biaxial tension one by one of at first carrying out, in length and breadth the order of direction either party preferentially all can.
Secondly the optimum condition when making heat-shrinkable polystyrene type film of the present invention is illustrated.
Stretching ratio is preferably in 1 times to 6 times scope, a fixed direction multiplying power and can be the same or different with the multiplying power of this direction vertical direction.Preferably carry out preheating in the stretching process in the temperature more than the glass transition temperature (Tg) of the resinous principle that constitutes film, below (Tg+50) ℃.Preferably before above-mentioned stretching, implement online coating simultaneously.
In the heat setting after the stretching, preferably after stretching with 1 second～30 seconds heating regions by 30 ℃～150 ℃.In addition also can be behind oriented film, before the heat setting, or after heat setting, carry out the relaxation processes of appropriateness.Can also be after above-mentioned stretching, and then the operation of under the condition of additional maintenance stretching or stretched condition film side stress application limit being cooled off maybe removes the operation of cooling off again behind the extended state after this processing.
In the good heat-shrinkable polyester film of the lubricity of the application's the 1st invention, being formed with the solid constituent coating amount that contains the silicone composition in the one side at least of polyester film is 0.002～0.5g/m
2The easy glide layer, coefficientoffriction d≤0.27 of easy glide interlayer is preferably coefficientoffriction d≤0.27.Heat-shrinkable polyester film of the present invention can be 0.002～0.5g/m by the solid constituent coating amount that will contain the silicone composition
2The easy glide layer be laminated in heat-shrinkable polyester film surface and obtain.The solid constituent coating amount is the amount that is coated with application that is present in after coating, the drying on the polyester film.Recommend to contain the material of silicone composition and adhesive resin composition as above-mentioned easy glide layer.Silicone (silicone) composition is meant the organosiloxane class, comprise have oil, the material of proterties such as rubber, resin, be called silicone oil, silicon rubber, silicones respectively.Owing to have hydrophobic effect, lubrication, a demoulding effect etc., when stacked, be effective therefore to the friction that reduces the surface as the film top layer.When using as the container for drink label, utilize steam and hot blast to shrink, adorn subsides mostly, if the low easy glide layer of resistance to water then uses above-mentioned contraction place to comprehend remarkable reduction lubricity, but because the hydrophobicity effect of silicone also can keep good lubricity after the steam treatment.
Special recommendation silicones wherein.Silicones is meant the organopolysiloxane with tridimensional network, is laminated in when curling rolling behind the polyester film surface as the easy glide layer, is difficult for causing the back side transfer printing to institute's contact membrane.In addition, when using as the beverage label, being subjected to printing, to add the printing in man-hour good.Also have,, be suitable for using as the hot drink containers labels owing to contain methyl its excellent heat resistance of silicones as organic group, thereby special recommendation.
As the content of silicone composition, the amount in the easy glide layer is preferably 10～80 weight %, is preferably 40～70% especially.If amount is lower than 10 weight %, lubricity to improve effect little, surpass 80 weight %, cause the transfer printing of overlay composition easily.
In addition, silicone composition and other lubricant composition also can and be used, as and the lubricant of usefulness, preferably add paraffin, microwax, polypropylene wax, Tissuemat E, ethylene, propylene acids wax, stearic acid, behenic acid, the 12-hydroxy stearic acid, stearmide, oleamide, erucyl amide, the di-2-ethylhexylphosphine oxide stearmide, ethylenebisstearamide, ethylenebisoleoamide, butyl stearate, glyceryl monostearate, pentaerythritol tetrastearate, hardened castor oil, the stearic acid stearyl ester, siloxanes, the higher alcohols macromolecule, stearyl alcohol, calcium stearate, zinc stearate, dolomol, lead stearate etc.Wherein, the interpolation of low molecular weight polyethylene wax can make laminar surface level and smooth and have to adhere to and prevent from effect to be expected to improve lubricity thus.
In addition, by adding organic filler such as inorganic particulate, polymethyl methacrylate (PMMA), styrene-divinylbenzene class, Lauxite, silicones, polyamide-(acyl) imines, benzoguanamines such as silica, titanium oxide, mica, talcum, calcium carbonate or their surface treatment product etc., can further improve lubricity, but because the generation of concave-convex surface etc. might reduce the film transparency, therefore suggestion is suitably adjusted addition according to the requirement of the transparency.
