CN203311748U - In mold label for stretch blow molding and stretch blow molding product with in mold label - Google Patents
In mold label for stretch blow molding and stretch blow molding product with in mold label Download PDFInfo
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- CN203311748U CN203311748U CN201320173863XU CN201320173863U CN203311748U CN 203311748 U CN203311748 U CN 203311748U CN 201320173863X U CN201320173863X U CN 201320173863XU CN 201320173863 U CN201320173863 U CN 201320173863U CN 203311748 U CN203311748 U CN 203311748U
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Abstract
The utility model provides an in mold label for stretch blow molding and a stretch blow molding product with the in mold label, wherein the in mold label is superior in adhesion performance after being formed. The in mold label for the stretch blow molding is characterized by comprising a base material layer (I) and a heat sealing resin layer (II). The base material layer (I) comprises thermoplastic resin and inorganic finely pulverized powder. The heat sealing resin layer (II) is composed of a coating layer which is formed by coating the base material layer (I) with coating liquid comprising ethylene-vinyl acetate multipolymer and drying the base material layer (I).
Description
Technical field
The utility model relates to for in-molded stretch-blow with in-mold labels and is pasted with the stretch blow-molded product with in-mold labels of this label, describedly in-moldedly be, in advance the mode of label with the face side contact mould wall that is applied with printing of this label is placed in mould, to import the preform formed by thermoplastic resin in mould and carry out stretch blow-molded, thereby manufacture label sticking products formed.
Background technology
In the past, for the synthetic resin to tape label carries out one-body molded, proceed as follows: in mould, insert in advance blank or label, then by methods such as injection moulding, slush molding, differential pressure formed, foamings at this in-mold molding synthetic resin, adhesive label paint etc. on this synthetic resin.
As such label, such as known, have: take crystalline polypropylene, tygon etc. are carried out to extrusion molding, calendering formation and the film that obtains is base material, with the solution of the low melting point ethylene series resins such as coating ethylene-vinyl acetate copolymer on this base material such as intaglio plate coating machine dry, thus obtained label; Thereby use low melting point ethylene series resin film to be laminated in as bonding agent the label that this base material obtains; Low melting point ethylene series resin is connect to the label (for example,, with reference to patent documentation 1, patent documentation 2) that is laminated in this base material and obtains by the extruding layer straightening.
On the other hand, as by the method for synthetic resin at in-mold molding, have in slush molding: based on the method for the direct blow molding of the parison that uses resin with based on the stretch blow-molded method of the preform that uses resin.
The former forms parison more than resin is heated to the fusing point of material resin under the state of resin melting, make its expansion with pressurized air; And the latter is heated to preform the softening point of material resin, under the state that resin can be out of shape, preform is stretched with bar, and then make its expansion with pressurized air.
Even both are in the situation that use the same materials resin, the heat that also can cause because of the difference of making molten condition or making soft state putting on resin is obviously different.Therefore, the heat that the aforesaid label of considering direct blow molding and designing is given label by molten parison makes low-melting-point resin melting activation fully, thereby obtain the not products formed of in-problem tape label of the quality aspects such as bonding strength, and on the other hand, this aforesaid label is when stretch blow-molded, there are the following problems: preform can't be given the heat of the low-melting-point resin melting activation that is enough to make label, thereby can't adhesive labels, or the bonding strength of label poor, be easy to peel off.
Therefore, in order to tackle low stretch blow-molded of forming temperature, attempted using following label: the base film of label and the formation of bonding agent occur change, on the base film that can absorb as early as possible liquid, be provided with the resin-coated label of water system heat sealability (for example,, with reference to patent documentation 3); In the resin that the bond layer of label is used, be provided with the label (for example,, with reference to patent documentation 4) of bonding agent (delayed adhesive) admittedly late that the melting heat is low.
Yet clear and definite: (the liquid absorption coefficient is 5ml/m in patent documentation 3 liquid absorption excessive velocities such, base material
2(ms)
1/2Above) in situation, on base film during resin-coated dose of coating water system heat sealability, easy a large amount of crawlings that cause because of bubble that occur in filming, can't stably obtain desired bonding strength in this case.
In addition, clear and definite: in the situation that patent documentation 4 such, use the bonding agent admittedly late that the melting heat is low in bonding agent, although can obtain sufficient bonding strength, but during at the strip goods that batch this tag blank or by the stacked keeping of this tag blank, if the low molecular weight compositions such as plastifier contained in this bonding agent ooze out and transfer on the printing predetermined face of tag blank from bond layer, the transfer of the printer's ink while printing after can seriously hindering.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 58-069015 communique
Patent documentation 2: Japanese kokai publication hei 02-217223 communique
Patent documentation 3: TOHKEMY 2004-255864 communique
Patent documentation 4: TOHKEMY 2010-168117 communique
The utility model content
The problem that utility model will solve
Thereby, the inventor etc. be take provides a kind of in-mold labels newly developed to be the purpose of this utility model, be studied, even this in-mold labels is also abundant with the bonding strength of products formed under stretch blow-molded low-temperature adhesion condition, and the metastatic of the printer's ink during label printing is good.In addition, the purpose of this utility model is to provide a kind of by using the stretch blow-molded product of the tape label that this label obtains.
For the scheme of dealing with problems
The inventor etc. conduct in-depth research, and found that, the label that has an ad hoc structure by use carries out in-molded, can realize desired purpose.That is, the means as solving problem, provide the utility model be comprised of following technical scheme.
[1] a kind of stretch-blow in-mold labels, it is characterized in that, it is for comprising the in-mold labels of substrate layer (I) and heat sealability resin bed (II), this substrate layer (I) is formed by the resin combination that comprises thermoplastic resin and inorganic attritive powder, this heat sealability resin bed (II) is formed by coating layer, and described coating layer is that the coating fluid that will comprise ethylene-vinyl acetate copolymer is coated on the upper also drying of this substrate layer (I) and forms.
[2] according to [1] described stretch-blow in-mold labels, it is characterized in that, the liquid absorption coefficient of the face that heat sealability resin bed (II) side is set of substrate layer (I) is 4ml/m
2(ms)
1/2Below.
[3] according to [1] or [2] described stretch-blow in-mold labels, it is characterized in that, this thermoplastic resin comprises polypropylene-based resin.
[4] according to the described stretch-blow in-mold labels of any one in [1]～[3], it is characterized in that this substrate layer (I) forming without oriented film by resin combination.
[5] according to the described stretch-blow in-mold labels of any one in [1]～[3], it is characterized in that, this substrate layer (I) is included in the oriented film of the resin combination stretched on single shaft direction at least.
[6] according to [5] described stretch-blow in-mold labels, it is characterized in that, this substrate layer (I) comprises resin combination was stretched on single shaft direction at least oriented film, and described resin combination comprises thermoplastic resin and through the inorganic attritive powder of hydrophilicity-imparting treatment.
[7] according to the described stretch-blow in-mold labels of any one in [1]～[6], it is characterized in that, this ethylene-vinyl acetate copolymer is the ethylene-vinyl acetate copolymer of maleic acid modification.
[8] according to the described stretch-blow in-mold labels of any one in [1]～[7], it is characterized in that, this coating fluid that comprises ethylene-vinyl acetate copolymer comprises ethylene-vinyl acetate copolymer is dispersed in to the emulsion formed in aqueous medium.
