CN100564002C - The in-molded body of tape label and the in-molded label of using - Google Patents
The in-molded body of tape label and the in-molded label of using Download PDFInfo
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- CN100564002C CN100564002C CNB2005800396578A CN200580039657A CN100564002C CN 100564002 C CN100564002 C CN 100564002C CN B2005800396578 A CNB2005800396578 A CN B2005800396578A CN 200580039657 A CN200580039657 A CN 200580039657A CN 100564002 C CN100564002 C CN 100564002C
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Abstract
The present invention relates to the in-molded body and the in-molded label of using of tape label, on formed body (D), have in-molded in the in-molded body (E) of described tape label with label (C), describedly in-moldedly comprise basic unit (A) and hot sealing layer (B) with label (C), thermoplastic resin is contained in described basic unit (A), described hot sealing layer (B) contains heat sealing resin and water-soluble binder, and the in-molded body (E) of described tape label soaks 4 days in-molded features of also not peeling off with label (C) and formed body (D) even have in 40 ℃ water.The in-molded body (E) of this tape label has both the label stickiness and removes label.
Description
Technical field
The present invention relates to the in-molded body of tape label and make the used in-molded label of using.More particularly, the present invention relates to contain the in-molded in-molded body (E) of basic unit (A) and hot sealing layer (B) with label (C) and tape label, thermoplastic resin is contained in described basic unit (A), the in-molded body (E) of described tape label has described in-molded with label (C) on formed body (D), and described in-molded good with the label (C) and the stickiness of described formed body (D), the in-molded body (E) of described tape label under given conditions go the label excellence.
Background technology
The moulded work of polyethylene, polypropylene, polyvinyl chloride, PET, polybutylene terephthalate, PEN, polyamide, Merlon, polystyrene etc. in light weight, anti-falling property, resistance to impact etc. are strong, with glass and ceramic phase ratio, this moulded work safe is so be used as packing container in a lot of fields.Particularly be bottle excellence aspect the transparency, lustrous surface, chemical resistance, internal pressure-resistant that the mylar drawn blow molding of representative obtains, have common ideal characterisitics as packing container with the PET.Therefore, in a lot of fields such as food, washing agent, generally use this packing container.
Stretch blow molding is the preform stretch blow that will be inserted in the blowing mould, is shaped to the stretch blow molding body of regulation shape.At this moment, in the blowing mould, label is installed in advance, is carried out in-mould labeling formed, when in-mould labeling formed, along with stretch blow, label also is attached to the surface (for example the spy opens the 2002-355886 communique) of stretch blow molding body, in-mould labeling formedly in fact is used in a lot of aspects.
On the other hand, along with formulation, the utilization again of formed body is also become a kind of social demand about laws (container package utilizes method (container package リ サ イ Network Le method) again) such as the classification recovery that promotes container package and secondary commercializations.Therefore, proposed formed body is separated with label, utilized the technology (for example opening flat 06-55727 communique in fact) of formed body again.
But for this technology, label is not fitted on the formed body fully, so the shortcoming that this technology exists label meeting nature to come off.In addition, if use a large amount of adhesives in order to strengthen stickiness, then with formed body with after label separates, residual on formed body have an adhesive, has the shortcoming that in fact can not utilize again.
Summary of the invention
Therefore, label of the prior art can not realize having stickiness with formed body and the characteristic of adhesive-free residual (this postscript removes label) during from the formed body separation tags simultaneously.Therefore, the objective of the invention is to solve these prior art problems, a kind of in-molded body of tape label is provided, it can realize label simultaneously to the stickiness of formed body with remove label, and formed body can utilize again.In addition, purpose of the present invention also comprises provides the in-molded label of using that can make this formed body.
The present inventor has carried out conscientiously research, found that, carry out in-molded by having hot sealing layer (this hot sealing layer has specific 26S Proteasome Structure and Function) or having the in-molded of this hot sealing layer and printed layers with label, can access the in-molded body of tape label, thereby finish the present invention with desirable characteristics.
In other words, the invention provides a kind of in-molded body (E) of tape label, it is to have the in-molded in-molded body (E) of using the tape label of label (C) on formed body (D), described in-moldedly have basic unit (A) and hot sealing layer (B) with label (C), thermoplastic resin is contained in described basic unit (A), and described hot sealing layer (B) contains heat sealing resin and water-soluble binder; Even the in-molded body (E) of described tape label was soaked 4 days in 40 ℃ water, the in-molded label (C) of using can not break away from formed body (D) yet.In addition, the present invention also provides described in-molded with label (C).
Of the present invention in-moldedly preferably have basic unit (A), hot sealing layer (B) and the printed layers (F) that contains thermoplastic resin successively with label (C), and the printing area of printed layers (F) is 1%～90% of a label integral body, is preferably 5%～80%.
The in-molded body (E) of tape label of the present invention preferably soaked in 80 ℃ 1.5 weight % sodium hydrate aqueous solutions after 15 minutes, in-moldedly comes off from formed body (D) with label (C), and residual heat seal (B) not on the formed body (D).
Wherein, the preferred in-molded label of using that comprises following basic unit (A) and hot sealing layer (B) that uses, thermoplastic resin is contained in described basic unit (A), and it is 50 ℃～120 ℃ thermoplastic resin and the water-soluble binder of 70 weight %～1 weight % that described hot sealing layer (B) contains 30 weight %～99 weight % fusing points.
Among the present invention, the density of preferred basic unit (A) is 0.40g/cm
3～0.98g/cm
3, and the thermoplastic resin of basic unit (A) is a polyolefin.In addition, hot sealing layer (B) preferably is coated on by the water paint that will contain heat sealing resin and water-soluble binder and carries out in the basic unit (A) that drying forms.Herein, water-soluble binder cationic water-soluble binder preferably.In addition, preferred formed body (D) is made of polyethylene, polypropylene, polyvinyl chloride, PET, polybutylene terephthalate, PEN, polyamide or polystyrene, and formed body (D) is by injection moulding, directly blow molding, injection blow molding, stretch blow molding, thermoforming or compression forming and moulding obtains.
Description of drawings
Fig. 1 is an in-molded profile of using a form of label of the present invention.
Fig. 2 is an in-molded profile of using another form of label of the present invention.
Fig. 3 is the profile of in-molded machine that is used to make the PET bottle of tape label.
Fig. 4 is the profile that is used to make the in-molded machine of the polypropylene vial of tape label or polyethylene bottle.