As the adhesive resin composition, esters resin is for example arranged, the amide-type resin, the polyurethanes resin, epoxylite, the phenolic resins resinoid, acrylic resin, the vinyl acetate esters resin, olefine kind resin such as polyethylene or polypropylene, cellulosic resin, melamine resinoid or its copolymer or modified resin, or has heat, the material of luminous energy curing property, wherein, when with esters resin, the polyurethanes resin, or during the combination of its copolymer and lubricant, except demonstrating good lubricity, owing in tube processing, may use solvent welding, thereby obtain special recommendation.And then, from security, the viewpoint that conforms, more preferably use the material of aqueous dispersion class.This adhesive resin composition is except having the effect as adhesive, improves outside the adhesive force with the polyester film of easy glide layer, when stacked easy glide layer after-drawing film, also has the effect of the stretching auxiliary agent that makes surface smoothing.When being stretched, have more the effect that strengthens surface strength.
Among the present invention, as above-mentioned adhesive resin composition, it is suitable containing the mylar composition that has the styrene part in the molecule in the easy glide layer.
As resinous principle with styrene part, for example can enumerate polystyrene resin or in polyolefin resin, celluosic resin, melmac or its copolymer or modified resin such as mylar, polyamide, polyurethane resin, epoxy resin, phenolic resins, polyvinyl acetate resin, polyethylene or polypropylene, introduce cinnamic material by the method for monomer copolymerization or block copolymerization or graft copolymerization.
Wherein, owing to contain the mylar of styrene part the effect that improves layer hardness is arranged, can demonstrate good lubricity when therefore making up with the silicone composition, in addition, the solvent welding in tube processing is good, thereby recommended.Here said mylar is meant the macromolecular compound that the polycondensation by polyacid and polyalcohol obtains, and also can be copolymerization or modified resin.
This resinous principle is except having the effect as adhesive, can improve outside the adhesion of thin film with the easy glide layer, layer by layer during the poststack oriented film, also has the effect of the stretching auxiliary agent that makes surface smoothing at easy glide.As the resinous principle that contains styrene part,, more preferably use the material of aqueous dispersion class from security, the viewpoint that conforms.
In addition, if stacked easy glide layer after-drawing film is that effectively thin layerization also is possible to strengthening surface strength then.
Formation method as the easy glide layer, have the easy glide resin is melt extruded the coating (off-line coating) etc. that the coating (online coating) of easy glide coating liquid in the method that is laminated in the top layer, the film film making process, easy glide behind the film system film apply liquid, but from the cost aspect and be expected to obtain to have good adhesive force between overlay and film, make that layer is tough because of the stretching heat treatment after the coating makes, thin layer changes into to may, improving the angle of effect such as the transparency, the manufacture method of preferred online coating.As an example, can enumerate anti-roller mode, air knife blade coating mode, spraying (Off ァ ゥ Application テ Application) mode etc.
In the working procedure of coating of online coating, after preferably the polyesters feedstock composition being formed the film shape, maybe will form behind the material uniaxial tension of film shape above-mentioned easy glide coating liquid with level and smooth and homogeneous thickness is coated on film surface by extrusion by melting etc.Then, add hot-stretch by further two-way or unidirectional, self also is stretched overlay with film, therefore can be improved to the effect of adhesion of thin film, intensity, thereby recommended.
As embodiments of the present invention, special recommendation uses silicones as lubricant, the polyester resin that use esters resin, polyurethanes resin, acrylic resin or its copolymer, preferably contains the styrene part forms easy glide layer by online coating process on the top layer of heat-shrinkable polyester film as the adhesive resin composition.
Amount as being present in the overlay on the film after stretching, the drying is preferably 0.001～0.5g/m
2, especially be preferably 0.002～0.2g/m
2If at 0.001g/m
2Below, it is big that frictional resistance becomes, if surpass 0.5g/m
2, the transparency of film can reduce, and wears away the generation of considering to be worth doing because the friction of roller and laminate surface can cause in the manufacturing procedure simultaneously.
Below tube is illustrated.When making label by heat-shrinkable polyester film of the present invention, carry out tube processing, use this moment solvent to carry out bonding mostly, consider from this viewpoint, preferably with 1, when 3-two oxa-s penta ring, oxolane equal solvent are coated on that film is simultaneously gone up and the another side pressure of film sticked at this applicator surface, can realize bonding.When this adhesive strength was not enough, when the thermal contraction of label dress pastes or when handling beverage bottle, the bonding position of label might be peeled off.
