CN100559427C - In-mold labels with removable part - Google Patents
In-mold labels with removable part Download PDFInfo
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- CN100559427C CN100559427C CNB2003801006490A CN200380100649A CN100559427C CN 100559427 C CN100559427 C CN 100559427C CN B2003801006490 A CNB2003801006490 A CN B2003801006490A CN 200380100649 A CN200380100649 A CN 200380100649A CN 100559427 C CN100559427 C CN 100559427C
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Abstract
The present invention relates to a kind of in-mold labels, it comprises thermoplastic resin membrane's basalis and heat sealing resin layer, wherein the wettable index of this thermoplastic resin membrane's basalis surface and/or this heat sealing resin laminar surface is 34mN/m to 73mN/m, this label comprises label body and removable part, between this label body and this removable part, provide lacerable perforation, and, when adhering to this container when this label is made the process of thermoplastic resin container in mould in, the adhesion strength between removable part and container is 80gf/10mm to 270gf/10mm.This in-mold labels can two-sidedly be printed, and during transportation and using labelled container, the removable part of described label does not unclamp from container.This removable part can easily be torn from container, and can not break.
Description
Technical field
The present invention relates to have the in-mold labels of removable part, it adheres to this container when making thermoplastic resin container, and described thermoplastic resin container is through the pattern manufacturing of differential pressure forming or blow molding.
Background technology
Known that some are used in the in-mold labels in the technology in the mould, in these moulds in the technology, in advance label is placed in the mould, in this mould, introduce thermoplastic resin then, and mould with injection moulding, blow molding, differential pressure forming or foam-formed pattern and to make container, and simultaneously described label is adhered to the container (referring to JP-A 58-69015 and EP-A 254,923) of manufacturing.
As an example of this type of label, the in-mold labels (referring to JP-A 6-51701,6-95593,6-308886) with separable complimentary ticket (coupon ticket) or similar portions is proposed.Proposed certain methods and designed this label with removable part so that buy back the buyer of the product of labelling can be easily from the label removable part of tearing.For example, by tearing removable part along perforation and itself and label body being separated, the amount of bonding agent reduces (referring to USP 5,172,936) on the removable part back side in addition, or not at the removable part applied adhesives.
But there is a shortcoming in the label with this removable part, that is, removable part is easy to unclamp from the surface of the container of labelling.For example, when the plastic holding device of labelling and filling content in transportation or be placed on the display rack and when being subjected to certain impact that is applied thereto, maybe when giving the plastic holding device certain load when extruding content, described removable part can easily unclamp from this labelled container because of impact or the load that is applied thereto.On the other hand, if give the bonding agent that this part is crossed volume for preventing that removable part from unclamping, may cause another problem so, promptly, although can itself and label body be separated by tearing removable part perforation on every side, but this part may not successfully be torn along perforation, and therefore separates with label body unsatisfactorily.
When described removable part was used as complimentary ticket, it was bonded in the back side of container may not only to need to print the surperficial of removable part but also needs printing.But, when surface activation process is stood so that abundant when compatible and when when printing ink print with seal China ink in the back side, removable part and the adhesiveness between container of having labelled can reduce greatly and therefore a problem occur, that is, removable part easily unclamps from the surface of the container of labelling.
Summary of the invention
We specialize in as inventor of the present invention, be devoted to provide a kind of in-mold labels that can two-sided printing, and its other advantage is: the removable part of this label does not unclamp from the surface of this container in transportation and during using labelled container; Removable part is easy to tear from labelled container; And removable part damages and also can not break tearing Shi Buhui.We find as a result, and when the adhesion strength between the plastic holding device of the wettable exponential sum removable part of label surface to be printed and label all was limited in the particular range, the problems referred to above can be solved.
Particularly, the invention provides the in-mold labels of a kind of thermoplastic resin membrane's of comprising basalis and heat sealing resin layer, the wettable index that it is characterized by this thermoplastic resin membrane's basalis surface and/or this heat sealing resin laminar surface is 34mN/m to 73mN/m, this label comprises label body and removable part, between this label body and this removable part, provide lacerable perforation, and when adhering to this container when this label is made thermoplastic resin container in mould during, the adhesion strength between removable part and container is 80gf/10mm to 270gf/10mm.
In in-mold labels of the present invention, need described removable part to have the part extracted and on 55% to 80% area of the heat sealing resin laminar surface of removable part, use lubricant.The length that equally preferably constitutes the slit of perforation is 4mm to 10mm, and the distance between adjacent slits is 0.3mm to 0.6mm.Equally preferably, the thermoplastic resin membrane's basalis surface and/or the heat sealing resin laminar surface of in-mold labels of the present invention stand activation processing, and coating antistatic layer or print thereon.
The present invention also provides the container that is stained with described in-mold labels.
In in-mold labels of the present invention, the adhesion strength between removable part and container is controlled in the scope of 80gf/10mm to 270gf/10mm.The problem that the described container that is stained with this label does not have removable part to unclamp, even and after pushing 10 times, still have good surface appearance, and removable part can easily be torn with have gentle hands.
Description of drawings
Fig. 1 shows the structure of in-mold labels of the present invention.Wherein, 1 is in-mold labels; 2 is removable part; 3 is label body; 4 for extracting part; 5 is container.
Fig. 2 is for showing the view of the container that is stained with embodiment 1 label.
Embodiment
Hereinafter describe in-mold labels of the present invention in detail.In this explanation, be scope between previous numerical value and a back numerical value by the meaning of " numerical value is to another numerical value " represented numerical range, the lower limit that previous numerical value is indicated this a scope then numerical value is indicated its upper limit.
＜label construction 〉
In-mold labels with removable part of the present invention mainly comprises thermoplastic resin membrane's basalis and heat sealing resin layer, and this heat sealing resin layer is formed at a side of waiting to adhere to basalis of container.This basalis surface is printed with various information, comprises coupon information, and this label has removable part, and this removable part can be torn from label body along the perforation that is formed at around this part.For ease of the removable part of tearing, the lubricant reagent of adhesion (reduce) is applied to the heat sealing resin laminar surface of removable part, and the adhesion strength of regulating removable part is in the proper range.In addition, can form on an edge of removable part at least and extract part, the amount of wherein regulating the lubricant of this extraction part makes it be higher than the remainder of removable part.
