CN1520992B - Label for shaping in mould and container for shaping in mould having the label - Google Patents

Abstract

The oriented resin film is obtained by forming an aqueous heat-sealable resin coat layer (E) on a base material film having a liquid absorption coefficient of >=5ml/m<SP>2</SP>(ms)<SP>1/2</SP>.

Description

The mould internal shaping is with label and the mould internal shaping container that posts this label

Technical field

The present invention relates to use label with the mould internal shaping (shaping of イ Application モ one Le De) of when container is shaped, being adhered in the thermoplastic resin container of differential pressure shaping, hollow forming, injection moulding, foaming and molding, draw blow molding or compression molding manufacturing.Particularly relate to the mould internal shaping of on bonding plane, implementing printing and stick to the mould internal shaping container that has label of transparent vessel with label and it.

Background technology

In recent years, people are developing the mould internal shaping label that must have resistance to water, drug resistance, durability always.For example, the part type of merchandise of having developed has, on the white films single faces such as (synthetic papers) that hyaline membrane that is made of the polyolefin-based resins that stretches or do not stretch and the polyolefin-based resins that is combined with the stretching of inorganic fine powder and organic filler or do not stretch constitute, in the film manufacture process, extrude the type (the Japanese documentation spy opens flat 2-84319 communique) of various heat sealability resins jointly, and bonding or laminate in advance heat sealability resin molding through embossing processing, and with various coating apparatus heat sealability resin-coating (spy open flat 2-122914 communique) such as types from the teeth outwards.

These existing mould internal shaping labels, when the mould internal shaping,, in manufacture process, need or bonding or laminate or design during at coating process the pattern that trapezoidal mould is arranged at the film that carries out embossing processing on the heat sealability resin or embossing is in advance processed in order to allow the air that is enclosed between forming containers and label discharge.In addition, in the time of can not being formed for discharging the pattern of these air from the teeth outwards, propose to have the pore that utilizes label itself to discharge the method (spy opens flat 2-108516 communique) of air.But, no matter take the sort of method, existing problems have problems such as manufacturing process complexity, productivity ratio are low, percent defective increase, manufacturing cost height inevitably.

In addition, utilize co-extrusion to be provided with in the existing method of heat sealability resin bed at the mould internal shaping in the label manufacture process, existing problems are that the viscosity during because of the hear resistance of the heat sealability resin that uses, corrosivity, fusion has nothing in common with each other the resin that restriction can be used.

In addition, in the existing method that adopts various coating processes equipment to be coated with, have in the method (spy opens flat 5-249895 communique) of having carried out coating heat sealability resin on the base material film surface of embossing processing in advance etc., because of the solvent absorbing of base material film low, most of smears concentrates on the recess of embossing on the base material film when drying, existing problems are to be difficult to reproduce on coating surface the embossing shape.Using under the situation of no absorptive film, the method for employing be with the intaglio plate coating machine heat melt type resin and solvent be the heat sealability cold coating after being coated with under the high viscosity state, usefulness engraved roll groove affix trapezoidal pattern on substrate surface.But in this case, because of using the high viscosity smears, existing problems are that productivity ratio is low, manufacturing cost is high, with an organic solvent easily cause fire and environmental pollution etc.

In addition, with in the label,, can not carry out even and distinct stable printing at existing mould internal shaping although want the bonding plane on the container is implemented printing.In addition, because of not recognizing these necessity, so, do not inquire into significantly for printing to the label bonding plane of mould internal shaping.

The present invention is a problem to solve these problems of the prior art.Promptly the objective of the invention is to, when base material film surface design heat sealability resinous coat, needn't design specific pattern and make the perforation pore, can improve the resin-coated printing applicability of heat sealability simultaneously at coating surface.The label that the present invention also aims to provide constitutes the selectivity of heat sealability resinous coat material by expansion, and reduces the restriction to coating process and process equipment, thereby boosts productivity and the in-mold labels performance.In addition, the mould internal shaping container that the present invention also aims to provide is that label is adhered to mould internal shaping container on the transparent vessel, and can see the printing of implementing clearly because of container transparent on the label bonding plane.

Summary of the invention

The inventor shows by conscientious result of study, is 5ml/m at the liquid absorption coefficient ²(ms) ^1/2Or above base material film surface coating water system heat sealability resin paint, on water system heat sealability resinous coat, implement printing again, just can solve the problems in producing, and the label of the mould internal shaping with good characteristic can obviously be provided, thereby finish the present invention.

The mould internal shaping label that promptly the present invention relates to is to be 5ml/m by the liquid absorption coefficient ²(ms) ^1/2Or the resin stretched membrane that above base material film is provided with water-soluble heat sealability resinous coat (E) constitutes, and implemented printing on this water system heat sealability resinous coat (E).