With regard to heat-shrinkable polystyrene type film of the present invention, at least coefficientoffriction d≤0.25 between the single face of film, and film flooded in 80 ℃ hot water 20 seconds and make it simultaneously take out 10% back, air dry after 24 hours in the atmosphere of 23 ℃ of relative humidity 65%, coefficientoffriction d≤0.28 between the film single face at least shrinking on the main shrinkage direction.Coefficient of friction between the film single face surpasses under 0.25 the situation in any one side, when this film being made label-like and making its contraction be covered in container with the hot-air channel method, lubricity between label surface becomes insufficient, drops in the automatic vending machine or stops up easily when discharging.In addition, with this film in 80 ℃ hot water, flood made in 20 seconds its shrink on the main shrinkage direction that 10% back is taken out and in the atmosphere of 23 ℃ of relative humidity 65% the coefficientoffriction d between at least film single face of air dry after 24 hours surpass under 0.28 the situation in any one side, when this film being made label-like and making its contraction be covered in container with the steam channel method, it is insufficient slightly that lubricity between label surface becomes, and drops in the automatic vending machine or still stop up easily when discharging.
Heat-shrinkable polystyrene type film of the present invention, coefficient of friction between above-mentioned film single face is preferably below 0.23, in addition, this film is flooded in 80 ℃ hot water made in 20 seconds its shrink on the main shrinkage direction that 10% back is taken out and in the atmosphere of 23 ℃ of relative humidity 65% coefficient of friction between at least film single face of air dry after 24 hours be preferably below 0.23.
Such coefficient of friction can form the easy glide layer that contains the lubricant composition by the top layer in the one side at least of heat-shrinkable polystyrene type film to be guaranteed.By contain the easy glide layer of lubricant composition in outermost layer one side setting, reduction of the shortcoming that produces in the time of can avoiding making film all contain the lubricant composition such as the reduction of the transparency and painted, film strength etc., owing to can reduce the absolute magnitude of lubricant composition, also be favourable aspect cost in addition.If adopt the method that forms the easy glide layer by coating process, with in addition method such as coextrusion layered manner etc. relatively, can form thinner easy glide layer, also be favourable aspect the embodiment solvent welding described later.
This easy glide layer (is converted into coating amount and is about 0.1g/m with following about 0.1 μ m in the outermost layer side of heat-shrinkable polystyrene type film
2Below), more preferably followingly about 50nm (be converted into coating amount and be about 0.05g/m
2Below) thin layer form.This be because, though the thickness of easy glide layer according to the formation raw material of easy glide layer and different, if blocked up, solvent welding has the tendency of decline.If the thickness of easy glide layer is abovely about 0.4 μ m (to be converted into coating amount and to be about 0.4g/m
2More than), except above-mentioned solvent welding is low, can cause the transparency of film to descend, in manufacturing procedure, can cause the generation of abrasion bits simultaneously owing to the friction of roller and laminate surface.On the contrary, if the easy glide layer is thin excessively, the lubricity deficiency, 5nm is above (to be converted into coating amount and to be about 0.005g/m so preferably be made as
2More than), be made as more preferably that 8nm is above (to be converted into coating amount and to be about 0.008g/m
2More than).
The concrete grammar that forms the easy glide layer with coating process has no particular limits, but preferably on raw material, apply after-drawing before the stretching when the system film, it is online application pattern, adopt this application pattern, can be used as more uniform film and form the easy glide layer expeditiously, also is favourable aspect cost.
Also have, heat-shrinkable polystyrene type film of the present invention preferably can enough solvent weldings.This be because, if can realize the material of solvent welding, just can adopt the conventional method (for example central seal method etc.) that common heat-schrinkable film is carried out solvent welding processing to process, compare, can simplify working process with the mode of lamination behind the adhesive coating and ageing certain hour.
Preferred implementation of the present invention is the heat-shrinkable polystyrene type film that the online coating when the one side at least of foregoing film applies the easy glide layer also preferably by the system film forms the easy glide layer, this easy glide layer, on the solvent welding this point that improves film, consider, contain the adhesive resin composition when also preferably containing the lubricant composition.
Use emboliform lubricant composition as lubricant, influence the transparency of film sometimes, in addition, particle condenses sometimes, should be noted.As the preferred emollient that does not produce such problem, can enumerate paraffin, microwax, polypropylene wax, Tissuemat E, ethylene, propylene acids wax, stearic acid, behenic acid, the 12-hydroxy stearic acid, stearmide, oleamide, erucyl amide, the di-2-ethylhexylphosphine oxide stearmide, ethylenebisstearamide, ethylenebisoleoamide, butyl stearate, glyceryl monostearate, pentaerythritol tetrastearate, hardened castor oil, the stearic acid stearyl ester, siloxanes, the higher alcohols macromolecule, stearyl alcohol, calcium stearate, zinc stearate, dolomol, lead stearate, silicone (dimethyl siloxane) class low-molecular-weight thing (oil) or silicone (dimethyl siloxane) resinoid etc., these as required also can two or more and usefulness except using separately.Wherein, silicone low-molecular-weight thing (oil) and silicone resin are owing to the dynamic friction coefficient that can reduce film surface, and the difficult solvent welding that influences film, thereby are particularly preferred.