Fig. 1 shows the specific embodiment of in-mold labels of the present invention.In the figure, 2 is removable part; 3 is label body; 4 for extracting part.When mentioning this extraction part 4 with finger or other similar fashion and when direction of arrow b spurs, removable part 4 is promptly peeled off and is torn along described perforation from the container of labelling, and this removable part 4 can separate with container and label body 3 fully thus.About the structure of removable part 2 and label body 3 and the specifically qualification of details of extracting the shape of part 4, and can have various embodiment, for example, (1) is to (4) among Fig. 1.
For example, the material of formation thermoplastic resin membrane basalis can be the film of following resin: propylene resin; Polyvinyl resin, for example high density polyethylene, intermediate density tygon; Other polyolefin resin, for example poly-Methyl-1-pentene, ethene-cyclic olefine copolymer; Pet resin; Polyvinyl chloride resin; Polyamide, for example nylon-6, nylon-6,6, nylon-6,10, nylon-6,12; ABS resin; Ionomer resin or analog.In these resins one or more can be used for the present invention alone or in combination.
In the above-mentioned resin, preferably has the thermoplastic resin of fusing point between 130 ℃ and 280 ℃, for example propylene resin, high density polyethylene and pet resin.More preferably its fusing point is than the resin of at least 15 ℃ of the thermoplastic resin fusing point height that constitutes heat sealing resin layer (will be described below).In satisfying the resin of this requirement, propylene resin especially becomes first-selection because of factors such as its chemical resistance, costs.Described propylene resin comprises: have the stereospecific Noblen of isotaxy or syndiotaxy; And propylene and alpha-olefin (such as, ethene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene) multipolymer.This multipolymer can be binary, ternary or quadripolymer, and also can be random copolymers or segmented copolymer.
Can suitably inorganic fine powder or organic fine powder be added into above-mentioned thermoplastic resin.
The kind of inorganic fine powder and organic fine powder does not limit especially.The example of inorganic fine powder is ground chalk, precipitated calcium carbonate, calcined clay, talcum, barium sulphate, zeyssatite, magnesium oxide, zinc paste, titanium dioxide, silicon dioxide.Wherein, be preferably ground chalk, calcined clay and talcum, because these materials are cheap and can guarantee good plasticity.
In order to form micropore by it, this organic fine powder is preferably incompatible with the thermoplastic resin of described basalis and have the fusing point that is higher than this thermoplastic resin or a resin of glass transition point.The example of this organic fine powder comprises: polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, poly-naphthalene first diacid second diester, polystyrene, acrylate or methacrylate polymers and multipolymer, melamine resin, poly-ethylene sulfite, polyimide, polytrimethylene ether ketone, polyphenylene sulfide, cycloolefin homopolymers and cycloolefin-ethylene copolymer (COC).Particularly, when polyolefin resin was used as above-mentioned thermoplastic resin, this stand-by organic fine powder was preferred: polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, poly-naphthalene diacid second diester, polystyrene, cycloolefin homopolymers and cycloolefin-ethylene copolymer (COC).
Can be used alone the fine powder of type among the present invention, maybe can select and be used in combination two or more fine powder.When selecting, making up and using two or more fine powder, use inorganic fine powder capable of being combined and organic fine powder.
Can add any spreading agent, antioxidant, compatilizer, UV stabilizing agent, detackifier and similar reagents thereof in addition in case of necessity to this resin.
Described thermoplastic resin membrane's basalis can be single or multiple lift.When it has sandwich construction, can comprise core layer and superficial layer and bottom, this superficial layer and bottom are positioned at the two sides of this core layer.Wherein, each layer can be formed by identical thermoplastic resin, or can be formed by different thermoplastic resins.In the time of in inorganic or organic fine powder being added to these layers, type of being added and amount can be identical or different.
The film of described formation thermoplastic resin membrane basalis preferably stretches at least in one direction.When thermoplastic resin membrane's basalis has sandwich construction, need the one deck at least in this structure of stretching.When the stretched multi-layer structural sheet, can before its lamination, stretch respectively, or can carry out lamination stretching as a whole subsequently earlier.In case of necessity, the gained laminated material that behind lamination drawn layer, can stretch once more.In addition, after forming the heat sealing resin layer on thermoplastic resin membrane's basalis, resulting structures can be stretched as a whole.
Can adopt the whole bag of tricks this film that stretches.Preferably to utilize the pattern oriented film of different rolling type (roll-to-roll) pulling method of circumferential speed between running roller.According to this method, the draw ratio in the stretching can any required mode be regulated.In addition because resin be oriented to the drawn film vertically, so the tensile strength of the label that is formed by this drawn film is higher than unstretched film, and the change in size that causes because of the tension force that is applied thereto during printing is less.About draft temperature, when using noncrystalline resin, can under the temperature of the glass transition point that is not less than used thermoplastic resin, stretch; And when using crystalline resins, can in the temperature range between between the fusing point of the glass transition point of its noncrystalline part and crystalline portion, stretch.
The preferred embodiment of thermoplastic resin membrane's basalis of the present invention is: by adding the film that the above-mentioned inorganic or organic fine powder of 8 weight % to 80 weight % is made in the above-mentioned thermoplastic resin; Through single shaft to or biaxial stretching and from the teeth outwards coating contain the film of latex of inorganic filler; Reach the film that is coated with aluminium in the mode of vapour deposition or lamination.
Wherein, preferred thermoplastic resin membrane's basalis is the resin film of poriness drawn, it comprises: a kind of core layer of biaxially drawn films of resin combination, this resin combination contain the inorganic fine powder of 5 weight % to 30 weight %, the high density polyethylene of 3 weight % to 20 weight % and the propylene resin of 92 weight % to 50 weight %; And the superficial layer and the bottom of the uniaxially-stretched film of another kind of resin combination, this superficial layer and bottom are positioned on the two sides of described core layer, and this resin combination contains the inorganic fine powder of 35 weight % to 65 weight %, the high density polyethylene of 0 to 10 weight % and the propylene resin of 55 weight % to 35 weight %.Such film has good printability and good anti-hot shortness.