[9] according to [8] described stretch-blow in-mold labels, it is characterized in that, the mean grain size of the emulsion of this ethylene-vinyl acetate copolymer is 0.01～3 μ m.
[10] according to the described stretch-blow in-mold labels of any one in [6]～[9], it is characterized in that, this heat sealability resin bed (II) is dry under the state that absorbed by this oriented film of the part at the coating fluid that comprises ethylene-vinyl acetate copolymer and coating layer that form.
[11] according to the described stretch-blow in-mold labels of any one in [1]～[10], it is characterized in that, the surface of this substrate layer (I) also is provided with printable layer (III).
[12] a kind of stretch blow-molded product with in-mold labels, it is characterized in that, it is for being pasted with in [1]～[11] the described stretch-blow of any one with the stretch blow-molded product with in-mold labels of in-mold labels, and this label is 200～1000g/15mm to the bonding strength of this products formed.
[13] according to [12] described stretch blow-molded product with in-mold labels, it is characterized in that, the resin that forms these stretch blow-molded product comprises at least a kind in polyester based resin, polycarbonate-based resin, polystyrene resin, polypropylene-based resin and polyethylene-based resin.
The effect of utility model
According to the utility model, a kind of in-mold labels is provided, even this in-mold labels is also abundant with the bonding strength of products formed under stretch blow-molded low-temperature adhesion condition, and the metastatic of the printer's ink during label printing is good.In addition, provide that a kind of high and label and products formed appear as the stretch blow-molded product of integrated tape label with the bonding strength of label by using this label.
The accompanying drawing explanation
Fig. 1 is the sectional view of stretch-blow of the present utility model by a kind of form of in-mold labels.In Fig. 1,1 means the stretch-blow in-mold labels; 2 mean substrate layer (I), are single layer structure; 3 mean thermoplastic resin (II), and it is that coating fluid forms by coating solvent.
Fig. 2 is the sectional view of stretch-blow of the present utility model by the another kind of form of in-mold labels.In Fig. 2,1 means the stretch-blow in-mold labels; 2 mean substrate layer (I), are single layer structure; 3 mean thermoplastic resin (II), and it is that coating fluid forms by the coating emulsion.
Fig. 3 is the sectional view of stretch-blow of the present utility model by the another kind of form of in-mold labels.In Fig. 3,1 means the stretch-blow in-mold labels; 2 and 4 mean substrate layer (I), are double-layer structure; 3 mean thermoplastic resin (II), and it is that coating fluid forms by coating solvent; The 4th, comprise thermoplastic resin and through the oriented film of the resin combination of the inorganic attritive powder of hydrophilicity-imparting treatment.
Fig. 4 is the sectional view of stretch-blow of the present utility model by the another kind of form of in-mold labels.In Fig. 4,1 means the stretch-blow in-mold labels; 2 and 4 mean substrate layer (I), are double-layer structure; 3 mean thermoplastic resin (II), and it is that coating fluid forms by the coating emulsion; The 4th, comprise thermoplastic resin and through the oriented film of the resin combination of the inorganic attritive powder of hydrophilicity-imparting treatment.
Fig. 5 is the sectional view of stretch-blow of the present utility model by the another kind of form of in-mold labels.In Fig. 5,1 means the stretch-blow in-mold labels; 2 and 4 mean substrate layer (I), are double-layer structure; 3 mean thermoplastic resin (II), and it is that coating fluid forms by the coating emulsion; The 4th, comprise thermoplastic resin and through the oriented film of the resin combination of the inorganic attritive powder of hydrophilicity-imparting treatment.5 mean printable layer (III).
Description of reference numerals
1 stretch-blow in-mold labels
2 substrate layers (I)
3 heat sealability resin beds (II)
4 comprise thermoplastic resin and through the oriented film of the resin combination of the inorganic attritive powder of hydrophilicity-imparting treatment
5 printable layers (III)
Embodiment
Below, for in-mold labels of the present utility model and used the products formed of this in-mold labels to be described in detail.The explanation of the technical scheme of below putting down in writing is based on representative embodiments of the present utility model, but the utility model is not limited to such embodiment.It should be noted that, in this manual, the numerical range of using "～" to mean refers to the numerical value that comprises respectively record before and after "～" scope as lower limit and higher limit.
(in-mold labels)
In-mold labels of the present utility model has the stepped construction that comprises at least substrate layer (I) and heat sealability resin bed (II).
And, it is characterized in that, substrate layer (I) is formed by the resin combination that comprises thermoplastic resin and inorganic attritive powder, heat sealability resin bed (II) is formed by coating layer, and described coating layer is that the coating fluid that will comprise ethylene-vinyl acetate copolymer is coated on the upper also drying of substrate layer (I) and forms.
The in-mold labels of the present utility model preferably surface of this substrate layer (I) also is provided with printable layer (III).
(substrate layer (I))
The substrate layer that in-mold labels of the present utility model is used (I) is the supporter of in-mold labels, label is given to the rigidity (power) of the degree of operations such as can printing, insert in mould.On the other hand, substrate layer (I) is that to make in-mold labels be the layer of White-opalescent, particularly, is formed by the resin combination that comprises thermoplastic resin and inorganic attritive powder.
Substrate layer (I) is for comprising the resin film of thermoplastic resin.As the thermoplastic resin that substrate layer (I) is used, can list the ethylene series resins such as polypropylene-based resin, poly-Methyl-1-pentene, ethene-cyclic olefin copolymer; Pet resin, polybutylene terephthalate resin, Corvic, nylon-6, nylon-6, the polyamide-based resins such as 6, nylon-6,10, nylon-6,12; The films such as polystyrene, polycarbonate, ionomer resin, optimization polypropylene are the thermoplastic resin of fusing point in 130～280 ℃ of scopes of resin, pet resin etc.These resins also can mix use more than 2 kinds.
In addition, the thermoplastic resin of the major component of formation substrate layer (I) is preferably and has than the high dystectic resin more than 15 ℃ of the fusing point of the ethylene series resin of formation heat sealability resin bed described later (II).Among these resins, especially from the aspects such as the transparency, thermotolerance, permanance, cost, more preferably polypropylene-based resin.As described polypropylene-based resin, can use the Noblen of the stereoregularity that shows isotactic or syndiotactic; Perhaps take the multipolymer of propylene as alpha-olefins such as major component and this major component and ethene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentenes.These multipolymers can be 2 yuan of systems, can be also 3 yuan of systems, can also be 4 yuan of systems, in addition, can be that random copolymers can be also segmented copolymer.
In addition, substrate layer (I) comprises inorganic attritive powder.Inorganic attritive powder is to make substrate layer (I) be the material of White-opalescent, is to make to put on the material that the visuality of the printing of in-mold labels improves.
As inorganic attritive powder, the use particle diameter is generally 0.01～15 μ m, is preferably the powder of 0.01～5 μ m.Particularly, can use calcium carbonate, potter's clay (baked clay), silicon dioxide, zeyssatite, carclazyte, talcum, titanium dioxide, barium sulphate, aluminium oxide, zeolite, mica, sericite, bentonitic clay, sepiolite, vermiculite, rauhkalk, wollastonite, glass fibre etc.