Fig. 5 is the outside drawing of a form of in-molded body of tape label of the present invention.Fig. 5 (a) is that isometric front view, Fig. 5 (b) are rear isometric view.
Among the figure, A be basic unit, A-1 be label substrate surface, B be hot sealing layer, C be in-molded with label, D be formed body, E be in-molded body, the F of tape label be printed layers, 2 and 12 for mould, 2-a and 12-a be that inwall, 3 is blown into nozzle for air for parison, 8 for die head, 7 for stretching bar, 6 for SS, 5 for preform, 4 and 14.
The specific embodiment
Below to the in-molded body of tape label of the present invention with in-moldedly be elaborated with label.It should be noted that the number range with "～" expression is meant that the numerical value that comprises record before and after "～" is the scope of higher limit and lower limit in this specification.
Of the present invention in-moldedly have the basic unit (A) that contains thermoplastic resin and contain heat sealing resin and the hot sealing layer of water-soluble binder (B) with label (C).The object lesson of typical in-molded structure with label (C) of the present invention is seen Fig. 1.
In addition, another mode of the present invention in-molded has basic unit (A), heat sealing resin (B) and the printed layers (F) that contains thermoplastic resin with label (C).The object lesson of the in-molded structure with label (C) of another mode of the present invention is seen Fig. 2.
The in-molded body (E) of tape label of the present invention has by in-molded and is added in structure on the formed body (D) with in-molded with label (C).
[basic unit (A)]
Basic unit among the present invention (A) is the layer that contains thermoplastic resin, and it is a layer of using the support of label (C) as in-molded.By containing thermoplastic resin, can obtain the in-molded of resistance to water, excellent in stability with label (C).
(material)
For the material of the basic unit among the present invention (A),, just be not particularly limited as long as it contains thermoplastic resin and resistance to water excellence.As the example of the contained thermoplastic resin of basic unit (A), can enumerate the polyolefin resin of high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), propylene resin, poly-Methyl-1-pentene etc.; Vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, maleic acid modified poly ethylene, maleic acid modified polypropene etc. contain the polyolefin resin of functional group; Nylon-6, nylon-6,6 polyamide-based resins such as grade; Thermoplastic polyester resins such as PET, polyethylene terephthalate copolymer, polybutylene terephthalate, aliphatic polyester; Merlon; Random isotactic polystyrene; Syndiotactic polystyrene etc.In these thermoplastic resins, polyolefin resin is owing to have excellent processability thereby preferred the use.
As the example more specifically of polyolefin resin, can enumerate the homopolymers of alkenes compounds such as ethene, propylene, butylene, butadiene, isoprene, chlorobutadiene, Methyl-1-pentene and contain the copolymer etc. of the monomer of functional group by the formed copolymer of these alkenes compounds more than 2 kinds and these alkenes compounds and styrene, AMS, vinyl acetate, vinyl alcohol, acrylic acid derivative, vinyl ethers compound etc.
In addition, in these polyolefin resins, from chemical resistance, cost aspect equal angles, preferred propylene resin.As propylene resin, the polypropylene that preferably uses the stereospecificity that shows isotaxy or syndiotactic and various degree in the Noblen as main component or use by the copolymerization of alpha-olefins such as propylene and ethene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene resulting with propylene as the copolymer of main component as main component.This copolymer can be 2 yuan of systems, also can be the system more than 3 yuan, and can be random copolymer, also can be block copolymer.During use, the fusing point that preferably adds 2 weight %～25 weight % in propylene resin is lower than the resin of Noblen.As this low-melting resin, can enumerate high density or low-density polyethylene.
As required, can add inorganic fine powder, organic filler, stabilizing agent, light stabilizer, dispersant, lubricant etc. in the basic unit (A).When adding inorganic fine powder, can use particle diameter usually is the inorganic fine powder of 0.01 μ m～15 μ m, and preferably using particle diameter is the inorganic fine powder of 0.01 μ m～5 μ m.Concrete example comprises calcium carbonate, fires clay, silica, diatomite, carclazyte, talcum, titanium dioxide, barium sulfate, aluminium oxide, zeolite, mica, sericite, bentonite, sepiolite, vermiculite, dolomite, wollastonite and glass fibre etc.In addition, when using inorganic fine powder, preferably handle by hydrophily in advance and/or lipophile processing etc. to carrying out surface treatment in its surface, by surface treatment, can improve dispersed and can give basic unit (A) printing, coating adaptability, anti-scratching, all be coated with adaptability, 2 various performances such as flexibility (adaptability) of operation.As for surface conditioning agent, can use known surface conditioning agent, specifically, when adding organic filler, preferential select with as the different types of resin of the thermoplastic resin of principal component.For example, thermoplastic resin film is under the situation of polyolefin resin film, as organic filler, can use fusing point (for example 170 ℃～300 ℃) or glass transition temperature (for example 170 ℃～280 ℃) be higher than polyolefin resin fusing point and with the inconsistent PET of thermoplastic resin film, polybutylene terephthalate, Merlon, nylon-6, nylon-6,6, polymer such as poly-cycloolefin, polystyrene, polymethacrylates.
(moulding)
Can come moulding basic unit of the present invention (A) by the film that uses these material systems.During moulding basic unit (A), can adopt following forming method: use and to be connected in the single or multiple lift T mould of screwe-type xtruder or the I mould is extruded molten resin with sheet cast molding, use circular mode that molten resin is extruded into tubular and utilize inner air pressure make its expansion hollow molding, will be processed into the roll forming, calendering formation etc. of sheet through mixing material with at least 2 hot-rollings calenderings.
(lamination)
For basic unit (A), can carry out lamination by known the whole bag of tricks.As concrete example, can enumerate the multilayer press moulding mode that uses feed head or multiple-branch manifold; Use the lamination mode etc. of extruding of a plurality of die heads etc.In addition, can also be used in combination multilayer mold pressing and extrude lamination.
(stretching)
For basic unit (A), can also stretch by any one method in the whole bag of tricks of common employing.
Draft temperature can be the known temperature scope that is suitable for stretched thermoplastic resin, and this temperature range is the fusing point of the glass transition temperature of the main thermoplastic resin that uses in the basic unit (A) to the crystal block section of this thermoplastic resin.Specifically, this temperature than thermoplastic resin fusing point low 1 ℃～70 ℃, when the thermoplastic resin of basic unit (A) was Noblen (fusing point: 155 ℃～167 ℃), draft temperature was 100 ℃～166 ℃; When thermoplastic resin was high density polyethylene (HDPE) (fusing point: 121 ℃～136 ℃), draft temperature was 70 ℃～135 ℃.In addition, draw speed is preferably set to 20m/ minute～350m/ minute.