The base materials employed film surface opening of the present invention rate preferably 7% or more than, opacity be preferably 70% or more than, preferably in a direction, be stretched at least and the area extensibility is 2～80 times.In addition, base material film preferably contains thermoplastic resin (A), carried out the inorganic attritive powder of surface-treated (B), organic filler, dispersant (C) by at least a surface conditioning agent (D), particularly with respect to being that 20 weight %～80 weight %, inorganic attritive powder (B) are that 80 weight %～20 weight %, organic filler are that 0 weight %～50 weight % cooperates for resin combination 100 weight portions that form by thermoplastic resin (A), the content of dispersant (C) is preferably 0.01～100 weight portion.Inorganic attritive powder preferably uses surface conditioning agent (D) that hydrophilicity-imparting treatment was carried out on the surface.

The thermoplastic resin that is contained in the base material film (A) preferably crystalline polyolefin is a resin, dispersant (C) is acid modified polyolefin (sour degree of modification is 0.01%～20%) and/or silanol improved polyalkene preferably, inorganic attritive powder is that water-soluble cationic polymer and/or water soluble anion are surfactant and the inorganic attritive powder handled through surface conditioning agent (D) preferably, and aforementioned water-soluble cationic polymer preferably uses has diallyl amine salt and/or cyclopolymers of alkyldiallylamine salt and nonionic hydrophilic ethylene base monomer for constituting the material of unit.

Go up the printing of implementing at water-soluble heat sealability resinous coat (E) and can use hectographic printing, letterpress, intaglio printing, aniline printing, serigraphy, electrophotographic printing, ink jet printing, melting heat hectographic printing and heat of sublimation hectographic printing, especially preferably ink jet printing and intaglio printing.In addition, printing is preferably formed literal or the figure with information specific.

Water system heat sealability resinous coat (E) preferably utilizes the dispersion of water system and the layer that is provided with, and its average grain diameter is preferably greater than average opening footpath, base material film surface.

In addition, finished behind coating heat sealability resin when dry, the film coated surface of coating forms the dispersed particle form, and the phase transition temperature of heat sealability resin is 50 ℃～140 ℃.In addition, the coating of water system heat sealability resin paint can be adopted online and/or the arbitrary mode of off-line (or dual mode) is carried out.

The present invention be provided with water system heat sealability resinous coat (E) if base material film satisfy above-mentioned condition, also can be the laminated structure on other resin moldings or other materials.Particularly preferably make the base material film that is provided with water system heat sealability resinous coat (E) become outermost layer and with the laminated structure of other resin molding laminations.Therefore, of the present invention is the resin stretched membrane that outermost layer is provided with water-soluble heat sealability resinous coat (E), its base material film both can be that single layer structure also can be a sandwich construction, can also on the opposing face of water-soluble heat sealability resinous coat (E), implement printing, as long as satisfy above-mentioned condition just within the scope of the present invention.

In addition, the present invention also provides above-mentioned mould internal shaping has been sticked to the mould internal shaping container that has label on the transparent mould internal shaping container with label.Mould internal shaping container preferably adopts differential pressure forming process, hollow forming method, injection molding method, foaming and molding method, draw blow molding method or compression molding manufactured, and material can be selected from high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene, polyester, polystyrene, polyvinyl chloride and Merlon.

Mould internal shaping of the present invention has good base material film of liquid-absorbent and water system heat sealability resinous coat (E) with label, can demonstrate good in-mold labels applicability.Mould internal shaping of the present invention can adopt the mode that is less than the prior art coating weight to make with label, need not to carry out the Surface Machining such as embossing of in the past carrying out in order to discharge air, can make efficiently.And mould internal shaping of the present invention can adopt material formation widely with the heat sealability resinous coat (E) of label, has compared with prior art reduced the restriction to coating process and manufacturing equipment significantly.In addition, of the present invention mould internal shaping label with sticking to the container that has label on the transparent vessel, its characteristics are, the printing of can Visual Confirmation implementing on the label bonding plane by transparent vessel.

Brief Description Of Drawings

Fig. 1 is the schematic diagram of explanation emptying aperture bond length.

Fig. 2 is illustrated in the forming machine profile that uses in polyethylene or the used in-mold labels employment and suitability test (E ﹠ ST) of polystyrene hollow container.

Fig. 3 is illustrated in the forming machine profile that uses in the used in-mold labels employment and suitability test (E ﹠ ST) of PETG hollow container.

Fig. 4 shows that the present invention has the oblique view of the concrete example of mould internal shaping container (left figure) of label, and described forming containers adhesion has the mould internal shaping label (right figure) that is printing chevron patterns down on its bonding plane.

Number in the figure represents that respectively 1-a label printing face, 1-b label bonding plane, 2 metal patterns, 2-a inwall, 3 mouthfuls of moulds, 4 parisons, 5 attract hole, 6 air to be blown into nozzle, 11-a label printing face, 11-b label bonding plane, 12 metal patterns, 12-a inwall, 13 preforms, 14 attraction holes, 15 stretching bars.

The specific embodiment of invention

Hereinafter describe in detail by base material film and be provided with the mould internal shaping label of the present invention that the resin stretched membrane (below be called " resin stretched membrane of the present invention ") of water system heat sealability resinous coat (E) is formed.In addition, the number range with "～" expression is meant that the numerical value that comprises with record before and after "～" is the scope of lower limit and higher limit in this specification.