The thickness of this thermoplastic resin membrane's basalis is preferably 20 μ m to 500 μ m, more preferably 30 μ m to 200 μ m.If thickness is less than 20 μ m, the so used device of labelling automatically can not be wrinkling in the regular stationkeeping label or the label possibility of mold.On the other hand, if thickness greater than 500 μ m, make in the mould so the intensity of the boundary member between resin article and label may be lower and also dropping impact strength this resin article may be lower.
Do not limit especially about the resinous type that constitutes the heat sealing resin layer, because it can be any resin with following function: can adhere to because of the heat that is produced in the technology in the mould of making the label container on the resin material that constitutes this container.The preferred embodiment of this resin is the polyethylene resin of fusing point between 80 ℃ and 130 ℃, and comprises: density is 0.900g/cm
3To 0.935g/cm
3Low-density or the high-pressure process tygon of intermediate density; Density is 0.880g/cm
3To 0.940g/cm
3The linear pattern tygon; Ethylene, ethylene/acrylic acid copolymer, ethylene/acrylic acid alkyl ester copolymer, ethylene/methacrylic acid alkyl ester copolymer (wherein alkyl has 1 to 8 carbon atom), and metal (for example Zn, Al, Li, K, the Na) salt of ethylene/methacrylic acid.
Wherein, more preferably high-pressure process tygon and linear pattern tygon, these tygon have above-mentioned density and have 10% to 60% crystallinity (according to x-ray method) and 10,000 to 40,000 number-average molecular weight.Especially with regard to the adhesion of itself and resin article, linear pattern tygon the best, it obtains by following steps: at metallocene catalyst (particularly, disclosed metallocene-alumoxane catalyst in international publication number WO92/01723 for example, or comprise metallocene compound and can form the catalyzer of stablizing anionic compound with the metallocene compound reaction) there are down the ethene of copolymerization 40 weight % to 98 weight % and the alpha-olefin of 60 weight % to 2 weight % with 3 to 30 carbon atoms.Can be used alone or in combination at these one or more these type of polyolefin resins.
Described heat sealing resin layer can contain any known resin additive, only otherwise damage the necessary characteristic of this heat sealing resin layer.Affiliated adjuvant comprises dyestuff, nucleator, plastifier, lubricant, antioxidant, detackifier, fire retardant, UV absorbing agent or the like.
The heat sealing resin layer can followingly form: heat sealing resin film that will be for this purpose on described basalis lamination to form required heat sealing resin layer thereon.With the emulsion of heat sealing resin or be dissolved in the solvent such as toluene or ethyl cellosolve prepared resin solution by heat sealing resin and be administered on the basalis and then dry thereon to form required heat sealing resin layer.
The thickness of described heat sealing resin layer is preferably 1 μ m to 100 μ m, more preferably 2 μ m to 20 μ m.This heat sealing resin layer must pass through tygon fusion, polythylene resin fusion or as the heat of the analog fusion of the parison that forms container and fusion, thereby makes the label melting in the plastic holding device of setting.For this reason, the thickness of heat sealing resin layer is preferably at least 1 μ m.On the other hand, when the thickness of this layer during greater than 100 μ m, to such an extent as to label will curl and difficultly reach lithography on label, in addition, label will be difficult to be fixed in the mold.
For guaranteeing the good printability of thermoplastic resin membrane's basalis and/or heat sealing resin layer, the wettable index on surface is adjusted between 34mN/m and the 73mN/m, be preferably between 38mN/m and the 70mN/m.China ink can not adhere well to the surface and the seal China ink can come off easily if the wettable index less than 34mN/m, prints so.If but this index is higher than 73mN/m, its two sides will cause adhesion when rolling film so.Wettable index mentioned in this article is the value of being measured according to JIS K-6768.
Thermoplastic resin membrane's basalis surface and/or heat sealing resin laminar surface can activate by known activating treatment method (for example Corona discharge Treatment or flame plasma are handled), and in case of necessity, can on described surface, form antistatic layer (hereinafter will mention), thereby the wettable index that can further regulate described surface thus improves the printability and the anti characteristic on surface.
After this thermoplastic resin membrane's basalis surface and/or this heat sealing resin laminar surface stand above-mentioned activation processing, can be coated with antistatic layer.This antistatic layer improves the movability of paper in printing machine, especially prevent paper during the offset printing double import into and in the transmission district of printing machine paper confuse and variety of issue such as pile up.
In the present invention, can form antistatic layer by following steps: have the aqueous solution that the independent following component (a) of antistatic behaviour or itself and following component (b) reach the potpourri that (c) (is adhesiveness to printing China ink) to the surface applied of above-mentioned layer; Dry thereon subsequently.
Component (a):
Acrylate copolymer 100 weight portions that contain uncle's nitrogen or quaternary nitrogen
Component (b):
Poly-group with imine moiety 0 to 300 weight portion
Component (c):
Polyamine polyamide-epichlorohydrin adducts 0 to 300 weight portion
In the component (a) contain uncle's nitrogen or quaternary nitrogen acrylate copolymer can be by the following monomer of copolymerization (i), (ii) reach (iii) and obtain:
Component (i):
At least a monomer that is selected from general formula as follows (I) to the compound of (VII)
4 weight % to 94 weight %
Component is (ii):
(methyl) acrylate 6 weight % to 80 weight %
Component is (iii):
Other hydrophobicity vinyl monomer 0 to 20 weight %
In formula (I) in (VII), R
1Expression hydrogen atom or methyl; R
2With R
3The alkyl (preferably have 1 to 4 carbon atom, more preferably have 1 or 2 carbon atom) of representing low carbon number separately; R
4Expression has the saturated or unsaturated alkyl or the naphthenic base of 1 to 22 carbon atom; X
-Expression and quaternary ammonium N
+The negative ion of balance (for example halogenide, especially chloride); M represents alkali metal ion (for example sodium, potassium); A represents to have the alkylene of 2 to 6 carbon atoms.In these monomers, preferred component (i) is the compound of formula (VI).