As drawing process, when the cast molding film is stretched, can enumerate the longitudinal stretching that the difference of utilizing the roller group is carried out; Use the cross directional stretch that stenter drying machine carried out; Calendering; It is biaxial stretch-formed etc. when combination stenter drying machine and linear motor carry out.In addition, as the drawing process of hollow molding film, can enumerate when utilizing tubular process to carry out biaxial stretch-formed.
Stretching ratio is not particularly limited, considers that the characteristic of the thermoplastic resin that basic unit (A) uses waits suitably definite stretching ratio.For example, when using as thermoplastic resin with Noblen or its copolymer, the stretching ratio when single orientation stretches is about 1.2～12 times usually, be preferably 2～10 times, and when biaxial stretch-formed, calculate with the area multiplying power, this multiplying power is generally 1.5～60 times, is preferably 4～50 times.When using other thermoplastic resin, when single orientation stretched, this stretching ratio was generally 1.2～10 times, is preferably 2～5 times, and when biaxial stretch-formed, calculated with the area multiplying power, and this multiplying power is generally 1.5～20 times, is preferably 4～12 times.
The laminated film that so obtains is the laminated film that film inside has trickle in a large number emptying aperture, and its void content of calculating with following formula (1) is generally 5%～60%, is preferably 10%～45%.Compare with the stretched film that does not have emptying aperture, because the existence of emptying aperture, this laminated film is more soft.
Void content (%)=((ρ
0-ρ)/ρ
0) * 100 ... (1)
(in the following formula, ρ
0Be real density, ρ is a density.)
As long as the material before stretching does not contain a large amount of air, the density before real density equals to stretch substantially.
In addition, because the formation of emptying aperture, the density of basic unit (A) descends, and when using label (C) from in-molded body (E) separation of tape label is in-molded, utilizes proportion to separate easily, easily in-molded body is utilized again.The density of basic unit of the present invention (A) is preferably 0.40g/cm
3～0.98g/cm
3, 0.50g/cm more preferably
3～0.96g/cm
3, 0.60g/cm more preferably
3～0.96g/cm
3The density of basic unit (A) is 0.98g/cm
3When following, utilize water to carry out proportion easily and separate, its density is 0.40g/cm
3When above, in-molded intensity with label (C) is abundant.
The thickness of basic unit (A) is generally 10 μ m～500 μ m, is preferably 20 μ m～300 μ m.Its thickness is 10 μ m when above, prints or label is added man-hour, because its body bone is strong thereby processing easily, in addition, its decals adaptability as label might as well.Its thickness is 500 μ m when following, and is in-molded suitable with the whole thickness of label (C), so can not influence the shape of the in-molded body (E) of tape label.
Basic unit (A) is preferably through uniaxial tension at least.It can be a double-decker, or having sandwich construction more than three layers, the tensile axis quantity of this sandwich construction can be for example single shaft/single shaft, single shaft/twin shaft, twin shaft/single shaft, single shaft/single shaft/twin shaft, single shaft/twin shaft/single shaft, twin shaft/single shaft/single shaft, single shaft/twin shaft/twin shaft, twin shaft/twin shaft/single shaft, twin shaft/twin shaft/twin shaft.By multilayer is made by basic unit (A), can provide various functions such as printing, coating adaptability, anti-scratching, decals adaptability and secondary operations adaptability.
[hot sealing layer (B)]
Hot sealing layer among the present invention (B) can be provided with by being coated with to wait in basic unit (A).Hot sealing layer of the present invention (B) contains heat sealing resin and water-soluble binder, so it shows excellent in water resistance, by handling, can selectively hot sealing layer (B) and base material (A) together be peeled off from formed body (D) simultaneously with the alkaline aqueous solution etc. of regulation.
Hot sealing layer (B) though in the water-soluble binder that can use in " the state-of-the-art technology trend and the commercial Application of water-soluble-water-dispersion type macromolecular material " (Japanese scientific information society periodical), record is at length arranged also, can use the following adhesive of enumerating.
At first, can enumerate starch as the adhesive that derives from natural materials, modified starch, carboxymethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, gelatin, pulullan polysaccharide, alginic acid, guar gum, locust bean gum, xanthans, pectin, carrageenan, Arabic gum, ghatti gum (Ghatti gum), Ke Laiya glue (Network ラ ヤ ガ system), tragacanth, flaxseed gum, soybean polysaccharides, tamarind gum, tara gum, agar, carrageenin (furcelleran), glucomannans (グ Le コ マ Application ア Application), microcrystalline cellulose, welan gum, curdlan, gellan gum, glucan, xanthans (キ サ Application ザ Application ガ system), chitin, shitosan etc.
Secondly, as the adhesive of making by chemical synthesis, can enumerate polyvinyl alcohol, polyacrylic polymer, the aziridine base polymer, polyoxyalkylene, polyacrylamide, poly styrene sulfonate, poly-amidine, isoprenoid sulfonic acid base polymer, polythene derivative, the PVP analog copolymer, PVAA, poly-dioxy silane, polyvinylphenol, polyglycerol, the poly analog copolymer, poly-itaconic acid analog copolymer, 2-acrylamido-2-methyl propane sulfonic acid sodium analog copolymer, naphthalene sulfonic acid condensate, ammonium polystyrene sulphonate salt, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, diallyl dimethyl ammoniumchloride, the guanidine ureas condensation product that contracts, table Chlorodimethyl amine condensation product (エ PVC Network ロ ジ メ チ Le ア ミ Application condensation product), dimethyl amine-vinyl chloride condensation product, amino methyl class polyacrylamide, polyvinylamine, polyacrylic hydrazide, the polyvinyl imidazol quinoline, the polyvinyl benzyltrimethylammonium chloride, PVAA-vinylamine copolymer etc.
Above-mentioned water-soluble binder roughly is divided into nonionic water-soluble binder and ionic adhesive by the kind of hydrophilic radical, and in addition, ionic water-soluble binder is subdivided into cationic adhesive, anionic property adhesive or double ion adhesive again.Among the present invention, in order to keep the stickiness with basic unit (A), the ionic water-soluble binder of preferred use, particularly contain under the situation of polyolefin resin in basic unit (A), when using the cationic water-soluble binder, with the stickiness excellence of basic unit (A), so more preferably use the cationic water-soluble binder.