Same with the heat-shrinkable polyester film of the application's the 1st invention, the lubricant composition preferably uses the silicone material, is preferably silicones in the silicone material especially.The content of silicones in the amount in the easy glide layer, is preferably 10～80 quality %, more preferably 20～70 quality %.When amount is lower than 10 quality %, lubricity to improve effect little, if surpass 80 quality %, the easy glide composition of layer is transferred to the back side easily when then being rolled into web-like.
As the adhesive resin composition that is matched with in the easy glide layer, can enumerate as various resins such as polyester resin, polyamide-based resin, polyurethanes resin, epoxylite, phenolic resinoid, acrylic resin, polyvinyl acetate resinoid, cellulosic resin, styrene resins, styrene-propene acid copolymerization resinoid particularly, by with the combination of above-mentioned lubricant, can give play to excellent lubrication, thereby be preferred.
About either party of above-mentioned lubricant and adhesive resin composition, consider from security and the viewpoint that conforms, preferably use the material of water-soluble or water dispersible.
Embodiment
Be described in further detail the present invention below by embodiment, but following embodiment does not limit the present invention, in the scope that does not break away from aim of the present invention, the situation that change is implemented also is contained among the present invention.Assay method by the rerum natura of embodiment and comparative example gained film is as follows.
(1) percent thermal shrinkage
Cut out the square of 10cm * 10cm from the film that stretches, make one side wherein parallel, with its 10 seconds of dipping in being heated to 95 ℃ tank with the film direction of travel.In the tank of 23 ℃～25 ℃ of temperature preparing in addition, flooded for 20 seconds immediately after 10 seconds, measure the length of film master shrinkage direction then, ask for percent thermal shrinkage.Shrink maximum direction and be made as main shrinkage direction.
Percent thermal shrinkage (%)=(size before the heating-heating back size)/(size before the heating) * 100
(2) coefficient of friction
According to JIS K-7125, at the dynamic friction coefficient μ d, the amplitude of variation R that measure under 23 ℃ of 65%RH environment between pellicular front.In addition, the coefficient of kinetic friction after the hot water treatment is that film was handled 20 seconds in 80 ℃ hot water, and it is shunk after 10% at main shrinkage direction, to measure with above-mentioned same method.
(3) turbidity
Turbidity is according to JIS K6714, uses nephelometer (Japanese precision optical machinery corporate system) to measure, and is estimated by following benchmark.
○：≤8.0％
×：＞8.0％
(4) solvent welding intensity
With 1,3-two oxa-s penta ring is coated on the film of stretching, and sealing is implemented in two opening and closing together.Cut main shrinkage direction at film, the direction vertical hermetic unit of wide 15mm respectively with main shrinkage direction, be fixed on the omnipotent stretching experiment machine STM-50 of (strain) ボ-Le De ゥ ィ Application corporate system, by 90 ° of disbonded tests, under 200mm/ minute draw speed, measure, estimate by following benchmark.
○：≥4N/15mm
×：＜4N/15mm
(5) mar proof
When carrying out the mar proof evaluation, use product dyed thereby friction fastness test machine (Co., Ltd.'s smart mechanism in peace field is done made) mensuration wear extent.Use becomes the sand paper of two gauzes and particle diameter #1000 friction (surface radius 45mm, arc length 59mm, wide 25mm) of the order installation on surface with sand paper, film sample is fixed on the sample bench (surface radius 200mm), and make the one side that coefficient of friction is little between film become the surface, load 40g, come and go apart from 100mm, 30 back and forth/minute condition under handle sample.Measure 10 weight change (g/m that handle pre-process and post-process position unit are back and forth
2).
(6) dynamic viscoelastic
Cut each drawing sheet not that obtains in the manufacturing process way of heat-shrinkable polystyrene type film, its MD direction is a length direction, and wide is 5mm, and the mensuration partial-length is 30mm, makes test piece.To each test piece, use ァ ィ テ ィ-note to survey the Measurement of Dynamic Viscoelasticity device of corporate system, under flexible pattern: frequency 50Hz ,-20 ℃～250 ℃ the condition of 2 ℃/minute of temperature range, programming rates, measure dynamic viscoelastic, in the temperature range that instrumentation comes the α of self-polystyrene to disperse, confirm that α disperses having or not of dispersion in addition.
(7) obstruction of automatic vending machine
Behind the film shaped tubular label that becomes the outside for the easy glide layer, utilize steam heat to shrink, dress is affixed on the trunk of 500mL beverage with the PET bottle, measures to drop into, when discharging automatic vending machine, discharges the number of packages (number) that obstruction takes place in 400 the process.