[thermoplastic resin (A)]

The base material film that is provided with water system heat sealability resinous coat (E) of the present invention contains thermoplastic resin.As the thermoplastic resin that uses in the base material film (A), that can give an example has a crystallinity propylene resin, perhaps high density polyethylene (HDPE), medium density polyethylene, crystallinity vinylites such as low density polyethylene (LDPE), crystalline polyolefins such as poly-Methyl-1-pentene are resin, nylon-6, nylon-6,6, nylon-6,10, nylon-6, polyamide-based resins such as 12, PETG or its copolymer, PEN, thermoplastic polyester resins such as aliphatic polyester, Merlon, amorphous polystyrene, syndiotactic polystyrene, thermoplastic resins such as polyphenylene sulfide etc.Also can mix and use two kinds or above this material.

Wherein, wait from resistance to chemical reagents and production cost, preferably using crystalline polyolefin is resin, more preferably uses the crystallinity propylene resin.

As the crystallinity propylene resin, preferred isotachyte or the syndyotactic polymer that forms by the propylene homopolymerization that use, also can use alpha-olefins such as ethene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene and copolymerization of propylene formation have various stereoregularities with the copolymer of propylene as principal component.Copolymer can be binary, ternary or above polynary system copolymer, both can be random copolymer, also can be block copolymer.

Thermoplastic resin in the base material film (A) content is generally 20 weight %～80 weight %, is preferably 25 weight %～75 weight %.

[inorganic attritive powder (B) and organic filler]

As the inorganic attritive powder (B) that can use in constituting the base material film of resin stretched membrane of the present invention, what can list has inorganic attritive powder such as powdered whiting, precipitated calcium carbonate, calcined clay, talcum, titanium oxide, barium sulfate, zinc oxide, magnesia, diatomite, silica, has the composite inorganic attritive powder, Hollow Glass Sphere of the oxide of aluminium or hydroxide etc. around inorganic attritive powder nuclear.Wherein, from reduce cost and when stretching, can form many holes aspect consideration, preferably use powdered whiting, calcined clay, diatomite.

Inorganic attritive powder (B) content in the base material film is preferably 20 weight %～80 weight %, more preferably 25 weight %～75 weight %.If the content of inorganic attritive powder (B) surpasses 80 weight %, the tendency that is difficult to stretch is then arranged, but when containing quantity not sufficient 20 weight %, the surface opening rate that can not obtain to wish, and the inadequate tendency of the improvement that makes the liquid absorption coefficient is arranged.

The organic filler that can use in constituting the base material film of resin stretched membrane of the present invention can select to use the resin of its fusing point or the glass transition temperature non-intermiscibility higher than above-mentioned thermoplastic resin (A), to reach the purpose that forms the hole.Polymer that PETG, polybutylene terephthalate (PBT), polyamide, Merlon, PEN, polystyrene, acrylate or methacrylate are arranged that instantiation can be enumerated or copolymer, melmac, poly-ethylidene thioether, polyimides, poly-ethylether ketone, polyphenylene sulfide, the homopolymers of cyclic olefin and the copolymer (COC) of cyclic olefin and ethene etc. etc.Using crystalline polyolefin at above-mentioned thermoplastic resin (A) is under the situation of resin, preferably selection use from the copolymer (COC) of the homopolymers of PETG, polybutylene terephthalate (PBT), polyamide, Merlon, PEN, polystyrene, cyclic olefin and cyclic olefin and ethene etc.

Organic filler content in the base material film is preferably 0～50 weight %, more preferably 0～40 weight %.

The average mark shot of the average grain diameter of the inorganic attritive powder that uses among the present invention or organic filler directly is preferably 0.1～20 μ m, the more preferably scope of 0.5～15 μ m.Consider the easy degree of mixing with thermoplastic resin (A), preferably using particle diameter is 0.1 μ m or above inorganic attritive powder.When particle diameter less than 0.1 μ m, having stretches is difficult to the tendency that forms the hole and can not obtain to have the stretched film on required surface, if when average grain diameter surpasses 20 μ m, has draftability to reduce and tension failure or cave mouth increase when being shaped tendency.

As an example, the average grain diameter of the inorganic attritive powder that the present invention uses can be measured with the particle metering device and try to achieve, and (the commodity special clarkes of Mike's labor by name (マ イ Network ロ ト ラ Star Network) produced of Co., Ltd.'s day machine dress system are measured and are accumulated in 50% particle diameter (accumulating 50% particle diameter) and calculate and try to achieve for example to use the laser diffraction particle gauge.

In addition, by dissolving mixing and disperseing, the particle diameter of the organic filler that disperses in thermoplastic resin can be used as mean value and calculates, and promptly uses electron microscope observation resin stretched membrane section, measures at least 10 particles, calculates particle diameter mean value.

Inorganic attritive powder and organic filler that the present invention uses can be used select in the above-mentioned substance a kind of separately, also can select two kinds or above being used in combination.Under two kinds or above situation about being used in combination, also can make inorganic attritive powder and organic filler combination.