As the example of cationic water-soluble binder, can enumerate aziridine base polymer, polyacrylamide, PVAA, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, diallyl dimethyl ammoniumchloride, guanidine in the example of above-mentioned water-soluble polymer contract ureas condensation product, table Chlorodimethyl amine condensation product, dimethyl amine-vinyl chloride condensation product, amino methyl class polyacrylamide, polyvinylamine, polyacrylic hydrazide, polyvinyl imidazol quinoline, polyvinyl benzyltrimethylammonium chloride, PVAA-vinylamine copolymer etc.
In the cationic water-soluble binder, optimal ethylene imines base polymer.
Hot sealing layer of the present invention (B) contains heat sealing resin.Heat sealing resin is thermoplastic resin preferably.Especially, if heat sealing resin is that fusing point is 50 ℃～120 ℃ a thermoplastic resin, aspect practical, be preferred then, preferred especially heat sealing resin is that fusing point is 60 ℃～110 ℃ a thermoplastic resin.The fusing point of heat sealing resin is more than 50 ℃ the time, can more effectively prevent between the label because bonding and adhesion.The fusing point of heat sealing resin is below 120 ℃ the time, further improves the stickiness to formed body (E) easily.
As operable heat sealing resin in the hot sealing layer (B), can use for example resins such as acrylic polymer, vinyl acetate esters polymer, styrenic polymer, polyvinyl chloride-base polymer, vinylidene chloride base polymer, polyethylene, polyurethane, polyester, epoxy resin, Petropols, rosin ester, silicones, alkyd resins, polybutadiene, butadiene copolymer, polybutene, butyl rubber, polypropylene, polychlorobutadiene, polyisoprene.In the middle of these, preferred acrylic polymer, vinyl acetate esters polymer, styrenic polymer, as example more specifically, can enumerate ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinyl-acrylate copolymer, acrylate polymer, vinyl-vinyl acetate copolymer, SB etc.
The heat sealing resin in the hot sealing layer among the present invention (B) and the mixed proportion of water-soluble binder are as follows: preferred heat sealing resin is 30 weight %～99 weight %, and water-soluble binder is 70 weight %～1 weight %, more preferably heat sealing resin is 50 weight %～99 weight %, and water-soluble binder is 50 weight %～1 weight %, further preferred heat sealing resin is 75 weight %～99 weight %, and water-soluble binder is 25 weight %～1 weight %.The ratio of water-soluble binder is 70 weight % when following, further improves stickiness easily, and the ratio of water-soluble binder is 1 weight % when above, and further label is removed in raising easily.
Preferred form with water paint is prepared hot sealing layer (B) owing to contain water-soluble binder.Specifically, the water paint that preferably this composition is formed through the preparation surface that is coated on basic unit (A) forms hot sealing layer (B) by drying.Aspect environment, the not solvent-laden water paint of also preferred use, so heat sealing resin preferably uses for example emulsion polymeric product, suspension polymerisation product or the aqueous dispersions such as dispersion liquid that after mechanical crushing it are dispersed in the aqueous solvent with extruder etc. are prepared.
In order further to improve resistance to water, hot sealing layer (B) preferably contains crosslinking agent, as the object lesson of crosslinking agent, can enumerate epoxidation polyamide polyamine, urea-formaldehyde resin, melamine formaldehyde resin, DAS, multi-functional epoxy's class crosslinking agent, carbodiimide class crosslinking agent, glyoxal, oxazoline class crosslinking agent, borax, nitric acid zirconates etc.As required, can also suitably add anti-blocking agent, lubricant, antistatic agent, dispersant, tackifier, defoamer, anticorrisive agent, ultra-violet absorber, ultra-violet stabilizer, antioxidant, surfactant, water soluble dyestuffs, coloring pigment etc.
Basic unit (A) utilizes known coating process to carry out with the lamination of hot sealing layer (B).Specifically, can adopt print roll coating, scraper coating, bar type coating, airblade coating, intaglio plate coating, anti-phase coating, pattern coating, the coating of lip formula, spraying coating, comma coating, size press coating or these the coating method that constitutes.
Suitably select the drying coated amount of hot sealing layer (B) according to employed base material film, this coating weight is preferably 0.05g/m usually
2～30g/m
2, 0.1g/m more preferably
2～20g/m
2, 0.2g/m more preferably
2～10g/m
2
Drying coated amount is 0.05g/m
2When above, carrying out to bring into play enough adhesion strengths when in-molded.In addition, drying coated amount is 30g/m
2When following, carry out when in-molded, the hot sealing layer of fusion (B) can not be bonded on the mould owing to overflowing from label, so even carry out moulding continuously, can not influence the aesthetic property of the in-molded body (E) of tape label because of the shape that stays label on the mould yet.
In addition, when coating weight increases, can not finish coating, must repeatedly repeat coating, and produce problems such as production cost increases by once being coated with.
[printed layers (F)]
As required, the in-molded label (C) of using of the present invention can be in the arranged outside printed layers (F) of hot sealing layer (B).Clip printed layers (F) and be positioned on the transparent formed article (D) with label (C), thus, can see through formed body (D) and see figure and the literal (Fig. 4) that is added on the printed layers (F) in-molded.In this case, can obtain the more excellent in the past in-molded body (E) of ornamental ratio.In addition, as obtaining this in-molded method with label (C), also be included in and form hot sealing layer (B) before, the method of printed layers (F) is set in basic unit (A), but owing to must after printing, seal processing at every turn, so process complicatedly, have the instability quality shortcoming of hot sealing layer (B).Therefore, among the present invention, after formation hot sealing layer (B) is gone up by basic unit (A), printed layers (F) is set on this hot sealing layer (B) further.According to the present invention, can control the in-molded stickiness of using label (C) to formed body (D) by the area occupation ratio of printed layers (F), can easily separate formed body (D) and in-molded with label (C).
Of the present inventionly in-moldedly printed layers (F) can be set on hot sealing layer (B) with label (C), but, if the area of printed layers (F) surpasses 90% of the label gross area, for example when the whole face of hot sealing layer (B) prints, can not obtain in-molded with the sufficient stickiness of label (C) to formed body (D).In addition, be preferably designed among the present invention and can see through formed body (D) and see the figure of printed layers (F) and the pattern of literal, the printing area of printed layers (F) be typically designed to in-molded with label (C) whole 1%～90%, be preferably 5%～80%, more preferably 5%～70%.