(experiment 1)
(1) polyester resin and non-stretched film
With PETG 40 weight %, the polyester 50 weight % that constitute by 100 moles of % of terephthalic acid (TPA), 30 moles of % of neopentyl glycol and 70 moles of % of ethylene glycol, and polybutylene terephthalate (PBT) 10 weight % mix the formation polymer blend, make said composition 280 ℃ of fusions, extrude by the T die head, cool off rapidly with chilled roll, obtain non-stretched film.
(2) mediation of coating liquid
(メ ガ Off ァ ッ Network F442: big Japanese ink chemical industry system) the IPA-aqueous solution of solid constituent 5 weight % makes coating liquid with the solid constituent 95 weight %, the surfactant that contain the aqueous dispersion (Network リ-テ ッ Network ス KT-290 day new chemistry institute corporate system) of dimethyl-silicon ketone resin and copolymer in cinnamic acrylic ester in the solid constituent.
(3) manufacturing of coating film
With the coating liquid that is in harmonious proportion in (2), be coated on non-stretched film with spraying method by (1) gained, be heated to after film temperature reaches 70 ℃, 4.0 times of cross directional stretch, then 80 ℃ of heat settings, obtaining coating amount is 0.02g/m with the tentering device
2, thickness is the heat-shrinkable polyester film of 50 μ m.
(experiment 2)
In the experiment 1, as containing silicone aqueous dispersions (TSM6343: solid constituent 40 weight % Toshiba's silicone corporate system) in the coating liquid use solid constituent, Tissuemat E aqueous dispersions (Ha ィ テ ッ Network E-8237: solid constituent 15 weight % Dong Bang chemical company system), esters resin aqueous dispersions (バ ィ ロ Na-Le MD1500: solid constituent 30 weight % Japan's textile company system), surfactant (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution of solid constituent 15 weight % big Japanese ink chemical industry system), in addition, with with experiment 1 same method, obtain heat-shrinkable polyester film.
(experiment 3)
In the experiment 1, as containing silicone aqueous dispersions (TSM6343: solid constituent 50 weight % Toshiba's silicone corporate system) in the coating liquid use solid constituent, Tissuemat E aqueous dispersions (Ha ィ テ ッ Network E-8237: solid constituent 15 weight % Dong Bang chemical company system), esters resin aqueous dispersions (バ ィ ロ Na-Le MD1500: solid constituent 30 weight % Japan's textile company system), surfactant (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution of solid constituent 5 weight % big Japanese ink chemical industry system), in addition, with with experiment 1 same method, obtain heat-shrinkable polyester film.
(experiment 4)
Except testing in 1 behind cross directional stretch with 0.7g/m
2The coating amount coating liquid coating outside, use and test 1 same method and obtain heat-shrinkable polyester film.
(experiment 5)
Except the coating amount that will test in 2 changes 0.7g/m into
2Use and test 2 same methods and obtain heat-shrinkable polyester film outward.
(experiment 6)
In the experiment 1, (Ha ィ テ ッ Network E-8237: (バ ィ ロ Na-Le MD1500: (TB214: the IPA-aqueous solution of solid constituent 20 weight % this grease of pine corporate system), coating amount is 0.01g/m for solid constituent 50 weight % Japan's textile company system), surfactant for solid constituent 30 weight % Dong Bang chemical company system), esters resin aqueous dispersions as containing the Tissuemat E aqueous dispersions in the coating liquid use solid constituent
2, in addition, use and test 1 same method, obtain heat-shrinkable polyester film.
(experiment 7)
Use contains the solid constituent 70 weight % of dimethyl-silicon ketone resin (S4005: day new chemistry is made) in the total solid composition of coating liquid as coating liquid in the experiment 1, (AGN709: (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution of solid constituent 10 weight % big Japanese ink chemical industry system), coating amount is 0.02g/m to the aqueous dispersions of styrene copolymerized mylar for solid constituent 20 weight % Japan's weaving system), surfactant
2, in addition, use and test 1 same method and obtain heat-shrinkable polyester film.
(experiment 8)
Use as coating liquid in the experiment 1 and in the total solid composition of coating liquid, contain the silicone aqueous dispersions (TSM6343: (AGN709: (TB214: the IPA-aqueous solution of solid constituent 5 weight % this grease of pine corporate system), coating amount is 0.02g/m for solid constituent 35 weight % Japan's weaving system), surfactant for solid constituent 60 weight % Toshiba's silicone corporate system), styrene copolymerized mylar aqueous dispersions
2, in addition, use and test 1 same method and obtain heat-shrinkable polyester film.