Dispersant (C)

In base material film, can also preferably use dispersant (C).As the dispersant that in base material film, uses (C) can enumerate as acid modified polyolefin, silanol improved polyalkene etc.Wherein preferably use acid modified polyolefin.Enumerate as maleic anhydride as acid modified polyolefin and to carry out the polyolefin that contains anhydride group that random copolymerization or graft copolymerization form, perhaps unsaturated carboxylic acid such as methacrylic acid, acrylic acid carries out the polyolefin that contains the carboxylic acid group that random copolymerization or graft copolymerization form, and perhaps GMA carries out polyolefin that contains epoxy radicals that random copolymerization or graft copolymerization forms etc.As specific embodiment, enumerate polypropylene as maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, acrylic acid modified polypropylene, ethylene methacrylic acid random copolymer, ethylene methacrylic acid ethylene oxidic ester random copolymer, ethylene methacrylic acid glycidol ester graft copolymer, GMA modification etc., no matter be the sort of, wherein, preferred maleic anhydride modified polypropylene and maleic anhydride modified polyethylene.

Maleic anhydride modified polypropylene and maleic anhydride modified poly specific embodiment are enumerated improvement AP (モ デ イ Star Network AP) " P513V " (trade name) of producing as Mitsubishi Chemical's (strain) or improvement AP " M513 " (trade name), Sanyo and are changed into the HPR " VR101 " (trade name) that Yumex 1001,1010 (trade name) that industry (strain) produces or Yumex2000 (trade name), Mitsui Du Pont chemistry (strain) are produced.

The sour degree of modification of acid modified polyolefin is preferably 0.01%～20%, and more preferably 0.05%～15%.

The words of acid degree of modification less than 0.01%, surface treated inorganic attritive powder (B) has the inadequate tendency of dispersion effect in thermoplastic resin (A), if surpass 20%, the softening point that then has an acid modified polyolefin reduce and with the tendency of the compound difficulty of thermoplastic resin.

With respect to cooperate resin combination 100 weight portions that form by thermoplastic resin (A), inorganic attritive powder (B) and organic filler for, the content of dispersant in the base material film (C) is generally 0.01～100 weight portion, be preferably 0.05～90 weight portion, more preferably 0.1～80 weight portion.

If amount less than 0.01 weight portion of dispersant (C), because of surface treated inorganic attritive powder can not spread fully, the surface opening rate that can not obtain to expect has the inadequate tendency of improvement of liquid absorption coefficient.Otherwise, if 100 parts of overweights have the tendency that draftability descends significantly and the tension failure when being shaped increases.

[surface conditioning agent (D)]

The used inorganic attritive powder (B) of the present invention preferably carries out surface-treated through surface conditioning agent (D).The surface conditioning agent (D) that uses in the inorganic attritive powder (B) preferably carries out hydrophilicity-imparting treatment to the surface of inorganic attritive powder (B).Preferably as the water-soluble cationic polymer of the copolymer that is selected from the monomer (d1) of diallyl amine salt or cyclopolymers of alkyldiallylamine salt and nonionic hydrophilic ethylene base monomer (d2), perhaps water soluble anion is a surfactant as surface conditioning agent (D).Can be selected from chloride ion, bromide ion, sulfate ion, nitrate ion, methyl sulfate ion, ethyl sulfate ion and methanesulfonic acid ion for the anion that forms " salt " under the situation of water-soluble cationic polymer.

(d1) instantiation is enumerated as the cyclopolymers of alkyldiallylamine salt of carbon number 1～4 scope and dialkyl diallyl amine salt, be methyl diallyl amine salt and ethyl diallyl amine salt, the dimethyl diallyl amine salt, the methacryloxyethyl trimethyl ammonium, the acryloxy ethyl trimethyl ammonium, the chloride of methacryloxyethyl dimethyl one ethyl ammonium and acryloxy ethyl dimethyl one ethyl ammonium, bromide, mesylate, esilate, perhaps methacrylic acid N, N-dimethyl aminoethyl ester and acrylic acid N, N-dimethyl aminoethyl ester chloropropylene oxide, glycidol, epoxides such as glycidol trimethyl ammonium chloride carry out alkylation and the quaternary ammonium salt that obtains.Wherein preferred especially diallyl amine salt, methyl diallyl amine salt and dimethyl diallyl amine salt.

(d2) specific embodiment has been enumerated acrylamide, Methacrylamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl pyrrolidone, methacrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy ester, (methyl) acrylic acid 3-hydroxypropyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate.Wherein preferred propylene amide and Methacrylamide.

(d1) can set arbitrarily with (d2) combined polymerization ratio, but (d1) be preferably 10～99 moles of %, more preferably be preferably 50～97 moles of %, further be preferably 65～95 moles of %; (d2) be preferably 90～1 moles of %, more preferably 50～3 moles of % further are preferably 35～5 moles of %.