The amount of the inorganic attritive powder added in substrate layer (I) is preferably 10～70 % by weight of the general assembly (TW) of substrate layer (I), more preferably 20～60 % by weight, more preferably 30～50 % by weight.
And then can use the powder of the surface of these inorganic attritive powders having been implemented to hydrophilicity-imparting treatment.By being implemented to surface hydrophilic, process these inorganic attritive powders, and substrate layer (I) is implemented stretching described later and is made into Porous, can as shown in TOHKEMY 2001-226507 communique, to substrate layer (I), give the characteristic that absorbs liquid.
As this surface conditioning agent, be preferably water-soluble cationic multipolymer and water soluble anion and be at least one in surfactant.As the water-soluble cationic multipolymer of surface conditioning agent, be preferably at least one and the multipolymer of (2) nonionic hydrophilic ethylene base monomer in (1) diallyl amine salt or cyclopolymers of alkyldiallylamine salt herein.
As the diallyl amine salt of (1), the object lesson of cyclopolymers of alkyldiallylamine salt, can list the scope of diallyl amine salt, carbon number 1～4 cyclopolymers of alkyldiallylamine salt and dialkyl diallyl amine salt, be chloride, bromide, dimethyl suflfate or the ethyl-sulfate of methyl diallyl amine salt, ethyl diallyl amine salt, dimethyl diallyl amine salt, methacryloxyethyl trimethyl ammonium, acryloxy ethyl trimethyl ammonium, methacryloxyethyl dimethyl ethyl ammonium, acryloxy ethyl dimethyl ethyl ammonium; With epoxy compound alkylation methacrylic acid-N such as epichlorokydrin, epoxy prapanol, epoxypropyltrimethylchloride chlorides, N-dimethylaminoethyl or acrylic acid-N, the quaternary ammonium salt that N-dimethylaminoethyl ester obtains, among these, especially preferred diallyl amine salt, methyl diallyl amine salt and dimethyl diallyl amine salt.
Be used to form the diallyl amine salt of (1), the negative ion of cyclopolymers of alkyldiallylamine salt, can list chloride ion, bromide ion, sulfate ion, nitrate ion, methylsulfuric acid radical ion, ethyl sulfuric acid radical ion, methane-sulforic acid ion etc.
Object lesson as the nonionic hydrophilic ethylene base monomer of (2) has, acrylamide, Methacrylamide, N-vinyl formamide, N-vinyl acetamide, NVP, methacrylic acid-2-hydroxy methacrylate, 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, among these, especially be preferably acrylamide, Methacrylamide.
(1) with the copolymerization ratio of (2), be arbitrary value, (1) is preferably 10～99 % by mole, more preferably 50～97 % by mole, more preferably 65～95 % by mole, (2) be preferably 90～1 % by mole, more preferably 50～3 % by mole, more preferably 35～3 % by mole.
On the other hand, the water soluble anion that can be used as surface conditioning agent is to have anionic property functional group in the molecule of surfactant.It as water soluble anion, is the object lesson of surfactant, can list the salt of the sulfonate of the alkyl of the scope with carbon number 4～40, the mono phosphoric acid ester of higher alcohol of scope of phosphate ester salt, carbon number 4～40 of alkyl of scope with carbon number 4～40 or dibasic acid esters, the alkyl betaine, alkyl sulfo betaines etc. of alkyl with scope of carbon number 4～40, can suitably select.
In addition, substrate layer (I) can be used the adjuvants such as antioxidant, light stabilizer, spreading agent, lubrication prescription, antistatic agent as required.
While using antioxidant, particularly, usually add the antioxidant of sterically hindered phenol system in the scope of 0.001～1 % by weight, phosphorus system, amine system, sulphur system etc.While using light stabilizer, particularly, usually use the light stabilizer of bulky amine system in the scope of 0.001～1 % by weight, benzotriazole system, benzophenone series.
The thickness of substrate layer (I) is 20～200 μ m, be preferably the scope of 40～150 μ m.If thickness is that more than 20 μ m, while printing, label is difficult to produce wrinkle, in addition, also be difficult to produce while inserting in mould the problem that tram can't be fixed on and depart from.In addition, if the thickness of substrate layer (I) is below 200 μ m, be difficult to produce by the strength decreased of the boundary member of the label of the products formed of gained tape label and the problems such as reduction of the anti-whereabouts intensity caused.
(heat sealability resin bed (II))
The heat sealability resin bed (II) that in-mold labels of the present utility model is used is formed by coating layer, and described coating layer is that the coating fluid that will comprise ethylene-vinyl acetate copolymer is coated on the upper also drying of substrate layer (I) and forms.Heat sealability resin bed (II) is even under stretch blow-molded low-temperature adhesion condition, also can give the sufficient bonding strength with products formed to label.
(ethylene-vinyl acetate copolymer)
As the ethylene-vinyl acetate copolymer that forms heat sealability resin bed (II), preferably use melt flow rate as more than 20g/10 minute and comprise the multipolymer of ethene and vinyl acetate.
Among these multipolymers, even the bonding strength of ethylene-vinyl acetate copolymer label and blow molding product under the low-temperature adhesion condition is also excellent, thereby preferably.
Vinyl acetate content in ethylene-vinyl acetate copolymer is preferably 5～50 % by weight.If the vinyl acetate content in multipolymer is more than 5 % by weight, exists and improve the tendency of label to the cementability of stretch blow-molded product.In addition, make ethylene-vinyl acetate copolymer be easy to be dissolved in medium, be easy to manufacture the carboxyl acid modified thing of following explanation.On the other hand, if the vinyl acetate content in multipolymer is below 50 % by weight, even be used to form in the resin of aforesaid substrate layer (I), stretch blow-molded product described later while using the ethylene series resin, also have the tendency that can obtain high adhesiveness.
In addition, the acid number of carboxyl acid modified ethylene-vinyl acetate copolymer is preferably 1～60 scope.If acid number is more than 1, easily obtain aqueous liquid dispersion.On the other hand, if acid number is below 60, be easy to improve water tolerance, moisture-proof.
In addition, as this multipolymer, in order to improve its cementability, water dispersible, further preferably use with the carboxyl acid modified carboxyl acid modified ethylene-vinyl acetate copolymer formed.
Carboxyl acid modified ethylene-vinyl acetate copolymer can be manufactured with known method.For example, as in TOHKEMY 3-112836 communique, putting down in writing, make ethylene-vinyl acetate copolymer be dissolved in toluene or dimethylbenzene etc. aromatic hydrocarbon based in, add the lower alcohols such as methyl alcohol or ethanol, under the existence of the water of specified quantitative, use the alkali alcoholate catalyzer to carry out saponification, then for example, by the saponified and unsaturated carboxylic acid of gained ethylene-vinyl acetate copolymer (maleic acid, fumaric acid, itaconic acid, citraconic acid, the allyl succinic acid, mesaconic acid, aconitic acid) and acid anhydrides, with in its acid esters at least a kind, together react with radical initiator, thereby can obtain carboxyl acid modified ethylene-vinyl acetate copolymer.
Among these, most preferably use by with at least one in maleic acid and maleic anhydride, react the maleic acid obtained ethene improved-vinyl acetate co-polymer.