When forming printed layers (F), can adopt known method such as hectographic printing, letterpress, intaglio printing, aniline printing, typographic printing, ink-jet recording, hotness recording mode, hot tranfer recording mode, electrophotographic recording mode.In addition, used printing ink in the formation of printed layers (F), (printing-ink is crossed the threshold can to adopt known document, mutually former youth's work, the distribution of publishing department of printing association) all printing ink that describe in detail in, but preferably printing-ink consumption (printing イ Application キ Sheng amount) is less and offset ink, the flexographic ink of matching in color property excellence.As the drying mode of printing ink, preferably with oxidation polymerization drying type, hot polymerization drying, the photopolymerization drying type printing ink of the stickiness excellence of base material.Specifically, as offset ink, can enumerate TSP-400, T﹠amp that Toyo Ink manufacturing (strain) society produces; BEST SP and T﹠amp that K TOKA society produces; The BC-161 that K TOKA society produces etc. as flexographic ink, can enumerate UV-AceFX-1, T﹠amp that Kubo well printing ink (strain) society produces; Flexo PAC-MP and T﹠amp that K TOKA society produces; The UV flexo CF that K TOKA society produces etc.
[other printing]
Of the present invention in-moldedly can also print on the surface of base material (A) (with the opposite one side of face that hot sealing layer (B) is set) as required with label (C).Described printing can be adopted and the same method of above-mentioned printed layers (F).Can also implement printing known decorations in addition such as metal evaporation on this surface.
[formed body (D)]
Of the present invention in-molded can be with label (C) by on the in-molded formed body (D) that is added in various materials.For example can be used for the formed body that forms by polyethylene, polypropylene, polyvinyl chloride, PET, polybutylene terephthalate, PEN, polyamide, Merlon, polystyrene etc., wherein preferably use polyethylene, polypropylene, PET.If uses such as the polyethylene that the combination melt temperature is high, polypropylene can obtain stronger stickiness, be preferred therefore.When being used in combination proportion greater than the PET of water, PEN, polystyrene etc., label (C) separates by proportion easily with formed body (D), so be preferred.
Known method is adopted in the moulding of formed body (D).For example the resin of fusion is flowed into the injection moulding of mould, the resin of fusion is extruded into tubular and keeps making under the molten condition the direct blow molding of its expansion at mould inside from circular die, make it be expanded to the injection blow molding of container shapes after will adjusting to suitable forming temperature by the preform (small containers shape formed body) that injection moulding forms, make the preform of moulding expand into the stretch blow molding of container shapes in the temperature that is lower than melting point resin by stretching bar and air pressure, heating utilizes pressure reduction to be processed into the thermoforming of mold shape after making the resin that is shaped to sheet softening, resin is become compression forming of mold shape etc. after the fusion by pressure processing in mould.
The present invention can adopt in these forming method arbitrarily, particularly has the advantage that can adapt to stretch blow molding, and in-molded with label in the past, because forming temperature is low thereby be difficult to by the stretch blow molding power of being fitted fully.
[in-molded stickiness] with label
In-molded stickiness height in the in-molded body (E) of tape label of the present invention with label (C) and formed body (D), and to the durability height of water.That is to say, promptly use hand etc. to make in-molded body (E) distortion of tape label, but label (C) is to the servo-actuated height of formed body (D), so incrust.In addition, even the in-molded body (E) of tape label was soaked 4 days in 40 ℃ water, label (C) is not peeled off with formed body (D) [for example PET formed body (D)] yet.In addition, alleged herein " not peeling off " comprises two aspects, be that label (C) is not a bit from formed body (D) state that peels off and the part of the peeling off state less than half (label (C) peels off 50% of not enough whole area, and is attached to more than 50% on the formed body (D)).
[the in-molded label that goes] with label
By soaking in being higher than 40 ℃ warm water, in-molded in the in-molded body (E) of tape label of the present invention separates with formed body (D) with label (C).The temperature of described warm water is preferably 70 ℃～100 ℃, and more preferably 75 ℃～100 ℃, more preferably 80 ℃～95 ℃ can be common warm water, also can be alkaline water.In order to realize separating, preferably use alkaline water in the short time.When using alkaline water, preferably use the PET bottle to utilize the alkaline water of the 1.5 such weight % concentration of being put down in writing in the recommendation association autonomous Design guide again.With in-molded with label (C) when formed body (D) separates, the in-molded body (E) of tape label of the present invention can be left standstill in warm water or alkaline water, by stirring warm water or alkaline water, the in-molded body (E) of tape label is applied vibration.In addition, also can be to in-molded with label (C) centralizedly supply warm water or alkaline water.In addition, also can make its porpoise, shorten disengaging time thus from in-molded exerting pressure on label (C).For the in-molded body (E) of tape label of the present invention, it has on these lock out operation aftershaping bodies (D) the not feature of residual heat seal (B).
Embodiment
Enumerate embodiment, comparative example and test example below, the present invention is carried out more specific description.
In the scope that does not exceed aim of the present invention, can suitably change material shown in following, consumption, ratio, operation etc.So, scope of the present invention be not subjected to following shown in the restriction of object lesson.
The resin combination that Production Example of the present invention is used gathers and is shown in table 1.