By (d1) and the surface conditioning agent (D) that (d2) obtains can followingly obtain, promptly, make above-mentioned monomer mixture use ammonium persulfate and 2 in aqueous medium, 2-azo (2-amidine propane) dihydrochloride etc. is that initator descended polymerisation 2 hours to 24 hours at 40 ℃～100 ℃ (for example 50 ℃～80 ℃).In order to reach purpose of the present invention, this polymer can adopt the spy to open flat 5-263010 communique, spy and open the method for record in the flat 7-300568 communique etc. and make.In addition, also can use the spy to open clear 57-48340 communique or the special part method of opening records such as clear 63-235377 communique.The wherein preferred diallylamine or hydrochloride, sulfate and the Methacrylamide of diallyl methyl amine, the copolymer of acrylamide.

The molecular weight of this polymer represents that with 25 ℃ inherent viscosity in the sodium-chloride water solution of 1mol/L concentration scope is 0.05～3 usually, and preferable range is 0.1～0.7, and more preferably scope is 0.1～0.45.In addition, represent with the weight average molecular weight that the gel osmoticing chromatogram analysis instrument is measured that it is about 5,000～950,000 that molecular weight ranges is generally, preferable range is 10,000～500,000, and more preferably scope is 10,000～80,000.

In addition, what use in inorganic attritive powder (B) is handled is the surface conditioning agent (D) that surfactant constitutes by water soluble anion, has anionic property functional group in its molecule.

Its specific embodiment can be enumerated, have the salt (d4) of the phosphoric acid one of higher alcohol of the sulfonate (d3) of the alkyl of carbon number 4～40 scopes, the phosphate ester salt of alkyl or carbon number 4～40 scopes or diester, the alkyl betaine of alkyl and alkyl sulfonation betaine (d5) etc., suitably select with the form that can obtain effect of the present invention with carbon number 4～30 scopes with carbon number 4～40 scopes." salt " in so-called (d3)～(d4) can be enumerated as lithium salts, sodium salt, sylvite, calcium salt, magnesium salts, primary～quaternary ammonium salt, uncle～quaternary alkylphosphonium salt, and preferred salt has lithium salts, sodium salt, sylvite, quaternary ammonium salt, more preferably sodium salt or sylvite.

(d3) sulfonate of alkyl that has carbon number 4～40 scopes in is for having carbon number 4～40, the sulfonate of the straight or branched of preferred 8～20 scopes or the alkyl of circulus, sulfo group alkanecarboxylic acid salt, specifically can enumerate carbon number 4～40, the alkylbenzenesulfonate of preferred 8～20 scopes, naphthalene sulfonate, carbon number 4～30, the alkylnaphthalene sulfonate that has straight or branched or circulus of preferred 8～20 scopes, has carbon number 1～30, the diphenyl ether of the alkyl of the straight or branched structure of preferred 8～20 scopes and the sulfonate of biphenyl, carbon number 1～30, the alkyl sulfate salt of preferred 8～20 scopes, the salt of sulfo group alkanecarboxylic acid ester, carbon number 8～30, the sulfonate of the epoxides addition product of the alkylol of preferred 10～20 scopes etc.

These material instantiations can be listed below: alkane sulfonate and aromatic sulphonate, the i.e. various isomers of the various isomers of Perfluorooctane sulfonate, dodecane sulfonate, hexadecane sulfonate, octadecane sulfonate, 1-or 2-dodecyl benzene sulfonate, 1-or 2-cetyl benzene sulfonate, 1-or 2-octadecane benzene sulfonate, dodecyl naphthalene sulfonate, beta-naphthalenesulfonic-acid formaldehyde condensation compound salt, octyl group xenyl sulfonate, dodecyl diphenyl ether sulfonate, dodecyl ligninsulfonate; Alkyl sulfate salt is lauryl sulfate, cetyl sulfate; Sulfo group alkanecarboxylic acid salt is the dialkyl of sulfosuccinic acid, alkyl has carbon number 1～30, the straight or branched of preferred 4～20 scopes or circulus, more particularly, the salt of sulfosuccinic acid two (2-ethylhexyl) ester, salt (the alkyl carbon atoms several 1～30 of N-methyl-N-(2-sulfo group ethyl) alkylamide, preferred 12～18), for example, derive from the amide compound of N methyl taurine and oleic acid, the 2-sulfoethyl salt of the carboxylic acid of carbon number 1～30 preferred 10～18, dodecyltriethanolamine sulfate, ammonium lauryl sulfate, polyoxyethylene ten diester sulfate, the polyoxyethylene cetyl sulfate; The sulfonate of the epoxides addition product of the alkylol of carbon number 8～30, preferred 10～20 scopes is the sulfuric acid etc. of ethylene oxide adduct of sulfuric acid, stearyl alcohol of ethylene oxide adduct of sulfuric acid, the cetyl alcohol of the ethylene oxide adduct of dodecyl alcohol.

As the phosphoric acid of the alkyl of the straight or branched with carbon number 4～40, preferred carbon number 8～20 scopes of (d4) or circulus-or the concrete example of diester salt or phosphotriester, that can enumerate has, the phosphotriester of the ethylene oxide adduct of the sodium salt of the disodium salt of the disodium salt of the disodium salt of monododecyl phosphte or di-potassium, phosphoric acid hexyl ester, the two dodecyl esters of phosphoric acid or di-potassium, the two hexyl esters of phosphoric acid or sylvite, dodecanol etc.