Compound (ii) in (methyl) acrylate represent by following general formula (VIII):
R wherein
1Expression hydrogen atom or methyl; R
5Expression has alkyl, alkylene or the naphthenic base of 1 to 24 carbon atom.Particularly, this compound comprises butyl acrylate, 2-ethyl hexyl acrylate and methacrylic acid stearyl or the like.
The example of component other hydrophobicity vinyl monomer (iii) is styrene and vinyl chloride.
For the aforesaid acrylate copolymer that contains uncle's nitrogen or quaternary nitrogen of component (a), especially preferred anlistatig water-soluble polymers, it comprises the monomer of the monomer of formula (VI) as component (i), wherein X
-Be Cl
-Such polymkeric substance can be buied from Mitsubishi chemical Co., Ltd, and commodity are called Saftomer ST-1000, Saftomer ST-1100, Saftomer ST-1300 and SaftomerST-3200.
Poly-group with imine moiety in the component (b) is the priming paint that is used to improve the adhesion of described layer.For example, it comprises that this poly-group with imine moiety is selected from the group of being made up of following material by the represented poly-group with imine moiety of following general formula (IX): the degree of polymerization is 200 to 3,000 polyethyleneimine; Polyamine polyamide-aziridine adduct; And through alkyl-modified, through the thiazolinyl modification, through the benzyl modification or through the derivant of aliphatic cyclic hydrocarbon modification, these derivants are by as modifier its modification being generated with halogenide (halogenated alkane, alkenyl halide, halo naphthenic hydrocarbon, benzyl halogenide or the similar halogenide that for example have 1 to 24 carbon atom); And poly-(aziridine-urea).Described poly-group with imine moiety has a detailed description in JP-B 2-2910 and JP-A 1-141736.
Wherein Z represent a group or-NH-R
9, or polyamine-polyamide residue; R
6To R
9Represent hydrogen atom independently of one another or have alkyl, thiazolinyl, naphthenic base or the benzyl of 1 to 24 carbon atom, but wherein at least one is the group beyond the dehydrogenation; M represents 0 to 300; And n, p and q represent 1 to 300 numeral independently of one another.
Polyamine polyamide-epichlorohydrin adducts also is the priming paint that is used to improve described layer adhesion.It comprises water-soluble cationic thermosetting resin, and this resin generates by polyamide and chloropropylene oxide reaction, and polyamide is to be made by saturated dicarboxylic acid and polyolefin-polyamine with 3 to 10 carbon atoms.These thermoset resins have a detailed description in JP-B 35-3547.Example with saturated dicarboxylic acid of 3 to 10 carbon atoms is dicarboxylic acid, the especially hexane diacid with 4 to 8 carbon atoms.
The example of polyolefin-polyamine is tygon-polyamine, especially ethylenediamine, diethylene triamine, trien, more especially diethylene triamine.
Except that these components, described layer can contain any other complementary material in addition when needing, for example, water-soluble inorganic compound is such as sodium carbonate, sodium sulphate, sodium sulphite, sodium thiosulfate, baryta hydrate, sodium metasilicate, sodium pyrophosphate, sodium tripolyphosphate, sodium dihydrogen phosphate, potassium alum, ammonia-alum; Water-soluble organic compounds is such as ethanol, isopropyl alcohol; Surfactant; Ethylene glycol; And water-soluble polymers, such as polyvinyl alcohol (PVA).
Described component (a) and (b) reach and (c) can be used as its aqueous solution use, and the total solid concentration of this solution is generally 0.1 weight % to 10 weight %, is preferably 0.1 weight % to 5 weight %.With its solid content meter, the dry-coated amount of described layer generally can be 0.005g/m
2To 2g/m
2, preferred 0.02g/m
2To 1g/m
2For example,, can adopt any common coating process, as pressing mold coating, bar type coating, running roller coating, scraper coating, airblade coating, size press coating or spraying process for the coating said composition.These methods of use capable of being combined in case of necessity.This coat can be dry under the temperature between room temperature and 100 ℃, and obtain the antistatic layer that thickness is 0.005 μ m to 2 μ m.
Described component (a) and (b) and blend ratio (c) can be as follows: when the amount of nitrogenous acryl resin (a) is 100 weight portions, the amount of poly-group with imine moiety (b) is 0 to 300 weight portion, be preferably 0 to 200 weight portion, and the amount of polyamine polyamide-epichlorohydrin adducts (c) is 0 to 300 weight portion, is preferably 0 to 200 weight portion.Owing to be coated with the composition antistatic layer, make thermoplastic resin membrane's basalis surface and/or heat sealing resin laminar surface be difficult to static, and obtain paper movability good in printing machine thus.
Measured according to JIS K-6911, the surface resistivity of this thermoplastic resin membrane's basalis surface and/or this heat sealing resin laminar surface is preferably about 10
9To 10
15The order of magnitude, more preferably 10
9To 10
12The order of magnitude.
Thermoplastic resin membrane's basalis surface and/or heat sealing resin laminar surface among the present invention can be printed various information, for example, and name of product, characteristic, bar code, manufacturer's title, dealer's title, operation instruction, complimentary ticket, lottery ticket or the like.For carrying out described printing from the teeth outwards, can adopt the whole bag of tricks, for example intaglio printing, lithography, letterpress, flexographic printing, serigraphy or similar approach.When printing on the heat sealing resin layer, Yin Mo or varnish can be used as lubricant, as described below.In addition, the mode coating metal (for example aluminium) that thermoplastic resin membrane's basalis surface can vapour deposition maybe can carry out hot padding, or can lamination or the mode that applies of varnish be coated with external protection.
Can at least one edge of removable part, form a wide 3mm to 10mm, and the extraction part of preferred 5mm to 8mm (Fig. 1, a).If the width that extracts part is less than 3mm, this part will can not cause peeling off of removable part and be difficult to portable so; If but greater than 10mm, so this extraction part may in mould, roll after the production technology and the outward appearance of manufacturing container with variation.In addition, when forming groove in the edge that is extracting between part and container, can more easily peel off described removable part.