Table 1
| The material name | Content |
| Thermoplastic resin composition a | (Japanese Polypro (strain) produces the Noblen of 70 weight %, Novatec PP:FY4) ((230 ℃ of MFR, load 2.16kg)=5g/10 minute, fusing point=165 ℃) and the high density polyethylene (HDPE) of 10 weight % (Japanese polyethylene (strain) is produced, Novatec HD:HJ360) ((190 ℃ of MFR, load 2.16kg)=5g/10 minute, fusing point=131 ℃) composition that has mixed 20 weight % calcium carbonate (shiraishi calcium (strain) is produced, and Softon 1800) (average grain diameter=1.2 μ m) in the mixture is through being set in the mixing thermoplastic resin composition who forms of extruder of 230 ℃ temperature |
| Thermoplastic resin composition b | (Japanese Polypro (strain) produces the Noblen of 70 weight %, Novatec PP:MA3) ((230 ℃ of MFR, load 2.16kg)=11g/10 minute, fusing point=165 ℃) composition of calcium carbonate (produce from stone calcium (strain), Softon 1800) (average grain diameter=1.2 μ m) that has mixed 30 weight % in is through the mixing thermoplastic resin composition who forms of the extruder that is set in 230 ℃ of temperature |
| Thermoplastic resin composition c | (Japanese Polypro (strain) produces the Noblen of 60 weight %, Novatec PP:MA3) ((230 ℃ of MFR, load 2.16kg)=11g/10 minute, fusing point=165 ℃) composition of calcium carbonate (shiraishi calcium (strain) is produced, and Softon 1800) (average grain diameter=1.2 μ m) that has mixed 40 weight % in is through the mixing thermoplastic resin composition who forms of the extruder that is set in 230 ℃ of temperature |
| Thermoplastic resin composition d | (Japanese Polypro (strain) produces the Noblen of 40 weight %, Novatec PP:MA3) ((230 ℃ of MER, load 2.16kg)=11g/10 minute, fusing point=165 ℃) in mixed the composition of the cationic polymer surface calcium carbonate (average grain diameter=1.5 μ m) that obtains by preparation example 2 of 60 weight % through the mixing thermoplastic resin composition who forms of the extruder that is set in 230 ℃ of temperature |
| Thermoplastic resin composition e | Noblen (Japanese Polypro (strain) produce, Novatec PP:FY5) (MFR (230 ℃, load 2.16kg)=3g/10 minute, fusing point=166 ℃) |
The preparation of (preparation example 1) surface conditioning agent
In the reactor that reflux condenser, thermometer, dropping funel, agitating device and gas introduction tube are housed, add 500 weight portion diallyl amine hydrochlorates (aqueous solution of 60 weight % concentration), 13 weight portion acrylamides (aqueous solution of 40 weight % concentration) and 40 weight parts waters, temperature in the system is increased to 80 ℃ while charge into nitrogen.Stir down, through dropping funel with 4 hours dropping polymerization initiator ammonium persulfate (aqueous solution of 25 weight % concentration) 30 weight portions.After dripping end, continue reaction 1 hour, obtain the light yellow liquid object of thickness.Get this liquid object of 50g, be injected in the acetone of 500ml, produce white precipitate.Filtering-depositing, and after fully washing 2 times with the acetone of 100ml, carry out vacuum drying, obtain white solid state polymer (water-soluble cationic copolymer).The weight average molecular weight that resulting polymer is obtained by GPC is 55000.
The preparation of (preparation example 2) surface treatment powdered whiting
(average grain diameter is 8 μ m with the powdered whiting of 40 weight %, the dry type that Japanese cement society produces is pulverized product) and the water of 60 weight % fully mix, form the slurries shape, ratio with corresponding 0.06 weight portion of per 100 weight portion powdered whitings adds the surface conditioning agent that preparation example 1 is made, use the desk-top type medium stirring mill (bead of diameter 1.5mm that grinds, filling rate is 170%, and peripheral speed is 10m/sec) carry out case of wet attrition.Then, adding 50 parts principal component is that carbon number is that 14 alkane sulfonate and carbon number are that the mixture (aqueous solution of 2 weight % concentration) of 16 alkane sulfonate stirs.By 350 purpose screen clothes, carry out classification then, will carry out drying with media flow drying machine ((strain) nara machinery is made the MSD-200 that is produced) by the slurries of 350 purpose screen clothes.
Measure the average grain diameter of the calcium carbonate that obtains with Microtrac (day machine dress (strain) produce), its result is 1.5 μ m.This calcium carbonate material of the thermoplastic resin composition d in the tabulation 1.
The manufacturing 1 of (Production Example 1) A of basic unit
With thermoplastic resin composition a with the extruder that is set in 230 ℃ carry out mixing after, supply to and be set at 250 ℃ extrusion die, be extruded into sheet, then, its cooling is obtained not having drawing sheet by cooling device.Longitudinal stretching is 4 times after should no drawing sheet being heated to 140 ℃.With thermoplastic resin c be set in 250 ℃ extruder mixing after, be extruded into sheet, be laminated to the back side of above-mentioned 4 times of stretched film then, in addition, with thermoplastic resin composition d be set in 250 ℃ extruder mixing after, be extruded into sheet, be laminated to the surface of above-mentioned 4 times of stretched film then, obtain the laminated film of 3-tier architecture.Then, the laminated film of this 3-tier architecture is cooled to 60 ℃, uses stenter drying machine to be heated to about 140 ℃ once more, and 10 times of cross directional stretch, after this, heat-treat with the heat set zone that is adjusted at 160 ℃.Thereafter, be cooled to 60 ℃, cut overlap, ((d/a/c)=(30/40/30) μ m: tensile layer structure (single shaft/twin shaft/single shaft)) the white layer press mold of structure, its thickness are that 100 μ m, density are 0.86g/cm to obtain 3 layers
3
The manufacturing 2 of (Production Example 2) A of basic unit
With thermoplastic resin composition a and thermoplastic resin composition b respectively with the extruder that is set in 230 ℃ mixing after, supply to a coextrusion die head that is set in 250 ℃, be extruded into sheet behind the sequential laminating with b/a/b in die head, by cooling device with the cooling of this sheet after, obtain 3 layers no drawing sheet.After should no drawing sheet being heated to 150 ℃, 5 times of longitudinal stretchings.
Then, be cooled to 60 ℃, and then be heated to 150 ℃, use 8 times of stenter cross directional stretch, and soften processing (annealing), be cooled to 60 ℃ then at 160 ℃.Thereafter, carry out Corona discharge Treatment, then, cut overlap, ((b/a/b)=(10/60/10) μ m: tensile layer structure (twin shaft/twin shaft/twin shaft)) the white layer press mold of structure, its thickness are that 80 μ m, density are 0.76g/cm to obtain 3 layers
3
The manufacturing 3 of (Production Example 3) A of basic unit
With thermoplastic resin composition e with the extruder that is set in 230 ℃ carry out mixing after, supply to and be set at 250 ℃ extrusion die, be extruded into sheet, then, it is cooled off by cooling device, obtain not having drawing sheet.This no drawing sheet is carried out Corona discharge Treatment, then cut overlap, obtaining thick is that 100 μ m, density are 0.89g/cm
3Hyaline membrane.
The manufacturing 4 of (Production Example 4) A of basic unit
With thermoplastic resin composition e with the extruder that is set in 230 ℃ carry out mixing after, supply to and be set at 250 ℃ extrusion die, be extruded into sheet, then, its cooling is obtained not having drawing sheet by cooling device.After should no drawing sheet being heated to 150 ℃, 5 times of longitudinal stretchings.Should indulge stretched film and be cooled to 60 ℃, and use stenter drying machine to be heated to about 150 ℃ once more, cross directional stretch is 8 times then, after this heat-treats with the heat set zone that is adjusted into 160 ℃.Thereafter be cooled to 60 ℃, cut overlap, obtaining thick is that 80 μ m, density are 0.91g/cm
3Hyaline membrane.