Aforementioned multipolymer and sour modified copolymer can be used separately, or are mixed with two or more.
These multipolymers are not from damage the viewpoint of the printing of its cementability, label, the preferably low-molecular-weight minor component of not compounding as far as possible.Yet, for these multipolymers are used with the form of dispersion liquid, emulsion in water described later, under the degree of the printing of not damaging its cementability, label, as required, can the compounding spreading agent etc.In addition, as required, can compounding rosin and derivant, terpenes and derivant thereof, petroleum resin, their the so-called tackifier such as hydride; The wax classes such as solid paraffin, microcrystalline wax, Brazil wax, Fischer-Tropsch wax; The inorganic micro powder ends such as silicon dioxide, talcum, zeolite are antiblocking agent; The organic system slip agents such as erucyl amide, oleamide, stearic amide; And then as the composition that improves cohesion, bonding force, can the compounding thermoplastic polyurethane, thermoplastic polyester, chlorinated polypropylene, haloflex etc.
The coating fluid that comprises the ethylene series resin can be used with the form that these multipolymers is dissolved in to the solution formed in organic solvent, also can be so that these multipolymers are dispersed in the form use of the ethylene series resin emulsion formed in aqueous solvent.
Use the in-mold labels of ethylene series resin emulsion opaque due to emulsion particle, had the advantage of easily finding unacceptable product when printing.And, in being pasted with the stretch blow-molded product with in-mold labels of this in-mold labels, by the ethylene series resin melting; emulsion particle can disappear; heat sealability resin bed (II) becomes transparent, and therefore, the outward appearance of label and products formed can not produce difference and appear as integrated.
As the method that obtains these multipolymers disperse the water-based emulsion formed in water, as No. 58-118843, Japanese kokai publication sho, No. 56-2149, Japanese kokai publication sho, No. 56-106940, Japanese kokai publication sho, Japanese kokai publication sho 56-157445 communiques etc. are described like that, in double screw extrusion machine, supply with copolymer resin, after melting mixing, liquid ingress pipe by the compression unit zone that is arranged at extruder or passage (vent) zone imports the water that contains dispersion liquid, rotary screw, thereby the copolymer resin of melting and water is mixing, make the housing internal phase inverse of this mixing thing at extruder, and be released into atmospheric pressure region by the outlet nozzle of extruder, as required, append and add water, and be housed in storage tank, thereby obtain water-based emulsion.
The average mark shot footpath of the copolymer resin particle in emulsion is preferably 0.01～3 μ m, more preferably 0.1～1 μ m.If the average mark shot footpath of copolymer resin particle in this scope, stable mutually under the state of dispersion liquid, the keeping of liquid, coating excellence.In addition, there is the tendency heat sealability resin bed (II) be easy to improve this dispersion liquid of coating and form, that be adhered to the transparency after the blow molding product.
Solid component concentration is preferably 8～60 % by weight, more preferably 20～50 % by weight.If the solid component concentration of the copolymer resin in emulsion is in this scope, stable mutually under the state of dispersion liquid, the keeping of liquid, coating excellence.
As this ethylene series resin emulsion, can utilize day LIFE BOND HC-12, HC-17, HC-38, the HCN-006 (trade name) of flourish Chemical Co., Ltd system; Toyo-Morton, the commercially available products such as the AD-37P295J of Ltd. system, EA-H700 (trade name).In addition, the coating fluid as the ethylene series resin dissolves forms in organic solvent, can utilize Toyo-Morton, the commercially available products such as the THS-4884 of Ltd. system, AD-1790-15 (trade name).
(coating)
As this comprises the method for the coating fluid of ethylene series resin in the upper coating of substrate layer (I), can use the apparatus for coating such as intaglio plate coating machine, miniature intaglio plate coating machine, reverse coating machine (reverse coater), knife type coater, Meyer rod painting machine, Kohler coater to implement.
After coating, make the dry solvent (being mainly water) of removing of coating layer, using the overlay film of generation as heat sealability resin bed (II).The thickness of heat sealability resin bed (II) is preferably 0.3～10 μ m, more preferably 1～5 μ m.If be more than 0.3 μ m, firmly welding of products formed and label, thus be easy to obtain high-adhesive-strength.In addition, if be below 10 μ m, the drying after the coating is also easy, in addition, also can't observe because the transparency reduces, the reduction of the not enough bonding strength caused of cohesion, thereby preferably.
(printable layer (III))
In-mold labels of the present utility model can further arrange printable layer (III) on the surface of substrate layer (I) makes it become the outermost layer of label.Printable layer (III) arranges for the printing adaptability that improves in-mold labels.
As the material of printable layer (III), can list the polyolefin-based resins such as the slaine (Zn, Al, Li, K, Na etc.) of polypropylene-based resin, high density polyethylene, medium density polyethylene, straight chain linear low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethylene-methyl methacrylate alkyl ester copolymer (carbon number of alkyl is 1～8), ethylene-methacrylic acid copolymer, poly--4-methyl-1-pentene, ethene-cyclic olefin copolymer; Pet resin, Corvic, nylon-6, nylon-6, the polyamide-based resins such as 6, nylon-6,10, nylon-6,12; The film such as ABS resin, ionomer resin, be preferably the thermoplastic resins of fusing point in 130～280 ℃ of scopes such as polypropylene-based resin, high density polyethylene, pet resin, and these resins also can be mixed with two or more.
Among these, preferably use polyolefin-based resins.And then, among polyolefin-based resins, from the aspect of cost face, water tolerance, chemically-resistant preparation, more preferably use polypropylene-based resin, high density polyethylene.As described polypropylene-based resin, can preferably use the Noblen (polypropylene) of the stereoregularity that shows isotactic or syndiotactic and various degree; Take the multipolymer of propylene as alpha-olefins such as major component and this major component and ethene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentenes.These multipolymers can be 2 yuan of systems, can be also 3 yuan of systems, can also be 4 yuan of systems, in addition, can be that random copolymers can be also segmented copolymer.
In addition, in order to improve black adhesion, preferably comprise ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ionomer, ethylene-methyl methacrylate alkyl ester copolymer (carbon number of alkyl is 1～8), the slaine (Zn, Al, Li, K, Na etc.) of ethylene-methacrylic acid copolymer, maleic acid modified polypropene, maleic acid modified poly ethylene, maleic acid ethene improved-vinyl acetate co-polymer etc. has the thermoplastic resin of polar group.Wherein, the maleic acid of preferred black adhesion excellence ethene improved-vinyl acetate co-polymer.As required, can add antioxidant, ultra-violet stabilizer etc.
The thickness of printable layer (III) is 1～30 μ m, be preferably the scope of 5～20 μ m.If thickness is more than 1 μ m, black adhesion improves, if be below 30 μ m, label is difficult to produce curling, not there will be and be difficult to label is carried out offset printing or is difficult to label is fixed in the situation of mould, thereby preferably.