In-mold labels of the present invention is characterised in that, even filling content or in transportation or be put on the showing stand or when the impact that is applied thereto during actual use the or load, removable part can not unclamp from the surface of the container of labelling yet when container; And be, can specifically regulate between removable part and plastic holding device adhesion strength so that this removable part can easily peel off from container, particularly the concrete scope of this adhesion strength is 80gf/10mm to 270gf/10mm, preferred 100gf/10mm to 250gf/10mm, more preferably 120gf/10mm to 240gf/10mm.If cohesive strength, will cause the problem that removable part may unclamp from the surface of the container of labelling so less than 80gf/10mm.On the contrary, if cohesive strength greater than 270gf/10mm, removable part will be difficult to peel off from labelled container so.
Can regulate adhesion strength by surface applied lubricant to the heat sealing resin layer of removable part.A kind of with adhesion strength be adjusted to method for optimizing in the above-mentioned scope be included in contact between removable part and container 55% to 80%, be preferably on 60% to 75% the area and use lubricant.If the area of using of lubricant exceeds 55% to 80% scope, the adhesion strength between removable part and plastic holding device may be difficult to be controlled in the above-mentioned particular range so.The amount of extracting part lubricant to be administered be preferably this extraction part area more than 80% to 95%, more preferably more than 80% to 90%.
For this lubricant, can use various seal China inks and varnish.The example of these printing ink is planographic ink, UV planographic ink, base gravure ink, silk-screen ink, flexographic ink, UV flexographic ink or the like, and wherein any can be used for the present invention.In addition, for example contain the demoulding varnish of silicones, the demoulding varnish and the wax of fluorochemicals also can be used for the present invention.The not concrete method of using lubricant that limits.Generally speaking, the coating that available letterpress, lithography, intaglio printing, flexographic printing, serigraphy or similar mode of printing are reached lubricant.
Can measure the degree that removable part unclamps from labelled container according to the test of pushing the plastic holding device of having labelled.Squeeze test among the present invention is to test according to following container deformation to reach, and its assumed conditions is: this plastic holding device of having labelled uses in normal way.
The in-mold labels of printing through single or double is carried out die-cut to obtain having for adhering to the label of plastic holding device required form and size.During the die-cut operation or before, need form perforation on every side the removable part through printing (extract part except) and be beneficial to peeling off of this part.Can form perforation by using hot pin, electron beam, laser beam or similar fashion, and can be designed so that constitute the slit length be 4mm to 10mm, preferred 5mm to 8mm, and the distance between adjacent slits is 0.3mm to 0.6mm, preferred 0.3mm to 0.5mm.The meaning of the gap length that this paper is mentioned is to pass the length that hole forms the slit in the vertical.If it is too short to constitute the gap length of these perforation, if or the distance between adjacent slits oversize, removable part will be difficult to peel off along perforation so.On the contrary, if if the distance that constitutes between the oversize or adjacent slits of the gap length of these perforation is too short, can cause the problem that removable part will fold or damage when the operation label so.
When the heat sealing resin aspect from in-mold labels forms perforation towards the front through printing, slit wall on the heat sealing resin aspect can be level and smooth, and therefore the slit outer wall section of these perforation is not cut during the technology in mould in the outer wall of container, and makes removable part easily to peel off thus.
In-mold labels of the present invention is fit to differential pressure forming (for example vacuum forming or pressure forming) or blow molding in die cavity, wherein under pressure, a parison is depressed into the mold inwall, its mode is: the contacting with the wall of mold of the basalis of in-mold labels through printing face, and the suction by mold is fixed in the mold inwall with label subsequently.Then, molten material of film or the parison that forms the resin material of container imported this mold and then moulding in normal way, and then form the complete container that is melted on its outer wall of a label.
In this mode, after label is fixed in the mold, label is combined to obtain desired labelled container with plastic holding device to be formed.Therefore, so any bad label distortion can not take place in the labelled container of gained, and the adhesion strength between this container body and label is higher.In addition, this labelled container does not have blister, and has the good appearance of ornamental label.When spurring when the extraction part of mentioning the label removable part with finger and with it, this removable part can easily be peeled off along perforation from container.
Being used for the described type of the thermoplastic resin material of label container for the treatment of does not specifically limit.The preferred embodiment of this resin material is the thermoplastic resin identical with the in-mold labels type, for example propylene resin, tygon (especially preferred high density polyethylene), Polyvinylchloride, polyethylene terephthalate, polyamide.The type that is used for the thermoplastic resin of this container can suitably be selected according to purposes, purpose, environment for use and service condition that desire is made the mould inner pressurd vessel.
With reference to following examples and comparative example feature of the present invention is described more specifically.Under the situation that does not surmount spirit of the present invention and scope, similar factor such as used material, amount, blend ratio, processing mode, technology can any required mode change in following examples.Therefore, provide following examples and being not intended to limit the scope of the invention.
(embodiment 1)
The preparation of＜heat sealing resin material 〉
The preparation of＜ethylene/alpha-olefin copolymer 〉
The method that is disclosed according to JP-A 61-130314 prepares catalyzer.Particularly, in 2.0mmol ethylidene-two (4,5,6, the 7-tetrahydro indenyl) zirconium dichloride compound, add MAO (available from Toyo Stofer) with respect to 1,000 mole of multiple of this compound.With toluene it is diluted to 10 liters, and makes catalyst solution thus.Use this solution, followingly carry out polymerization: the potpourri of ethene and 1-hexene is sent in the agitated autoclave type flow reactor of 1.5 liters of capacity, the content of 1-hexene is 80 weight % in the wherein said potpourri.Pressure in the reactor remains on 1,600kg/cm
2, temperature of reaction is 160 ℃.
After the reaction, obtain ethylene/alpha-olefin copolymer (1-hexene content is 22 weight %), its MFR is 18g/10min, and density is 0.898g/cm
3And the Q value is 1.9.A peak is arranged in the TREF of this polymkeric substance elution curve, and the peak temperature is 50 ℃.The H/W of this peak temperature is 1.5.Its total elution amount is 3.0% and be 100% during at 80 ℃ when being 2.1%, 20 ℃ in the time of 10 ℃.
The preparation of＜high-pressure process low density polyethylene 〉
Under 260 ℃ of temperature of reaction, reach 1 according to autoclave process, 500kg/cm
2Preparation high-pressure process low density polyethylene under the reaction pressure.This poly MFR is 4g/10min, and density is 0.92g/cm
3, ME is 2.4 and the Q value is 10.