(embodiment 1～5, comparative example 1～2) in-molded manufacturing of using the in-molded body of label and tape label
Dispersion liquid, water-soluble binder, paper power reinforcing agent, anti-blocking agent and the water of the heat sealability resin of record in the table 2 are mixed into composition and the solid component concentration that table 3 is put down in writing, preparation water paint (aqueous coating agent).With this water paint is the table side of the basic unit (A) of the 20m/min Production Example 1～4 that is coated on table 3 record respectively with the linear velocity with narrow slit type coating apparatus (Slot Die Coater), and be set at 80 ℃ the long drying machine of 10m with baking temperature and carry out drying, obtain 7 kinds in-molded with labels (C).The drying coated amount of the in-molded hot sealing layer with label (C) of each that obtains (B) sees Table 3.
(embodiment 6～9, comparative example 3) in-molded manufacturing of using the in-molded body of label and tape label
Further go up the site UV aniline printing of using as shown in Figure 2 at the in-molded hot sealing layer (B) that the foregoing description 1～4 obtains, obtain 5 kinds of in-molded labels (C) of using with label (C) with the printing condition of following record.Carry out printing at the bottom of the reality with 100% area occupation ratio in the comparative example 3.
The area occupation ratio of the in-molded printed layers with label (C) (C) that obtains sees Table 3.
Printing machine: MA-830 (production of Mark Andy society)
Printing ink: UV-Ace FX-1 indigo plant (Kubo well printing ink (strain) production)
Anilox roll: 300 lines
Print speed printing speed: 30m/min
UV exposure: 80W/m
2
[table 2]
The in-molded label that cuts high 70mm, wide 90mm with label (C) that obtains from each embodiment, comparative example, from vacuum decompression SS (4) suction of reducing pressure, so that Fig. 1, shown in Figure 2 in-molded with (ヨ one キ industry (strain) is produced with stretch blow molding machine shown in Figure 3 back to the label substrate surface (A-1) of hot sealing layer (B) in the label, trade name: the inwall (2-a) that is set in 25 ℃ mould (2) the PET-2W type) contacts, thereby the label that cuts is installed and fixed.Thereafter, to be shaped to preform (3 with injection (mo(u)lding) machine in advance with infrared heater, the small containers shape) (Japanese Unipet (strain) produces PET, trade name: Unipet RT543) be heated to 95 ℃, with the mould retention time is to carry out stretch blow molding in 10 seconds, obtains the in-molded body (E) that high 200mm, body enclose the cylinder type tape label of 210mm.
In addition, the in-molded label that cuts high 70mm, wide 90mm with label (C) that obtains from each embodiment, comparative example again, from vacuum decompression SS (14) suction of reducing pressure, with as shown in Figure 4, make back to the label substrate surface (A-1) of hot sealing layer (B) to contact with the inwall (12-a) that make-up machine is set in 25 ℃ mould (12), this label is installed and fixed with the hollow container manufacturing.To be heated to polypropylene (Japan polypropylene (strain) production: trade name " EG8 ") with ejaculation cycle 12 second carry out direct blow molding, obtain the in-molded body (E) of tape label of 200 ℃ molten condition thereafter.
In addition, the in-molded label that cuts high 70mm, wide 90mm with label (C) that obtains from each embodiment, comparative example, from vacuum decompression SS (14) suction of reducing pressure, with as shown in Figure 4, make back to the label substrate surface (A-1) of hot sealing layer (B) to contact with the inwall (12-a) that make-up machine is set in 15 ℃ mould (12), thereby this label is installed and fixed with the hollow container manufacturing.To be heated to high density polyethylene (HDPE) (Japanese polyethylene (strain) system: trade name " HB330 ") with ejaculation cycle 18 second carry out direct blow molding, obtain the in-molded body (E) of tape label of 180 ℃ molten condition thereafter.
(test example)
As follows to stickiness, the water-fast stickiness of the in-molded body (E) of each tape label of obtaining, go label evaluation.
(1) stickiness
With hand the in-molded body (E) of tape label is out of shape, observes the servo-actuated of label and formed body, and estimate by following 4 ranks.
Fabulous (◎) label is not peeled off along with formed body is out of shape.
Well (zero) label takes place partly to peel off.
Good slightly (△) label area over half is peeled off.
Difference (*) label peels off fully.
(2) water-fast stickiness
The in-molded body (E) of tape label was soaked 4 days in 40 ℃ water (running water), observe the servo-actuated of label and formed body, and estimate by following 4 ranks.
Fabulous (◎) label is not peeled off along with formed body is out of shape.
Well (zero) label takes place partly to peel off.
Good slightly (△) label area over half is peeled off.
Difference (*) label peels off fully.
(3) remove label
With the in-molded body (E) of tape label dissolved 1.5 weight % NaOH (with the pure medicine production of light: soaked 15 minutes in 80 ℃ of warm water (running water) 1 grade of reagent), observe the extent of exfoliation of label, and estimate by following 4 ranks.
Fabulous (◎) label was peeled off with interior at 10 minutes, did not have the residual heat seal on the formed body.
Well (zero) label was peeled off with interior at 15 minutes, did not have the residual heat seal on the formed body.
Good slightly (△) taken place to peel off, but has hot sealing layer residual on the formed body.
Difference (*) is not peeled off.
Above-mentioned evaluation result is summarized in table 3.
Utilizability on the industry
When using label for in-mold molding of the present invention, can easily make label to the stickiness of formed body and remove all in-molded bodies of excellent tape label of label. In addition, the in-molded body of tape label of the present invention can be made container of cold drink, wine, soy sauce, oil, washing agent etc. and utilize in many aspects, and its range of application is extremely wide. And after the use, label separates easily with container, and recycling property is excellent, so demand is also very large.
Claims (21)
1, a kind of in-molded body (E) of tape label, it is to have the in-molded in-molded body (E) of using the tape label of label (C) on formed body (D), describedly in-moldedly comprise basic unit (A) and hot sealing layer (B) with label (C), thermoplastic resin is contained in described basic unit (A), and described hot sealing layer (B) contains the heat sealing resin of 30 weight %～99 weight % and the water-soluble binder of 70 weight %～1 weight %; Wherein, even the in-molded body (E) of described tape label was soaked 4 days in 40 ℃ water, in-moldedly do not peel off with label (C) and formed body (D) yet.
2, the in-molded body (E) of tape label as claimed in claim 1, wherein, described in-moldedly have the basic unit (A) that contains thermoplastic resin, the hot sealing layer (B) that contains heat sealing resin and water-soluble binder and printed layers (F) successively with label (C), and the printing area of described printed layers (F) is 1%～90% of a label integral body.