In-mold labels of the present utility model can come in advance the printing on the surface of this printable layer (III) is improved by activation processing as required.As activation processing, for being selected from least a oxidation treatment method in Corona discharge Treatment, flame treatment (flame processing), Cement Composite Treated by Plasma, glow discharge processing, ozone treatment, preferred corona treatment, flame treatment.About treatment capacity, in the situation that corona treatment is generally 600～12,000J/m
2(10～200W minute/m
2), preferred 1200～9000J/m
2(20～150W minute/m
2).If be 600J/m
2(10W minute/m
2) more than, can fully obtain the effect of Corona discharge Treatment, the adhesion of China ink improves.In addition, surpass 12,000J/m
2(200W minute/m
2) time, the effect of processing reaches capacity, so treatment capacity is at 12,000J/m
2(200W minute/m
2) below be namely sufficient.And in the situation that flame treatment is used 8,000～200 usually, 000J/m
2, preferably use 20,000～100,000J/m
2.If be 8,000J/m
2Above, can fully obtain the effect of flame treatment, the adhesion of China ink improves.In addition, surpass 200,000J/m
2The time, the effect of processing reaches capacity, so treatment capacity is at 200,000J/m
2Namely below sufficient.
Substrate layer in the utility model (I) has been endowed in the situation of the characteristic that absorbs liquid for film and the substrate layer (I) of the porous that process stretching process described later obtains, while being coated with the aforesaid coating fluid that comprises ethylene-vinyl acetate copolymer, a part by the coating fluid comprising ethylene-vinyl acetate copolymer is coated with under the state of substrate layer (I) absorption, under this state by the coating fluid dry solidification, thereby on the surface of substrate layer (I), form heat sealability resin bed (II).
Now, the ability of the absorption liquid of substrate layer (I) can be adjusted by absorbing volume and infiltration rate.When the volume of substrate layer (I) absorption liquid is excessive, may cause basically all being contained in substrate layer (I) for the coating fluid of coating, possibly can't bring into play fully cementability.The volume that substrate layer (I) absorbs liquid can change by the thickness of substrate layer (I), the amount of hole in substrate layer (I).In addition, when the speed of substrate layer (I) absorption liquid was excessive, the solvent composition that is coated on the coating fluid that comprises ethylene-vinyl acetate copolymer on substrate layer (I) was rapidly absorbed in substrate layer (I), and drying accelerates.Yet the rapid draing meeting in painting process becomes the reason of damaging the levelling (uniformity coefficient) of filming, in addition, in filming, become and easily produce bubble, result, likely can't obtain desired bonding strength.The hydrophilicity-imparting treatment amount of the inorganic attritive powder that the speed of substrate layer (I) absorption liquid can be passed through to use, the amount of the hole in substrate layer (I) change.
Therefore, the liquid absorption volume in substrate layer (I) is with the transfer amount V (ml/m of the liquid of the liquid-absorbent test method (Bristow method) of JAPAN TAPPI No.51
2) meter, be preferably 100ml/m
2Below, 50ml/m more preferably
2Below, 10ml/m more preferably
2Below.On the other hand, the liquid absorption volume is preferably 0.5ml/m
2Above, 3ml/m more preferably
2Above, 5ml/m more preferably
2Above.
In addition, the liquid absorption speed in substrate layer (I) is with the liquid absorption COEFFICIENT K α (ml/m of the liquid-absorbent test method (Bristow method) of JAPAN TAPPI No.51
2(ms)
1/2) meter, be preferably 4ml/m
2(ms)
1/2Below, 3.5ml/m more preferably
2(ms)
1/2Below, 3ml/m more preferably
2(ms)
1/2Below.On the other hand, liquid absorption speed is preferably 0.5ml/m
2(ms)
1/2Above, 1ml/m more preferably
2(ms)
1/2Above, 1.5ml/m more preferably
2(ms)
1/2Above.
To the printing that the printable layer (III) of label of the present utility model carries out, can implement by printing processes such as letterpress (letter press printing), intaglio printing, offset printing, flexible printing, serigraphys.Can be to label printing such as bar code, manufacturer, sales company's title, symbol (character), trade name, using method etc.Label after printing is processed and is separated into the label with necessary geomery by stamping-out.This in-mold labels can be the partial label that is pasted on the part surface of products formed, but usually can be used as the blank of the side of the container-like products formed of spooling, can also be as the table side that is pasted on respectively container-like products formed and/or the label of dorsal part.
(moulding of substrate layer (I) and printable layer (III))
The substrate layer of formation in-mold labels of the present utility model (I) and printable layer (III) can be manufactured by the combination that well known to a person skilled in the art the whole bag of tricks and method.The in-mold labels that no matter adopts any method to manufacture, the condition of putting down in writing in the utility model as long as meet, all be included in scope of the present utility model.
Method as moulding substrate layer of the present utility model (I) for example can list: use the individual layer T mould that is connected in screwe-type xtruder molten resin to be extruded into to the doctor-blade casting process of sheet; The O mould that use is connected in screwe-type xtruder is extruded into molten resin the blow molding method of tubulose; Rolling process; Rolling-molding method etc.
Substrate layer (I) itself can be single layer structure, can be also the sandwich construction more than 2 layers.By the multiple stratification of substrate layer (I), can additional instance if improved the function such as gas barrier property.
[multiple stratification]
Substrate layer in the utility model (I) can directly be used with the form of the resin film of individual layer, preferably with the form of the stacked resin film that is laminated with printable layer (III) on substrate layer (I), uses.
Therefore, in-mold labels of the present utility model can adopt the stepped construction that comprises substrate layer (I)/heat sealability resin bed (II) and printable layer (III)/substrate layer (I)/heat sealability resin bed (II).
At least one in substrate layer (I) and printable layer (III) can be carried out to moulding as stacked resin film in advance.On the surface of substrate layer (I) side of the stacked resin film of gained, by aforementioned rubbing method, heat sealability resin bed (II) is set, thereby can obtains in-mold labels of the present utility model.
As the manufacture method of these stacked resin films, can adopt known various thin film fabrication technology, their combination to carry out.For example, can list: the coextrusion mode of having used the multilayer T mould that is connected in screwe-type xtruder; The lamination mode of extruding, melting lamination mode, the heat lamination mode of a plurality of die heads have been used; Dry lamination mode, wet type lamination mode of various bonding agents etc. have been used.In addition, can also be used in combination multilayer film and extrude lamination.From the viewpoint of bonding each layer firmly, preferred coextrusion mode.
[stretching]
The substrate layer of formation in-mold labels of the present utility model (I) and printable layer (III) can be respectively unstretched without stretching, tensile layer not, can be also on the single shaft direction, stretched at least layer.The transparency of unstretched layer is more excellent, to the product having shape-following-up properties excellence of stretch blow-molded product.The layer of drawn is excellent because of the filming transparency, and quality is light and thickness evenness is excellent.
To these layers while stretching, can combine to carry out with any or its in known the whole bag of tricks.For example can list: the longitudinal stretching of difference that has utilized the peripheral speed of roller group; Used the cross directional stretch of Tenter oven; Continuous 2 axles that longitudinal stretching and cross directional stretch are combined stretch; In the time of based on the combination of Tenter oven and linear motor, 2 axles stretch; 2 axle stretchings in the time of based on the combination of Tenter oven and eidograph (pantograph), calendering etc.In addition, while using blow molding method, can list 2 axles when being blown into air capacity based on adjustment and stretch.