(experiment 9)
Japan's weaving system), the solid constituent 40 weight % of Tissuemat E aqueous dispersions, (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution of solid constituent 10 weight % big Japanese ink chemical industry system), coating amount is 0.02g/m to surfactant use as coating liquid in the experiment 1 and in the total solid composition of coating liquid, contain dimethyl-silicon ketone resin (S4005: solid constituent 50 weight % day new chemistry system), the aqueous dispersions of styrene copolymerized mylar (AGN707:
2, in addition, use and test 1 same method and obtain heat-shrinkable polyester film.
(experiment 10)
In the total solid composition of coating liquid, contain the dimethyl-silicon ketone resin (S4005: (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution of solid constituent 5 weight % big Japanese ink chemical industry system), coating amount is 0.02g/m for solid constituent 95 weight % day new chemistry system), surfactant except testing in 1 to use as coating liquid
2Use and test 1 same method and obtain heat-shrinkable polyester film outward.
(experiment 11)
Styrene copolymerized mylar aqueous dispersions, coating amount are 0.02g/m in the experiment 1 except the aqueous dispersions (the big Japanese ink of Ha ィ De ラ Application HW340 is learned the industry system) that uses polyurethane resin replaces
2Use and test 1 same method and obtain heat-shrinkable polyester film outward.
(experiment 12)
(S4005: solid constituent day new chemistry system) accounts for the aqueous dispersions of 5 weight %, styrene copolymerized mylar in all solids composition of coating liquid (AGN709: solid constituent Japan's weaving system) accounts for 85 weight % in solid constituent, (メ ガ Off ァ ッ Network F442: solid constituent big Japanese ink chemical industry system) accounts for 10 weight % at solid constituent to surfactant, coating amount is 0.02g/m except the dimethyl-silicon ketone resin
2Use and test 1 same method and obtain heat-shrinkable polyester film outward.
(experiment 13)
Change 0.7g/m into except testing film, the coating amount that will apply in 7 after liquid is coated on stretching
2Use and test 7 same methods and obtain heat-shrinkable polyester film outward.
The composition of raw materials of film easy glide layer is shown in table 1, and gained film rerum natura is shown in table 2 and table 3.
[table 1]
[table 2]
[table 3]
Use is rolled up each 500m * 2 by experiment 1～3, experiment 4, experiment 7～9, experiment 13 films that obtain, when passing through printing machine with the 100/min linear velocity, in experiment 1～3, the experiment 7～9, all deflector rolls are not all found the abrasion bits, use under the situation of experiment 4 and experiment 13, on roller that the easy glide applicator surface contacts, particularly roll out near the metal deflector roll (surperficial corrosion-resistant aluminium processing system, diameter 74mm) the part, by Visual Confirmation be attached with the abrasion bits of white powdery.
(experiment 14)
(1) polystyrene resins and non-stretched film
Syndiotactic polytyrene (the weight average molecular weight 300 that 40 moles of % of 4-methyl styrene are copolymerized into as constituent, 000) is equipped with the calcium carbonate particle 0.05 weight % of average grain diameter 1.0 μ m as lubricant, be mixed into the section of matrix resin raw material, with styrene-butadiene block copolymer (rubber constituent) the raw material section that this raw material is cut into slices and styrene 40 weight % are copolymerized into as constituent, and modifier high styrene rubber (the SB rubber of adjusting compatibility; Contain styrene 85 quality % as constituent) the raw material section, with the ratio of mass ratio 65/30/5 (matrix resin/rubber constituent/modifier), carry by quantitative screw feeder, mix in the hopper of inclination angle 70 degree directly over extruder.Make its fusion at 250 ℃, extruded by the T die head with 800 μ m compressed gaps, make it be attached to 40 ℃ chill roll cooling curing with the air knife knife coating, thin slice is not stretched.
(2) mediation of coating liquid
To contain and be converted into that solid constituent is the dimethyl-silicon ketone resin of 90 mass parts and the aqueous dispersions of copolymer in cinnamic acrylic ester (Network リ-テ ッ Network ス KT-290 day new chemistry institute corporate system), (メ ガ Off ァ ッ Network F442: the IPA-aqueous solution big Japanese ink chemical industry system) is as coating liquid to be converted into the surfactant that solid constituent is 10 mass parts.
(3) manufacturing of coating film
The coating liquid that will be in harmonious proportion by (1) is coated on non-stretched film by above-mentioned (2) gained with spraying method, is heated to after film temperature reaches 90 ℃, and with 5.0 times of tentering device cross directional stretch, then 60 ℃ of heat settings, obtaining coating amount is 0.015g/m
2, thickness is the heat-shrinkable polystyrene type film of 60 μ m.