As the alkyl betaine of the alkyl with carbon number 4～30, preferred carbon number 10～20 scopes of (d5) and the concrete example of alkyl sulfobetaines, can list dodecyldimethylammonium hydroxide inner salt, octadecyl dimethyl betaine, dodecyl dimethyl (3-sulfo group propylidene) ammonium inner salt, hexadecane dimethyl (3-sulfo group propyl group) ammonium inner salt, octadecyl dimethyl (3-sulfo group propyl group) ammonium inner salt, 2-octyl group-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betaine, 2-dodecyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline betaine etc.

The sulfonate (d3) that wherein preferably has the alkyl of carbon number 4～30 scopes, more preferably from the alkane sulfonate of carbon number 10～20 scopes, have the alkyl of carbon number 10～20 scopes aromatic sulphonate, have the sulfuric acid etc. of epoxides addition product of alkylol of alkyl of carbon number 10～20 scopes and select.

[water-soluble heat sealability resinous coat (E)]

Water system heat sealability resinous coat of the present invention (E), as for thermoplastic resin hollow die forming or injection moulding the time, being placed in label in the metal die in advance, the situation of the mould internal shaping of adhesion label when being shaped, can as utilize with metal die in melting resin contact by it hot and evenly adhere to coating on the plastic holding device when melting shaping at once.In this case, can suitably select to use the heat sealability resin of suitable mould internal shaping with the water-based of label.Water system heat sealability resinous coat of the present invention (E) makes it become the coating of adhering with other membrane material with various heat sealing machines and also can play a role, at this moment, and can be according to the suitable heat sealability resins of selecting water-based such as surface nature of institute's adhesive film.

The resin that is used for water system heat sealability resinous coat (E), the dispersion with resin of the heat sealability that is applicable to mould internal shaping and heat-sealing is desirable for being shaped.As dispersion with heat sealability resin, for example can comprise material, through the material of suspension polymerisation through emulsion polymerisation, or with being dispersed in material in the aqueous solvent etc. after the mechanical crushing such as extruder.

As used heat sealability resin in the water system heat sealability resinous coat of the present invention (E), for example can use the dispersion of acrylic acid series polymeric compounds, vinyl acetate polymer, styrenic, vinyl chloride-based polymer, vinylidene chloride based polymer, polyethylene, polyurethane, polyester, epoxy resin, Petropols, rosin ester, silicones, alkyd resins, polybutadiene, butadiene copolymer, polybutene, buttress rubber, polypropylene, polychloroprene, polyisobutene etc.

Preferred acrylic acid series polymeric compounds, vinyl acetate polymer, styrenic wherein can be the water system dispersions of ethylene acrylic acid co polymer, ethylene methacrylic acid copolymer, ethylene acrylate copolymer, acrylate polymer, ethylene vinyl acetate copolymer, styrene-butadiene-copolymer in these materials.

The drying coated amount of heat sealability resin can suit according to the liquid absorption coefficient of employed base material film to select, but is preferably 0.05～30g/m usually ², more preferably 0.1～20g/m ², further preferred 0.2～10g/m ²

If drying coated quantity not sufficient 0.05g/m ², tend to the intermembranous adhesion strength of performance fully and container or other when mould internal shaping or heat-sealing.If drying coated amount surpasses 30g/m ²Though adhesion strength is high, for example has and make the part be easy to generate the tendency of swelling (heaving) with entering air between label and container because of the mould internal shaping.

If the coating quantitative change is many, existing problems are once to be coated with to finish coating, must repeatedly repeat coating, also can produce problems such as production cost raising.

The average grain diameter of the dispersion of heat sealability resin is preferably big than average opening footpath, base material film surface.And, after the resin-coated drying of heat sealability, wish on the base material film surface, to exist with particle shape.For this reason, must under phase transition temperature of heat sealability resin (be converted to liquid temperature by solid-state, claim to make film temperature again) or following temperature conditions, carry out drying.Consider that from mould internal shaping applicability aspect the phase transition temperature of heat sealability resin is preferably 50～140 ℃ of scopes, more preferably 55～130 ℃ of scopes.When dry, can not keep particle shape under surpassing 140 ℃ temperature, because of covering with smooth shape on the base material film surface, the problem of tending to be easy to generate comprises or produces in the mould internal shaping to be heaved, perhaps when printing or label add and produce adhesion phenomenon man-hour.In addition, when 50 ℃ of the phase transition temperature deficiencies of hot sealing layer, label tends to when preserving that hot sealing layer is clamminess or adhesion easily.

In addition, be coated with 30% or above, preferred 40～90%, more preferably 50～80% the situation that dried heat sealability resin coating is placed on the base material film surface and be suitable for the mould internal shaping.

Under the situation of overlay capacity less than 30%, tend to reduce cementability during the mould internal shaping with forming containers.