The multiplying power stretched is not particularly limited, is considered as the characteristic of the thermoplastic resin of main use in the substrate layer (I) of supporter and the physical property of the stacked resin film of gained etc. and suitably determines.For example, as the thermoplastic resin of substrate layer (I) and use Noblen or its multipolymer, it is 1.2～12 times that stretching ratio when it is stretched on one direction is generally, be preferably 2～10 times, and carry out the area multiplying power of 2 axles while stretching, be generally 1.5～60 times, be preferably 4～50 times.Use other thermoplastic resin, the stretching ratio when it is stretched on one direction is generally 1.2～10 times, is preferably 2～5 times, is generally 1.5～20 times and carry out the area multiplying power of 2 axles while stretching, and is preferably 4～12 times.
The glass transition temperature of the temperature stretched main thermoplastic resin used in substrate layer (I) is above to suitably decision in below the fusing point of crystal block section, known temperature range that be suitable for thermoplastic resin.Particularly, when the thermoplastic resin of substrate layer (I) was Noblen (155～167 ℃ of fusing points), the temperature of stretching was 100～166 ℃, was than the temperature of low 1～70 ℃ of fusing point.In addition, the speed of stretching preferably is made as 20～350m/ minute.
Therefore, substrate layer of the present utility model (I) more preferably comprise inorganic attritive powder polypropylene-based resin without oriented film (CPP film) or oriented film (OPP film).Substrate layer (I) is during without oriented film, and the crystallization caused by the stretch orientation of polypropylene-based resin molecule is suppressed, and is easy to obtain can following when blow molding the flexibility of the change of shape of products formed.When substrate layer (I) was oriented film, substrate layer can be so-called pearl film, synthetic paper.By these base materials, can easily obtain higher opacity.
(in-molded)
In-mold labels of the present utility model can be compatibly as the resin preform of heating is crimped on to the in-mold labels that the slush molding that carries out figuration on mould inner wall is used (stretch blow-molded use) by bar and pressurized air.Use in the stretch blow-molded product of in-mold labels manufacture of the present utility model, the adhesive portion of label and the difference in appearance of non-adhesive portion are little, have higher one sense.
As the resin that is used to form these stretch blow-molded product, such as listing the polyester based resins such as polyethylene terephthalate, polybutylene terephthalate, poly butylene succinate, PLA; The phenylethylene resin series such as polycarbonate-based resin, polystyrene, styrene-acrylonitrile copolymer, Styrene-Butadiene; Polypropylene-based resin and polyethylene-based resin etc.
This resin can be for not comprising transparent, the technicolour resin of pigment, dyestuff etc., but also can be for comprising opaque, the painted resin of pigment, dyestuff etc.
Embodiment
Below enumerate Production Example, embodiment and test example the utility model is carried out to more specific description.Material shown in following embodiment, use amount, ratio, contents processing, processing sequence etc. are only otherwise breaking away from aim of the present utility model just can suitably change.Therefore, technical scope of the present utility model is not limited to the following object lesson illustrated etc.
It should be noted that, the assay method of the physical property in Production Example, embodiment and comparative example and evaluation method are implemented according to the following method illustrated.
(Production Example of substrate layer (I))
(Production Example 1)
Resin combination as substrate layer (I) use, use respectively different extruders at 240 ℃ of lower melting mixings in following potpourri (a), potpourri (b) and potpourri (c), they are supplied in 1 coextrusion T mould, at T mould internal layer, be stacked as 3 layers, then utilize the T mould to be extruded into sheet, it is imported between half mirror chill roll and delustring rubber rollers, (linear load: about 1.5kg/cm) limit is cooling, is had the white of the 3-tier architecture of (c/a/b), the stacked resin film of opaque nothing stretching in the limit clamping.Wherein, described potpourri (a) is Noblen (Japan Polypropylene Corporation system, trade name: NOVATEC PP MA3) 95 % by weight and titania attritive powder (Ishihara Sangyo Kaisha, Ltd.'s system, trade name: TIPAQUE CR-60) 5 % by weight; Potpourri (b) is ethene-1-hexene copolymer (Japan Polyethylene Corporation system, trade name: KERNEL KS340T) 85.7 % by weight, high-pressure process Low Density Polyethylene (Japan Polyethylene Corporation system, trade name: NOVATEC LD LC720) 9.5 % by weight and antistatic agent (Japan Polyethylene Corporation system, trade name: NOVATEC LL LX-AS) 4.8 % by weight; And potpourri (c) is as Noblen (Japan Polypropylene Corporation system, the trade name: NOVATEC PP MA3U) 70 % by weight and high-pressure process Low Density Polyethylene (Japan Polyethylene Corporation system, trade name: NOVATEC LD LC720) 30 % by weight of printable layer (III) with resin combination.
Then, with deflector roll, it is imported to the Corona discharge Treatment device, to the surface of printable layer (III) side with 50W minute/m
2Treatment capacity apply Corona discharge Treatment, the excision ear after, with coiling machine, batch.
As this half mirror chill roll, use following chill roll: after will being processed into half mirror through the metal cooling roller of the machining eyeglass (mirror finish) that hard chrome plating forms, carry out attrition process.Its surfaceness (according to the arithmetic average roughness Ra of JIS B-0601 mensuration) is that 0.3 μ m, maximum height (Ry) are that 2.9 μ m, 10 mean roughness (Rz) are 2.2 μ m, diameter is that 450mm, width are 1500mm, and chilling temperature is set as 70 ℃.
As this coarse rubber rollers, use has the roller of following characteristic: the rubber hardness (according to JIS K-6301:1995) that uses spring JIS sclerometer to measure is 70Hs, ratio with 20～55 % by weight contains the silica sand of particle diameter 31～37 μ m, the subparticle of silicate glass, and diameter is that 300mm, width are 1500mm.
During clamping, carry out moulding in the mode of half mirror chill roll contact mixture (b), coarse rubber rollers contact mixture (c).The thickness of the stacked resin film of gained is 100 μ m, and density is 0.89g/cm
3.
(Production Example 2)
Resin combination as substrate layer (I) use, by following potpourri (d) and potpourri (e) use respectively different extruders in being set as the extruder of 230 ℃, carry out mixing after, be supplied in a coextrusion T mould that is set as 250 ℃, in the T mould, carry out stacked, and extrude as sheet, utilize cooling device that it is cooling, thus obtain 3-tier architecture (e/d/e) without drawing sheet.Should be heated to 150 ℃ and on longitudinal direction, stretch 5 times without drawing sheet.Then, after being cooled to the temperature of 60 ℃, again be heated to the temperature of 150 ℃, with stenter, on transverse direction, stretch 8 times, at the temperature of 160 ℃, carry out annealing in process, be cooled to the temperature of 60 ℃, thereby had the white, opaque through biaxial stretch-formed stacked resin film of the 3-tier architecture of (e/d/e).Wherein, potpourri (d) is Noblen (Japan Polypropylene Corporation system, trade name: NOVATEC PP FY4) 70 % by weight, high density polyethylene (Japan Polyethylene Corporation system, trade name: NOVATEC HD HJ360) 10 % by weight and calcium carbonate attritive powder (standby northern efflorescence Industrial Co., Ltd system, trade name: SOFTON1800) 20 % by weight; Potpourri (e) is Noblen (Japan Polypropylene Corporation system, trade name: NOVATEC PP MA3) 70 % by weight and calcium carbonate attritive powder (standby northern efflorescence Industrial Co., Ltd system, trade name: SOFTON1800) 30 % by weight.