The preparation of＜basalis 〉
To comprise 67 weight % polypropylene homopolymer (trade name Nippon Polychem, Novatec PPMA-8,164 ℃ of fusing points), 10 weight % high density polyethylene (trade name Nippon Polychem, Novatec HD HJ580,134 ℃ of fusing points) and the resin combination (A) of 23 weight % calcium carbonate powders (particle mean size 1.5 μ m) in extruder in 250 ℃ of following melt kneading, and be squeezed into film via mould.It is cooled to about 50 ℃.Under about 150 ℃, heat this film again, and by utilize between running roller the circumferential speed difference and with 4 times of its longitudinal stretchings.Obtain thus as core through uniaxially-stretched film.
On the other hand, to comprise 51.5 weight % Noblen (trade name Nippon Polychem, Novatec PP MA-3), 3.5 weight % high density polyethylene (trade name Nippon Polychem, Novatec HD HJ580), the resin combination (B) of 42 weight % calcium carbonate powders (particle mean size 1.5 μ m) and 3 weight % titanium dioxide powders (particle mean size 0.8 μ m) in different extruders in 240 ℃ of following melt kneading, and via mould push in the film mode and on the surface of above-mentioned uniaxially-stretched film (B/A) lamination to obtain the laminated material of superficial layer/core layer.
In addition, the different extruder of same use, to comprise 51.5 weight % Noblen (trade name Nippon Polychem respectively, Novatec PP MA-3), 3.5 weight % high density polyethylene (trade name Nippon Polychem, Novatec HD HJ580), the composition (c) of 42 weight % calcium carbonate powders (particle mean size 1.5 μ m) and 3 weight % titanium dioxide powders (particle mean size 0.8 μ m) and the resin combination (D) that comprises the above-mentioned high-pressure process low density polyethylene that is used for the heat sealing resin layer of the above-mentioned ethylene/alpha-olefin of 75 weight % (1-hexene) multipolymer and 25 weight % are respectively at 200 ℃ of following melt kneading, subsequently it is sent into and have altogether in the extrusion die, the described two kinds of compositions of lamination in this mould, and via this mould with film mode co-extrusion pressure, lamination said composition thus so that this heat sealing resin layer can through the back side of uniaxially-stretched film as outermost layer (B/A/C/D).Therefore, obtain four of superficial layer/core layer/bottom/heat sealing resin layer and press material layer by layer.
This four-level membrane is imported in the tentering dryer,, and use 7 times of stenter cross directional stretchs, subsequently in 164 ℃ of following thermal fixations (heat-set), be cooled to 55 ℃ afterwards, and ream its edge 155 ℃ of heating down.Subsequently, with 50W/m
2/ min is to its two-sided Corona discharge Treatment of carrying out.Then, the aqueous solution that will contain following (a) and (b) and composition (c) is applied to superficial layer one side of this film, and dry to form antistatic layer thereon.
(a) contain the acrylic ternary copolymer of quaternary nitrogen, it comprises with lower unit: 0.5 weight %
(b) through butyl modified polyethylene imines 0.3 weight %
(c) water-soluble polyamine-polyamide/epichlorohydrin adducts
(Japan PMC Corp's system, trade name WS-570) 0.5 weight %
(d) water surplus
The wettable index of this thermoplastic resin membrane's basalis (superficial layer) surface and this heat sealing resin laminar surface is measured by the ACCU DYNE TEST that uses diversification enterprise, and is respectively 70mN/m and 42mN/m.Xsect with the electron microscope observation film.The thickness of this four-level membrane (except the antistatic layer) is 100 μ m (B/A/C/D=30/40/25/5 μ m).The gross density of this lamination stretching resin film is 0.78g/cm
3
With the thin slice cutting machine will be thus five the pressing stretching resin film layer by layer (antistatic layer/B/A/C/D) cut into thin slice as half (kiku-half) size of the royal badge of Japan to be used for in-mold labels of gained.
＜print
Use offset press (Komori Corporation ' s Lithlon) and UV planographic ink (T﹠amp; KTOKA ' s Bestcure), print in surface one side of the in-mold labels thin slice of gained thus with 6000 slices/hour speed.UV lithographic plate four looks are thereon printed thing and are comprised name of product, manufacturer's title, dealer's title, characteristic, bar code and operation instruction or the like.The adhesiveness of every kind of printing ink is all better.
Using of＜lubricant 〉
In addition, use identical UV planographic ink, coupon information be printed on the heat sealing resin laminar surface at the back side of these thin slices (label), the area of printing corresponding to the area of its removable part.Then, use identical offset press again, the demoulding varnish (T﹠amp of silicones is added in printing on thin slice; K, TOKA, trade name, Yusei Hakuri OP Nisu).Area through printing-ink and varnish accounts for 75% of the removable part total area.Varnish is applied to and extracts 90% of part area.The adhesiveness of printing ink and varnish is better.
＜die-cut
Then, around removable part (except extracting partly), printing like this is bored a hole with the thin slice that is used for in-mold labels.Particularly, form the slit of 0.5mm, length 6.0mm at interval in the vertical.Subsequently, carry out the thin slice corresponding to a label separately die-cut to obtain the label of long 11cm, wide 9cm.Thereby prepare in-mold labels with removable part.The detailed structure of this in-mold labels as shown in Figure 2.
The preparation of＜the container of having labelled 〉
In-mold labels is fixed on half of lobe mould (split mold) that is used for blow molding, wherein its superficial layer one side can contact with mould under pull of vacuum, and follow under 220 ℃ high density polyethylene (Nippon Polychem trade name, Novatec HD HB330,134 ℃ of fusing points) melt extruded is gone in this mould to form parison.Close the lobe mould immediately, and apply 4.2kg/cm
2Pressure to this parison so that parison swell becomes container, this in-mold labels of heat fusing in mould simultaneously.After such moulding, cooling die is opened subsequently to obtain the blowing plastic holding device of capacity 1000ml.Fig. 2 shows gained thus labelled the front elevation and the viewgraph of cross-section of container.
In this blown container, the label trace is colour-fast, and label neither shrinks also non-foaming.In addition, the removable part of this label does not unclamp from container.