It is 90 ℃ ethylene methacrylic acid copolymer dispersion that the mould internal shaping is enumerated as average grain diameter 1.2 μ m, phase transition temperature with the instantiation of the used water system heat sealability resinous coat (E) of label.

In water system heat sealability resinous coat (E) in the used dispersion, can add various adhesive resins with the cementability of raising with base material film, add adhesion and prevent agent adhesion when preventing to process label, add the applicability of the sheet feeding/discharge when improving printing such as antiseize paste and antistatic agent.

In addition, can also suitably add dispersant, tackifier, defoamer, anticorrisive agent, ultra-violet absorber, ultra-violet stabilizer, antioxidant, surfactant, water soluble dyestuffs, coloring pigment etc. as required.

[surface treatment method of inorganic attritive powder]

The preferred at least a surface conditioning agent (D) that uses carries out surface treatment to inorganic attritive powder (B) among the present invention.As surface treatment method, go for known the whole bag of tricks, there is not particular determination.

Can suitably select mixing arrangement and temperature, time when mixing according to the proterties of employed surface conditioning agent composition and physical property.Also to suitably select the shape of the L/D (axial length/diameter of axle) of employed various mixers and stirring vane, shear velocity, specific energy, holdup time, processing time, treatment temperature etc. according to the proterties of using composition.

The surface treatment method example of inorganic attritive powder (B) such as following method, making with case of wet attrition under the situation of calcium carbonate, be to have for 100 parts of weight of 10～50 μ m calcium carbonate particles under the condition of surface conditioning agent (D) of institute's necessary amount with respect to particle diameter, case of wet attrition becomes desirable particle diameter in aqueous medium.Specifically, add water in calcium carbonate, the weight ratio that makes calcium carbonate/aqueous medium (being specially water) is in 70/30～30/70 scope, preferably in 60/40～40/60 scope; Wherein the amount with respect to the surface conditioning agent (D) that adds in calcium carbonate 100 weight portions is 0.01～10 weight portion, is preferably 0.1～5 weight portion, adopts conventional method to carry out case of wet attrition.Furthermore, be ready to the aqueous medium that predissolve has the surface conditioning agent of above-mentioned scope amount, this aqueous medium is mixed with calcium carbonate, just can use the conventional method case of wet attrition.Case of wet attrition can also can be used continous way with batch (-type), uses sand mill, Aunar to draw the grater etc. of the use reducing mechanism of his grinding machine (ア ト ラ イ タ one), ball mill etc.Adopt these case of wet attrition, just can obtain average grain diameter is the calcium carbonate that 0.1～20 μ m is preferably 0.5～15 μ m.

Subsequently, the case of wet attrition product are carried out drying, carry out grading technology before the drying, cross 350 mesh sieves and can remove meal.Drying can adopt known methods such as heated-air drying to carry out, and preferably adopts the media flow drying.So-called media flow drying is by following process various materials to be carried out dry method, promptly in drying tower, in the insulating particles group (fluidized bed) who is flow regime, supply with slurry like material by hot blast (80～150 ℃) effect, make the slurry like material supplied with on one side with membranaceous attached to the active medium particle surface that is flowing, in the hothouse that flows, disperse on one side, and the drying of accepting hot blast handles, thereby makes various materials obtain drying.The media flow drying device " medium slurry dried machine " that dry employing of this media flow as the manufacturing of (strain) nara machinery are produced etc. carries out easily.If use this media flow drying, can carry out the dismission (removal of primary particleization) of dry and condensed particles simultaneously.Adopting uses the same method can obtain the few calcium carbonate of meal amount.But, adopt desirable method to carry out that particle is pulverized and classification also is effective after the media flow drying.On the other hand, even dry and adopting common hot-air seasoning that case of wet attrition product are carried out under the dry situation, adopt the method for wishing to carry out the particle pulverizing and classification also is fine to the pie that is obtained without media flow.The dry pie of the case of wet attrition product that this method obtains is easy to cracked and obtains calcium carbonate microparticle easily, so needn't specially design the technology of pulverizing dry pie.

Available other the surface conditioning agent of the inorganic attritive powder (B) of Huo Deing is further handled like this.

The use amount of surface conditioning agent (D) is different because of the purposes of the resin stretched membrane that water system heat sealability resinous coat (E) is set of the present invention, usually for inorganic attritive powder 100 weight portions, its amount is in 0.01～10 weight portion, preferred 0.04～5 weight portion, the more preferably scope of 0.07～2 weight portion.

Use amount less than 0.01 weight portion of surface conditioning agent (D) tends to obtain surface treatment effect completely, if surpass 10 weight portions, the effect of tending to surface conditioning agent reaches capacity.