Then, with deflector roll, it is imported to the Corona discharge Treatment device, to the surface of both sides respectively with 50W minute/m
2Treatment capacity apply Corona discharge Treatment, the excision ear after, with coiling machine, batch.
The thickness of the stacked resin film of gained is that 80 μ m (e/d/e=10/60/10 μ m), density are 0.76g/cm
3.
(Production Example 3)
Resin combination as substrate layer (I) use, by Noblen (Japan Polypropylene Corporation system, trade name: NOVATEC PP FY6H) 75 % by weight, high density polyethylene (Japan Polyethylene Corporation system, trade name: NOVATEC HD HJ580N) 5 % by weight and calcium carbonate attritive powder (standby northern efflorescence Industrial Co., Ltd system, trade name: SOFTON1800) potpourri of 20 % by weight (f) is used extruder at 250 ℃ of lower melting mixings, it is supplied to and extrudes in the T mould, and be extruded into sheet, utilize cooling device that it is cooling, obtain single layer structure (f) without drawing sheet.
Then, should be heated to 145 ℃ without drawing sheet, and utilize the difference of the peripheral speed of roller group on longitudinal direction, to stretch 4.5 times, obtain drawing sheet.
On the other hand, resin combination as substrate layer (I) use, following potpourri (g) and potpourri (h) are used respectively to different extruders, at 240 ℃ of lower melting mixings, they are supplied to different extruding in the T mould, and they are extruded into to sheet stacked on two surfaces of above-mentioned drawing sheet, and then utilize cooling device cooling, obtain the laminates of 3-tier architecture (g/f/h).Wherein, described potpourri (g) is that (Japan Polypropylene Corporation system, trade name: NOVATEC PP MA1B) ground chalk attritive powder (FIMATEC LTD. system, the trade name: AFF-Z) 60 % by weight of hydrophilicity-imparting treatment carried out on 38 % by weight, maleic acid modified polypropene (Sanyo Chemical Industries Co., Ltd.'s system, trade name: YUMEX 1001) 2 % by weight and surface to Noblen; And potpourri (h) is Noblen (Japan Polypropylene Corporation system, trade name: NOVATEC PP MA3) 55 % by weight and calcium carbonate attritive powder (standby northern efflorescence Industrial Co., Ltd system, trade name: SOFTON1800) 45 % by weight.
Then, this laminates is heated to 154 ℃, utilizes stenter on transverse direction, to stretch 8.5 times, at the temperature of 155 ℃, carry out annealing in process, be cooled to the temperature of 55 ℃, had the stacked resin film of the white of the 3-tier architecture of (g/f/h), opaque drawn.
Then, with deflector roll, it is imported to the Corona discharge Treatment device, to the surface of both sides respectively with 50W minute/m
2Treatment capacity apply Corona discharge Treatment, the excision ear after, with coiling machine, batch.
The thickness of the stacked resin film of gained is that 95 μ m (g/f/h=10/75/10 μ m), density are 0.81g/cm
3, each layer the stretching number of axle be: the g layer is that 1 axle, f layer are that 2 axles, h layer are 1 axle.
(Production Example 4)
Obtain inside contain empty white, the biaxially oriented film of opaque polyester (Toyo Boseki K. K's system, trade name: CRISPER G2311), using it as stacked resin film.
Then, it is imported to the Corona discharge Treatment device, to the surface of a untreated side with 50W minute/m
2Treatment capacity apply Corona discharge Treatment, with coiling machine, batch.
The thickness of the stacked resin film of gained is that 38 μ m, density are 1.1g/cm
3.
(Production Examples of the blow molding product of in-mold labels and tape label)
(embodiment 1)
Use miniature intaglio plate coating machine, the surface-coated maleic acid of (b) of the stacked resin film obtained in Production Example 1 layer one side is ethene improved-emulsion solution (Toyo-Morton of vinyl acetate co-polymer, Ltd. system, trade name: EA-H700, solid component concentration: 50%), with the baking oven that is set as 95 ℃, make its drying and heat sealability resin bed (II) is set, obtain the stretch-blow in-mold labels of embodiment 1.The thickness of gained heat sealability resin bed (II) is 3 μ m.
Then, by the in-mold labels stamping-out obtained in each embodiment, comparative example, it is the rectangle of long limit 8cm, minor face 6cm, use electrostatic charger device to make it charged, (NISSEI ASB MACHINE CO., LTD. system, trade name: the inside of mold for forming ASB-70DPH) arranges in the mode (heat sealability resin bed (II) is towards the mode of cavity side) of printable layer (III) contact mould at stretch blow moulding.Label arranges in the mode of circumferencial direction that the long limit of label is pasted on the trunk of products formed abreast in mould.
Then, the preform of technicolour polyethylene terephthalate is preheated to 100 ℃, in mould with 5～40kg/cm
2Blowing pressure this preform is carried out to the stretch blow-molded of 1 second, thereby obtain the stretch blow-molded product with in-mold labels.
The products formed of gained tape label is the container with square metastomium of height 12cm, the about 7cm in one side.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(embodiment 2)
As substrate layer (I), use the stacked resin film obtained in Production Example 2, this film the layer (e) side surface heat sealability resin bed (II) is set, in addition, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(embodiment 3)
As substrate layer (I), use the stacked resin film obtained in Production Example 3, this film the layer (g) side surface heat sealability resin bed (II) is set, in addition, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(embodiment 4)
As substrate layer (I), use the stacked resin film obtained in Production Example 4, surface in the Corona discharge Treatment face side of this film arranges heat sealability resin bed (II), in addition, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(embodiment 5)
Except the emulsion solution of using olefin resin (day flourish Chemical Co., Ltd system, trade name: LIFE BOND HCN-006, solid component concentration: 50%) as comprising the coating fluid of ethylene series resin, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(embodiment 6)
Except using the hot lacquering (Toyo-Morton of ethylene-vinyl acetate copolymer, Ltd. system, trade name: TOMOFLEX THS-4884-U, solid component concentration: 15%) as comprising beyond the coating fluid of ethylene series resin, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(comparative example 1)
(the first coating is manufactured made, trade name: BALLON BL-1, solid component concentration: 42.8%) replace ethylene series resin emulsion solution, obtain similarly to Example 1 stretch-blow with in-mold labels and with the stretch blow-molded product of in-mold labels except using modified styrene copolymer emulsion solution.The label bonding strength of the products formed of gained tape label the results are shown in table 1.
(evaluation)
About the evaluation method of the blow molding product of the stacked resin film in each Production Example and the tape label in embodiment and comparative example, implement according to the following method illustrated.
(1) label bonding strength
By the in-mold labels stamping-out growth limit 8cm obtained in each embodiment and comparative example, the rectangle of minor face 6cm, prepare the manufacture label of the products formed of tape label.
Use electrostatic charger device to make above-mentioned manufacture charged with label, (NISSEI ASB MACHINE CO., LTD. system, trade name: the inside of mold for forming ASB-70DPH) arranges in the mode (heat sealability resin bed (II) is towards the mode of cavity side) of the opposing face contact mould of heat sealability resin bed (II) at stretch blow moulding.Label arranges in the mode of circumferencial direction that the long limit of label is pasted on the trunk of products formed abreast in mould.