(embodiment 2)
Except that 60% area of removable part is used the lubricant, prepare a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 1.In this blown container, the label trace does not fade, and label neither shrinks also non-foaming.In addition, the removable part of this label does not unclamp from container.
(embodiment 3)
In the method for embodiment 1, aqueous solution is applied on the superficial layer of this film after, be applied to the back side of film with only containing the aqueous solution that 1.0 weight % contain the acrylic ternary copolymer (a) of quaternary nitrogen, thereby on the two sides of this film, form antistatic layer.The wettable index of the heat sealing resin laminar surface on the film back side is 50mN/m.Other is as shown in the embodiment 1, and can the mode identical with embodiment 1 makes a labelled plastic holding device of in-mold labels and with removable part.In the blown container that obtains like this, the label trace does not fade, and label neither shrinks also non-foaming.In addition, the removable part of this label does not unclamp from container.
(comparative example 1)
Except that 90% area of removable part is used the lubricant, make a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 1.
(comparative example 2)
Except that 50% area of removable part is used the lubricant, make a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 1.
(comparative example 3)
The labelled plastic holding device of in-mold labels and that has removable part according to the method manufacturing one of embodiment 1 described in the JP-A 6-308886.
(comparative example 4)
Divided by 10W/m
2The degree of/min is carried out outside the Corona discharge Treatment, makes a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 1.The surperficial wettable index of this thermoplastic resin membrane's basalis and this heat sealing resin layer is respectively 66mN/m and 32mN/m.
(comparative example 5)
Except that not carrying out Corona discharge Treatment, make a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 1.The surperficial wettable index of this thermoplastic resin membrane's basalis and this heat sealing resin layer is respectively 31mN/m and 30mN/m.
(comparative example 6)
Except that the end the hot sealing layer side is carried out Corona discharge Treatment, make a labelled plastic holding device of in-mold labels and with removable part in the mode identical with embodiment 3.The surperficial wettable index of this thermoplastic resin membrane's basalis and this heat sealing resin layer is respectively 70mN/m and 32mN/m.
(test case)
Test and estimate the thin slice that these are made, 100 characteristics according to following method in each embodiment and comparative example with in-mold labels and 20 labelled plastic holding devices of a removable part.The result provides in table 1.
＜estimate
(1) inserts performance
Use automated tag feeder (label inserter automatic equipment is available from the NR75W of Pentel) to be used for label is adhered to container, 100 labels are sent into continuously in the lobe mould of blow molding.During this period, check whether these labels exist the problem that any label is folding, label cuts off or label comes off, and estimate according to following standard.The result provides in table 1.
Zero: do not go wrong.
*: some problem that occur that label is folding, label cuts off, label slippage or label comes off.
(2) mensuration of adhesion strength
Cut the label adhesion section of this container of having labelled with cutter blade, and its removable part through the coating of demoulding varnish is cut into the wide band of 10mm.By force an end of the adhesion section of label is peeled off 10mm from container with hand.Be fixed in air chuck (air-chuck) portion of a tensile test machine (ShimadzuSeisakusho, Autograph AGS-5KND), and the other end is also fixing thereon in the same manner.Wherein, this label is peeled off from container with the haulage speed of 300mm/min and the direction of delaminate of 180 degree, and measures the adhesion strength between label and container.The result provides in table 1.
(3) extrusion performance
Prepare 20 and have removable part separately and through attaching the container of in-mold labels.This container remains under the condition that the interior pressure of container can freely discharge, and is with the side of continuous in the opposite direction 5 times or the 10 times squeeze receptacles of hand, approaching mutually with the inwall that causes these container both sides.Be the squeeze test of these containers.Behind extrusion operation, inspection tag determines whether its extexine is stripped from.The result provides in table 1.
In the foregoing description and comparative example, according to the outward appearance of following these samples of standard evaluation:
Zero: in all test containers, no label unclamps.
△: in the extraction part of the label of some container, find have label to unclamp, but do not have problems in actual use.
*: finding in the removable part of the label of some container has label obviously to unclamp, and these containers have no commercial value.
(4) stripping performance:
Prepare 20 containers that have removable part separately through the attaching in-mold labels.In fact the removable part of supposing this label can be stripped from, and peels off this removable part from container with hand.Be the disbonded test of removable part.
In this test, according to the rippability and the tearability of following standard evaluation removable part.The result provides in table 1.
＜rippability 〉
Zero: all can easily be peeled off.
*: not peelable.(the impaired and removable part of resin film basalis is peeled off unsatisfactorily in some containers.)
＜tearability 〉
Zero: in all these containers, removable part can be torn along perforation satisfactorily.
△: in some containers, removable part is damaged and tears unsatisfactorily when peeling off.
*: can not tear.(removable part is damaged when peeling off in some containers, and can not tear.)
(5) printing performance:
The mensuration of＜antistatic behaviour 〉
Use an isolation resistor, Toa Dempa Kogyo, DSM-8103 is according to JIS K-6911 its surface resistance of two-sided measurement at each label.The antistatic behaviour of this indicating label, i.e. its printability index.
＜paper movability 〉
Under above-mentioned printing condition, check the performance during these thin slices are printed continuously in printing machine.In addition, after with UV transmitter drying, check that also these thin slices are to determine whether its edge can be aimed in the transmission district of this printing machine.After tested, according to these thin slices of following standard evaluation:
Zero: thin slice is sent in the printing machine smoothly and is steadily moved therein, and its edge good alignment in transmitting the district.
*: when sending into, thin slice often goes wrong, and perhaps its edge can not be aimed in transmitting the district.
＜ink adhesion 〉
After with EV transmitter drying, the adhesiveness of test ink on these thin slices.Particularly, a viscosity paper tape Nichiban ' s Cellotape (trade name) is adhered to this printing thin slice and peel off, check the surface appearance of this thin slice.After tested, according to these thin slices of following standard evaluation:
Zero: printing ink can not be peeled off, and meets with material breaks at basalis described in some sample.
△: have certain resistance when peeling off paper tape, but nearly all printing ink is stripped from, and existing problems in actual use.
*: peel off all printing ink, and when peeling off paper tape, do not run into any resistance.