(experiment 15)
Except (TSM6343: solid constituent Toshiba's silicone corporate system) accounts for 40 quality % in solid constituent with the silicone aqueous dispersions, (Ha ィ テ ッ Network E-8237: solid constituent Dong Bang chemical company system) accounts for 10 quality % to the Tissuemat E aqueous dispersions in solid constituent, (バ ィ ロ Na-Le MD1500: solid constituent Japan's textile company system) accounts for 30 quality % to the esters resin aqueous dispersions in solid constituent, the solid constituent of surfactant (メ ガ Off ァ ッ Network F442: big Japanese ink chemical industry system) accounts for the IPA-aqueous solution of 20 quality % as outside the coating liquid in solid constituent, use and test 14 same methods and obtain heat-shrinkable polystyrene type film.
(experiment 16)
Except (TSM6343: solid constituent Toshiba's silicone corporate system) accounts for 45 quality % in solid constituent with the silicone aqueous dispersions, (Ha ィ テ ッ Network E-8237: solid constituent Dong Bang chemical company system) accounts for 15 quality % to the Tissuemat E aqueous dispersions in solid constituent, (バ ィ ロ Na-Le MD1500: solid constituent Japan's textile company system) accounts for 35 quality % to the esters resin aqueous dispersions in solid constituent, the solid constituent of surfactant (メ ガ Off ァ ッ Network F442: big Japanese ink chemical industry system) accounts for the IPA-aqueous solution of 5 quality % as outside the coating liquid in solid constituent, use and test 14 same methods and obtain heat-shrinkable polystyrene type film.
(experiment 17)
Except coating amount in the above-mentioned experiment 14 is decided to be 0.7g/m
2Obtain heat-shrinkable polystyrene type film equally with experiment 14 outward.
(experiment 18)
Except coating amount in the above-mentioned experiment 14 is decided to be 0.001g/m
2Obtain heat-shrinkable polystyrene type film equally with experiment 14 outward.
(experiment 19)
Except (TSM6343: solid constituent Toshiba's silicone corporate system) accounts for 10 quality % in solid constituent with the silicone aqueous dispersions in the above-mentioned experiment 14, (Ha ィ テ ッ Network E-8237: solid constituent Dong Bang chemical company system) accounts for 15 quality % to the Tissuemat E aqueous dispersions in solid constituent, (バ ィ ロ Na-Le MD1500: solid constituent Japan's textile company system) accounts for 60 quality % to the esters resin aqueous dispersions in solid constituent, the solid constituent of surfactant (メ ガ Off ァ ッ Network F442: big Japanese ink chemical industry system) accounts for the IPA-aqueous solution of 15 quality % as outside the coating liquid in solid constituent, use and test 14 same methods and obtain heat-shrinkable polystyrene type film.
(experiment 20)
Random polystyrene (the weight average molecular weight 300 that 40 moles of % of 4-methyl styrene are copolymerized into as constituent, 000) is equipped with the calcium carbonate particle 0.05 weight % of average grain diameter 1.0 μ m as lubricant, be mixed into the section of matrix resin raw material, with styrene-butadiene block copolymer (rubber constituent) the raw material section that this raw material is cut into slices and styrene 10 weight % are copolymerized into as constituent, and modifier high styrene rubber (the SB rubber of adjusting compatibility; Contain styrene 85 quality % as constituent) raw material section, cooperate with the ratio of mass ratio 40/55/5 (matrix resin/rubber constituent/modifier), in addition, use with the same method of above-mentioned experiment 19 and obtain heat-shrinkable polystyrene type film.
The composition of raw materials of the easy glide layer of film is shown in table 4, and the rerum natura of gained film is shown in table 5.
[table 4]
[table 5]
Use is rolled up each horizontal 500m * 2 by experiment 14～17 gained films, when passing through printing machine with the 100/min linear velocity, in the experiment 14～16, all deflector rolls are not all found the abrasion bits, use under the situation of experiment 17, the roller that contacts with the easy glide applicator surface, particularly roll out near the part the metal deflector roll (surperficial corrosion-resistant aluminium processing system, diameter 74mm), with Visual Confirmation be attached with white powdery abrasion consider to be worth doing.
Claims (11)
1. a heat-shrinkable polyester film is characterized in that satisfying following condition (A)～(C),
(A) in the one side at least of polyester film, being formed with the solid constituent coating amount that contains silicone composition and adhesive resin composition is 0.002～0.5g/m
2The easy glide layer;
(B) coefficientoffriction d≤0.27 of easy glide interlayer;
(C) percent thermal shrinkage of the maximum collapse direction of dipping after 10 seconds is more than 50% in 95 ℃ hot water.