Then, the preform of polyethylene terephthalate is preheated to 100 ℃, in mould with 5～40kg/cm
2Blowing pressure this preform is carried out to the stretch blow-molded of 1 second, thereby obtain the stretch blow-molded product with in-mold labels.
The products formed of gained tape label is the container with square metastomium of height 12cm, the about 7cm in one side.
Products formed for each tape label of gained, after under the environment of 23 ℃ of temperature, relative humidity 50%, taking care of 2, with cutting machine, cut the label sticking part, from the long limit with the circumferencial direction of container trunk on two containers, take 6 test samples, the length of described sample is 12cm (adhesive portion of label is that 9cm, non-adhesive portion are 3cm), wide 1.5cm (whole width all is pasted with label).
Then, from bare terminal end (exposed core) (non-stickup) part peeling label carefully, when peeling off about 1cm, label is pasted on to the PET film (50 μ m) of same width with bonding agent, as the bare terminal end part of label-side, make the sample that determining bonding strength is used.
Then, based on JIS K6854-2:1999, use cupping machine (Shimadzu Seisakusho Ltd.'s system) to implement 180 degree and peel off, measuring strip length is the mean value of the peeling force between 25mm to 75mm, and then the mean value of the measured value of 6 sample thiefs, measure bonding strength.
More than the label bonding strength is preferably 200gf/15mm, more preferably more than 300gf/15mm, more preferably more than 400gf/15mm.If the label bonding strength is more than 200gf/15mm, substantially no problem on actual the use.
It should be noted that, about the products formed of the tape label of comparative example 2, due to the poor attachment that the degree that label basically all floats from container, just peels off when the sampling occurs, therefore all can't measure bonding strength.
(2) thickness, thickness, density
Stretch-blow of the present utility model is used level pressure thickness tester (teclock corporation system, trade name: PG-01J) measure with the thickness of in-mold labels according to JIS K-7130.The thickness of each layer, thickness is following to be obtained: the determination object sample is cooling to the temperature below-60 ℃ by liquid nitrogen, with razor blade (Schick Japan Co., the Ltd system, trade name: the sample that Proline Blade) will be placed on glass plate cuts with right angle, make be used to observing the sample in cross section, use scanning electron microscope (Jeol Ltd.'s system, trade name: JSM-6490) the gained sample is carried out to cross-section, from forming outward appearance, judge the boundary line of filming with the thermoplastic resin composition, with the thickness of label integral body, be multiplied by observed bed thickness ratio, thereby obtain.
[table 1]
Utilizability on industry
According to stretch-blow in-mold labels of the present utility model, even can obtain under the low-temperature adhesion condition based on stretch blow-molded, the bonding strength of label and products formed is sufficient products formed also.
Claims (9)
1. stretch-blow in-mold labels, it is characterized in that, it is for comprising the in-mold labels of substrate layer (I) and heat sealability resin bed (II), this heat sealability resin bed (II) is formed by coating layer, and described coating layer is coated on the upper also drying of this substrate layer (I) by coating fluid and forms.
2. stretch-blow in-mold labels according to claim 1, is characterized in that, the liquid absorption coefficient of the face that heat sealability resin bed (II) side is set of substrate layer (I) is 4ml/m
2(ms)
1/2Below.
3. stretch-blow in-mold labels according to claim 1 and 2, is characterized in that, this substrate layer (I) forming without oriented film by resin combination.
4. stretch-blow in-mold labels according to claim 1 and 2, is characterized in that, this substrate layer (I) is included in the oriented film of the resin combination stretched on single shaft direction at least.
5. stretch-blow in-mold labels according to claim 1 and 2, is characterized in that, this coating fluid comprises emulsion.
6. stretch-blow in-mold labels according to claim 5, is characterized in that, the mean grain size of this emulsion is 0.01～3 μ m.
7. stretch-blow in-mold labels according to claim 4, is characterized in that, this heat sealability resin bed (II) is dry under the state that absorbed by this oriented film of the part at coating fluid and coating layer that form.
8. stretch-blow in-mold labels according to claim 1 and 2, is characterized in that, the surface of this substrate layer (I) also is provided with printable layer (III).
9. stretch blow-molded product with in-mold labels, it is characterized in that, it is to be pasted with in claim 1～8 the described stretch-blow of any one with the stretch blow-molded product with in-mold labels of in-mold labels, and this label is 200～1000g/15mm to the bonding strength of this products formed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201320173863XU CN203311748U (en) | 2013-03-01 | 2013-04-09 | In mold label for stretch blow molding and stretch blow molding product with in mold label |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310065448 | 2013-03-01 | ||
| CN201310065448.7 | 2013-03-01 | ||
| CN201320173863XU CN203311748U (en) | 2013-03-01 | 2013-04-09 | In mold label for stretch blow molding and stretch blow molding product with in mold label |
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| Publication Number | Publication Date |
|---|---|
| CN203311748U true CN203311748U (en) | 2013-11-27 |
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| CN201320173863XU Expired - Lifetime CN203311748U (en) | 2013-03-01 | 2013-04-09 | In mold label for stretch blow molding and stretch blow molding product with in mold label |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103745655A (en) * | 2013-12-13 | 2014-04-23 | 中山市美高力印刷有限公司 | Method for manufacturing in-mould label |
| WO2014131372A1 (en) * | 2013-03-01 | 2014-09-04 | 优泊公司 | In-mold label for use in stretch blow molding and stretch blow molding-molded product having the label |
| CN105102224A (en) * | 2014-03-03 | 2015-11-25 | 优泊公司 | Film and plastic container with label |
| CN110447060A (en) * | 2017-03-31 | 2019-11-12 | 优泊公司 | The synthetic resin of label for in-mold molding and tape label |
| TWI681001B (en) * | 2015-02-16 | 2020-01-01 | 日商優寶股份有限公司 | Thermoplastic resin film and its manufacturing method, label for in-mold forming, and plastic container with label and manufacturing method thereof |
-
2013
- 2013-04-09 CN CN201320173863XU patent/CN203311748U/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014131372A1 (en) * | 2013-03-01 | 2014-09-04 | 优泊公司 | In-mold label for use in stretch blow molding and stretch blow molding-molded product having the label |
| CN103745655A (en) * | 2013-12-13 | 2014-04-23 | 中山市美高力印刷有限公司 | Method for manufacturing in-mould label |
| CN105102224A (en) * | 2014-03-03 | 2015-11-25 | 优泊公司 | Film and plastic container with label |
| CN105102224B (en) * | 2014-03-03 | 2017-08-29 | 优泊公司 | Film and tape label plastic containers |
| TWI681001B (en) * | 2015-02-16 | 2020-01-01 | 日商優寶股份有限公司 | Thermoplastic resin film and its manufacturing method, label for in-mold forming, and plastic container with label and manufacturing method thereof |
| US10717223B2 (en) | 2015-02-16 | 2020-07-21 | Yupo Corporation | Thermoplastic resin film and production method thereof, in-mold molding label, and plastic container with label and production method thereof |
| CN110447060A (en) * | 2017-03-31 | 2019-11-12 | 优泊公司 | The synthetic resin of label for in-mold molding and tape label |
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