Claims (17)
1. in-mold labels, it comprises thermoplastic resin membrane's basalis and heat sealing resin layer, wherein the wettable index of this thermoplastic resin membrane's basalis surface and/or this heat sealing resin laminar surface is 34mN/m to 73mN/m, this label comprises label body and removable part, between this label body and this removable part, provide lacerable perforation, and when when this label is made the process of thermoplastic resin container in mould in, adhering to this container, adhesion strength between removable part and container is 80gf/10mm to 270gf/10mm, wherein uses lubricant on 55% to 80% surface area of the heat sealing resin layer of described removable part; And wherein said thermoplastic resin membrane's basalis comprises: a kind of core layer of biaxially drawn films of resin combination, this resin combination contain the inorganic fine powder of 5 weight % to 30 weight %, the high density polyethylene of 3 weight % to 20 weight % and the propylene resin of 92 weight % to 50 weight %; And the superficial layer and the bottom of the uniaxially-stretched film of another kind of resin combination, this superficial layer and bottom are on the two sides of this core layer, and this resin combination contains the inorganic fine powder of 35 weight % to 65 weight %, the high density polyethylene of 0 to 10 weight % and the propylene resin of 55 weight % to 35 weight %; Described heat sealing resin layer contains: the high-pressure process tygon, this tygon has 0.900g/cm
3To 0.935g/cm
3Density, according to 10% to 60% crystallinity of determination of x-ray, and 10,000 to 40,000 number-average molecular weight; Or containing Hi-fax always, it has 0.880g/cm
3To 0.940g/cm
3Density.
2. in-mold labels according to claim 1, the wettable index of wherein said thermoplastic resin membrane's basalis surface and/or described heat sealing resin laminar surface is 38mN/m to 70mN/m.
3. in-mold labels according to claim 1 and 2, the thickness of wherein said thermoplastic resin membrane's basalis are 20 μ m to 500 μ m, and the thickness of described heat sealing resin layer is 1 μ m to 100 μ m.
4. in-mold labels according to claim 1 and 2, wherein said thermoplastic resin membrane's basalis surface and/or described heat sealing resin laminar surface stand activation processing.
5. in-mold labels according to claim 4, wherein said thermoplastic resin membrane's basalis surface and/or described heat sealing resin laminar surface stand Corona discharge Treatment.
6. in-mold labels according to claim 4 wherein forms antistatic layer on the surface of activated processing.
7. in-mold labels according to claim 6, wherein said antistatic layer comprises the acrylate copolymer that contains uncle's nitrogen or quaternary nitrogen.
8. in-mold labels according to claim 6, wherein said antistatic layer contain poly-group with imine moiety and/or polyamine-polyamide/epichlorohydrin adducts.
9. in-mold labels according to claim 1 and 2, wherein said thermoplastic resin membrane's basalis surface and/or described heat sealing resin laminar surface are through printing.
10. in-mold labels according to claim 1 and 2 is wherein used lubricant on 60% to 75% surface area of the heat sealing resin layer of this removable part.
11. in-mold labels according to claim 1 and 2, the length that wherein constitutes the slit of described perforation is 4mm to 10mm, and the distance between adjacent slits is 0.3mm to 0.6mm.
12. in-mold labels according to claim 1 and 2, the length that wherein constitutes the slit of described perforation is 5mm to 8mm, and the distance between adjacent slits is 0.3mm to 0.5mm.
13. in-mold labels according to claim 1 and 2, the adhesion strength between wherein said removable part and described container is 120gf/10mm to 240gf/10mm.
14. in-mold labels according to claim 1 and 2, wherein said removable part has the extraction part.
15. in-mold labels according to claim 14, wherein described extract part to 95% surface area, use lubricant more than 80%.
16. in-mold labels according to claim 14, the width of wherein said extraction part is 3mm to 10mm.
17. a container, it is pasted with according to the described in-mold labels of arbitrary claim in the claim 1 to 16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP339325/2002 | 2002-11-22 | ||
| JP2002339325 | 2002-11-22 | ||
| JP036083/2003 | 2003-02-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101738657A Division CN101661687B (en) | 2002-11-22 | 2003-11-21 | In-mold label having removable part |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1692386A CN1692386A (en) | 2005-11-02 |
| CN100559427C true CN100559427C (en) | 2009-11-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801006490A Expired - Fee Related CN100559427C (en) | 2002-11-22 | 2003-11-21 | In-mold labels with removable part |
| CN2009101738657A Expired - Fee Related CN101661687B (en) | 2002-11-22 | 2003-11-21 | In-mold label having removable part |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101738657A Expired - Fee Related CN101661687B (en) | 2002-11-22 | 2003-11-21 | In-mold label having removable part |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007317421B2 (en) | 2006-11-02 | 2012-11-15 | Avery Dennison Corporation | Emulsion adhesive for washable film |
| BRPI1013652B1 (en) * | 2009-03-30 | 2019-05-07 | Avery Dennison Corporation | Removable adhesive label containing high tensile modulus polymer film layer |
| US20120018098A1 (en) | 2009-03-30 | 2012-01-26 | Avery Dennison Corporation | Removable Adhesive Label Containing Inherently Shrinkable Polymeric Film |
| CN101777284B (en) * | 2009-12-29 | 2013-05-08 | 吴桂谦 | In-mold label structure and manufacturing method thereof |
| CN102555153B (en) * | 2010-12-20 | 2014-07-09 | 宝理塑料株式会社 | Composite forming body, production method thereof and in-mould label |
| CN103366636B (en) * | 2012-03-28 | 2016-08-17 | 深圳坤邦标价用品有限公司 | A kind of in-mold labels and manufacture method thereof |
| JP5741878B2 (en) * | 2013-04-18 | 2015-07-01 | 住友ベークライト株式会社 | Steel sheet coating film |
-
2003
- 2003-11-21 CN CNB2003801006490A patent/CN100559427C/en not_active Expired - Fee Related
- 2003-11-21 CN CN2009101738657A patent/CN101661687B/en not_active Expired - Fee Related
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| CN101661687A (en) | 2010-03-03 |
| CN101661687B (en) | 2011-06-08 |
| CN1692386A (en) | 2005-11-02 |
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