2. heat-shrinkable polyester film as claimed in claim 1 is characterized in that, coefficientoffriction d≤0.24 of easy glide interlayer.
3. heat-shrinkable polyester film as claimed in claim 1 is characterized in that, the containing ratio of silicone composition is 10～80 weight % in the easy glide layer solid constituent, and the silicone component content is 0.001 to 0.4g/m
2
4. heat-shrinkable polyester film as claimed in claim 1 is characterized in that, contains the mylar composition that has the styrene part in the molecule in the easy glide layer.
5. heat-shrinkable polyester film as claimed in claim 1, wherein, one side can be bonding with organic solvent with another side.
6. a heat-shrinkable polystyrene type film is characterized in that, the polystyrene type film at least the one side be formed with the easy glide layer that contains silicone composition and adhesive resin composition, described heat-shrinkable polystyrene type film satisfies following condition (a)～(c),
(a) coefficientoffriction d≤0.25 between the film single face at least;
(b) film was flooded 20 seconds in 80 ℃ hot water, its thermal contraction 10% back on main shrinkage direction is taken out, air dry after 24 hours in 23 ℃, the atmosphere of relative humidity 65%, coefficientoffriction d≤0.28 between the film single face at least;
(c) percent thermal shrinkage of the maximum collapse direction of dipping after 10 seconds is more than 50% in 95 ℃ hot water.
7. heat-shrinkable polystyrene type film as claimed in claim 6 is characterized in that satisfying following condition (d), (e),
(d) coefficientoffriction d≤0.20 between the film single face at least;
(e) film was flooded 20 seconds in 80 ℃ hot water, its thermal contraction 10% back on main shrinkage direction is taken out, air dry after 24 hours in 23 ℃, the atmosphere of relative humidity 65%, coefficientoffriction d≤0.23 between the film single face at least.
8. heat-shrinkable polystyrene type film as claimed in claim 6 is characterized in that, in the single face side of film, is provided with the easy glide layer that contains the lubricant composition as outermost layer at least.
9. heat-shrinkable polystyrene type film as claimed in claim 8 is characterized in that described easy glide layer is provided with by coating process.
10. heat-shrinkable polystyrene type film as claimed in claim 6 is characterized in that, one side can be bonding with organic solvent with another side.
11. heat-shrinkable polystyrene type film as claimed in claim 6, it is characterized in that, at flexible pattern: frequency 50Hz ,-20 ℃ to 250 ℃ temperature range, programming rate: under 2 ℃/minute the condition, when main shrinkage direction is measured the film dynamic viscoelastic, the temperature range of the dispersion beyond the α that instrumentation derives from polystyrene disperses measures the dispersion of α beyond disperseing.
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| JP414518/2003 | 2003-12-12 | ||
| JP2003414518A JP4390046B2 (en) | 2003-12-12 | 2003-12-12 | Polyester heat shrinkable film |
| JP427537/2003 | 2003-12-24 | ||
| JP066635/2004 | 2004-03-10 |
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| CN1894101A CN1894101A (en) | 2007-01-10 |
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| JP2006181897A (en) * | 2004-12-28 | 2006-07-13 | Toyobo Co Ltd | Heat shrinkable polyester film, its manufacturing method and heat shrinkable label |
| JP4760186B2 (en) * | 2005-07-27 | 2011-08-31 | 東洋紡績株式会社 | Heat-shrinkable polyester film, method for producing the same, and heat-shrinkable label |
| JP4524718B2 (en) | 2008-08-08 | 2010-08-18 | 東洋紡績株式会社 | Heat-shrinkable polyester film |
| JP5534728B2 (en) | 2009-07-15 | 2014-07-02 | 日東電工株式会社 | Transparent film and use thereof |
| JP5737804B2 (en) * | 2011-04-13 | 2015-06-17 | フジコピアン株式会社 | Sticky functional film |
| WO2017029999A1 (en) * | 2015-08-19 | 2017-02-23 | 東洋紡株式会社 | Heat-shrinkable polyester-based film, and package |
| CN111335111A (en) * | 2020-03-03 | 2020-06-26 | 宝力科技(宁国)有限公司 | Novel plastic environmental protection type runway that breathes freely |
-
2003
- 2003-12-12 JP JP2003414518A patent/JP4390046B2/en not_active Expired - Fee Related
-
2004
- 2004-12-10 CN CNB2004800371218A patent/CN100515764C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1894101A (en) | 2007-01-10 |
| JP4390046B2 (en) | 2009-12-24 |
| JP2005169904A (en) | 2005-06-30 |
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