3, the in-molded body (E) of tape label as claimed in claim 2, wherein, the printing area of described printed layers (F) is 5%～80% of a label integral body.
4, as the in-molded body (E) of each described tape label of claim 1～3, wherein, the in-molded body (E) of tape label soaked 15 minutes in 80 ℃ 1.5 weight % sodium hydrate aqueous solutions after, in-moldedly peel off from formed body (D), and do not have hot sealing layer (B) residual on the formed body (D) with label (C).
5, as the in-molded body (E) of each described tape label of claim 1～3, wherein, described water-soluble binder is the cationic water-soluble binder.
6, as the in-molded body (E) of each described tape label of claim 1～3, wherein, described hot sealing layer (B) is to be coated in the basic unit (A) and to carry out drying by the water paint that will contain heat sealing resin and water-soluble binder to form.
7, as the in-molded body (E) of each described tape label of claim 1～3, wherein, the fusing point that described hot sealing layer (B) contains 30 weight %～99 weight % is 50 ℃～120 ℃ thermoplastic resin and the water-soluble binder of 70 weight %～1 weight %.
8, as the in-molded body (E) of each described tape label of claim 1～3, wherein, the density of described basic unit (A) is 0.40g/cm
3～0.98g/cm
3
9, as the in-molded body (E) of each described tape label of claim 1～3, wherein, the thermoplastic resin in the described basic unit (A) is a polyolefin.
10, as the in-molded body (E) of each described tape label of claim 1～3, wherein, described formed body (D) be by be selected from by injection moulding, directly the forming method in the group formed of blow molding, injection blow molding, stretch blow molding, thermoforming and compression forming carries out moulding and obtains.
11, as the in-molded body (E) of each described tape label of claim 1～3, wherein, described formed body (D) is made of the material that is selected from the group of being made up of polyethylene, polypropylene, polyvinyl chloride, PET, polybutylene terephthalate, PEN, polyamide, Merlon and polystyrene.
12, a kind of in-molded with label (C), it comprises basic unit (A) and hot sealing layer (B), thermoplastic resin is contained in described basic unit (A), and described hot sealing layer (B) contains the heat sealing resin of 30 weight %～99 weight % and the water-soluble binder of 70 weight %～1 weight %; Wherein, even will in 40 ℃ water, soak 4 days, in-moldedly do not peel off with label (C) and formed body (D) by the in-molded body (E) that on formed body (D), has the described in-molded tape label that forms with label (C) yet.
13, as claimed in claim 12 in-molded with label (C), it is have the basic unit (A) that contains thermoplastic resin, the hot sealing layer (B) that contains heat sealing resin and water-soluble binder and printed layers (F) successively in-molded with label (C), and the printing area of wherein said printed layers (F) is 1%～90% of a label integral body.
14, as claimed in claim 13 in-molded with label (C), wherein, the printing area of printed layers (F) is 5%～80% of a label integral body.
15, as each described in-molded label (C) of using of claim 12～14, wherein, the in-molded body (E) of tape label soaked 15 minutes in 80 ℃ 1.5 weight % sodium hydrate aqueous solutions after, in-moldedly peel off from formed body (D), and do not have hot sealing layer (B) residual on the formed body (D) with label (C).
16, as each described in-molded label (C) of using of claim 12～14, wherein, the fusing point that described hot sealing layer (B) contains 30 weight %～99 weight % is 50 ℃～120 ℃ thermoplastic resin and the water-soluble binder of 70 weight %～1 weight %.
17, as each described in-molded label (C) of using of claim 12～14, wherein, described water-soluble binder is the cationic water-soluble binder.
18, as each described in-molded label (C) of using of claim 12～14, wherein, the density of described basic unit (A) is 0.40g/cm
3～0.98g/cm
3
19, as each described in-molded label (C) of using of claim 12～14, wherein, the thermoplastic resin in the described basic unit (A) is a polyolefin.
20, as each described in-molded usefulness label (C) of claim 12～14, wherein, described hot sealing layer (B) forms by water paint being coated in the basic unit (A) and carrying out drying.
21, as each described in-molded label (C) of using of claim 12～14, wherein, described formed body (D) is made of the material that is selected from the group of being made up of polyethylene, polypropylene, polyvinyl chloride, PET, polybutylene terephthalate, PEN, polyamide and polystyrene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004334963 | 2004-11-18 | ||
| JP334964/2004 | 2004-11-18 | ||
| JP334963/2004 | 2004-11-18 |
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| CN101084101A CN101084101A (en) | 2007-12-05 |
| CN100564002C true CN100564002C (en) | 2009-12-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102264606B (en) * | 2008-12-26 | 2013-03-13 | 优泊公司 | Container with label and production method therefor |
| MX2015013606A (en) * | 2013-03-28 | 2016-01-12 | Seiren Co Ltd | Decorative film for insert molding and decorative insert molded item. |
| CN103521278B (en) | 2013-10-18 | 2015-06-17 | 杭州百伴生物技术有限公司 | Biological sample storage pipe with identification code and manufacturing method thereof |
| CN105415904A (en) * | 2015-11-05 | 2016-03-23 | 广东金冠科技股份有限公司 | Printing production method capable of printable electrostatic adhesive film |
| BR112019020161B1 (en) * | 2017-03-31 | 2023-01-10 | Yupo Corporation | MOLD MOLDING LABEL, AND, LABELING ARTICLE MOLDED IN RESIN |
| CN107301817A (en) * | 2017-07-20 | 2017-10-27 | 粤港（广州）智能印刷有限公司 | In-mold labels |
| CN110998699A (en) * | 2017-08-21 | 2020-04-10 | 琳得科株式会社 | Peeling detection label |
| DE102019217560A1 (en) * | 2019-11-14 | 2021-05-20 | Loparex Germany Gmbh & Co. Kg | Transfer film for transferring coating materials to components |
| CN112677670B (en) * | 2020-12-17 | 2022-07-29 | 合肥菲力姆科技有限公司 | Waterproof thermosensitive film and preparation method thereof |
| CN113881106B (en) * | 2021-11-17 | 2023-05-23 | 广州市欣竹不干胶材料有限公司 | Environment-friendly degradable self-adhesive paper and preparation method thereof |
| CN114347605A (en) * | 2021-12-13 | 2022-04-15 | 安徽维龙新材料科技有限公司 | Multilayer co-extrusion BOPP (biaxially-oriented polypropylene) film with ultrahigh heat sealing strength and preparation method thereof |
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