[constituent amount ratio]

The amount that constitutes the composition of the base material film that is provided with water system heat sealability resinous coat (E) among the present invention is preferably as follows than scope, in the resin combination that the organic filler by the surface treated inorganic attritive powder (B) of the thermoplastic resin (A) of 20～80 weight %, 80～20 weight %, 0～50 weight % constitutes, 100 weight portions that relative aforementioned thermoplastic resin (A), inorganic attritive powder (B) and/or organic filler add up to, containing dispersant (C) is 0.01～100 weight portion.At this moment,, tend to be difficult to obtain the film of uniform film thickness, if thermoplastic resin (A) surpasses 80 weight %, because of not obtaining to have the liquid absorption coefficient (10ml/m of expectation if inorganic attritive powder (B) and/or organic filler content surpass 80 weight % ²(ms) ^1/2Or more than) and the base material film of surface opening rate (7% or more than), therefore when being coated with the hot resin dispersion of aforementioned water system, particle in the dispersion enters peristome and tails off, and tends to obtain the water system heat sealability resinous coat (E) good with the cementability on base material film surface during the mould internal shaping.In addition, as required, can be combined with heat stabilizer, ultra-violet stabilizer, antioxidant, adhesion and prevent agent, nucleator, lubricant, colouring agent etc. in each constituent, the cooperation ratio of these materials is preferably 3 weight % or following.

[being provided with the manufacturing of the resin stretched membrane of water system heat sealability resinous coat (E)]

The resin stretched membrane that is provided with water system heat sealability resinous coat (E) can be by those skilled in the art by making known the whole bag of tricks is combined.Adopt the resin stretched membrane of either party's manufactured, as long as the condition that satisfies the present invention's record just within the scope of the present invention.

The resin stretched membrane ratio in accordance with regulations that is provided with water system heat sealability resinous coat of the present invention (E) is thermoplastic resin (A), carried out the inorganic attritive powder (B) of hydrophilicity-imparting treatment with surface conditioning agent (D), organic filler, dispersant (C) mixes, with method system film such as extruding, subsequently in the temperature of the fusing point that is lower than thermoplastic resin (A), the temperature lower edge single shaft direction or the biaxially oriented that preferably are lower than 3～60 ℃ of its fusing points stretch, thereby acquisition has the liquid-absorbent base material film in the fine hole of homogeneous (hole) in film surface and inside, in the manufacturing process of acquisition film, outside (online) and/or the technology (off-line), adopt known method can reach 0.05～30g/m to convert by solid portion ²Mode be coated with dispersion as ethylene methacrylic acid copolymer etc., in phase transition temperature or the following drying of carrying out, so that dispersion particle is present in the surface with particle shape, thereby can obtain to be provided with the tree film stretched film of good water system heat sealability resinous coat (E).

Resin stretched membrane of the present invention is 5ml/m at the liquid absorption coefficient ²(ms) ^1/2Or on the above base material film, the surface of adopting above-mentioned the whole bag of tricks to obtain is provided with water system heat sealability resinous coat, for example, utilize and supply in the label that on polypropylene screen, is provided with the mould internal shaping of heat sealability resin bed with known off-line rubbing method or online co-extruded method etc., just can obtain good mould internal shaping applicability with few coating weight, thereby the cheap mould internal shaping that can obtain highly productive and have a label quality is with label and product.

The liquid absorption coefficient of the liquid-absorbent base material film made from preceding method is at 5ml/ (m ²Ms ^1/2) or more than, preferably at 10ml/ (m ²Ms ^1/2) or more than, 15～50ml/ (m more preferably ²Ms ^1/2).If the not enough 5ml/ (m of liquid absorption coefficient ²Ms ^1/2), the absorption speed the during coating of water-based paint is insufficient, and coating fluid viscosity improves few, the configuration of surface that can not obtain desirable coating weight and film.

So-called in this specification " liquid absorption coefficient " adopts the BLISTOW water absorption test to measure according to JAPAN TAPPI No.51-87 standard, water suction curves according to suction beginning 20 microsecond to 40 microseconds, adopt least square method to obtain straight line, be meant the value of trying to achieve with its slope.The liquid absorption coefficient can be measured with hereinafter described testing the concrete order of putting down in writing in the example.

In addition, base material film outermost surface aperture opening ratio (surface voids rate) 7% or more than, be preferably 10～30%.If surface opening rate less than 7% is tended to obtain liquid-absorbent completely, on the contrary,, to tend to substrate surface intensity and descend if surpass 30%, when adhering on mould internal shaping container, existing problems are to peel off from substrate surface simply in the practicality.

" surface opening rate " in this specification and " average opening footpath " are meant in the viewing area when the aforementioned substrates film surface that the present invention is provided with water system heat sealability resinous coat (E) is observed the mean value of the bond length in 20 holes in the hole area occupied ratio and viewing area respectively under electron microscope.Specifically, cut a base material film sample part arbitrarily, stick on the sample observation platform, vacuum evaporation gold or gold-palladium on its sightingpiston, use electron microscope (as the scan microscope S-2400 of Hitachi (strain) manufacturing), observe surface voids down in any multiplication factor that is easy to observe (as 500 times～3000 times amplifications) and just can try to achieve.Taken pictures in observed zone again etc., the hole is painted into describes to brush on the film, (Nikon (strain) is made: this (Le one ゼ Star Network ス) IID of model western Shandong storehouse) carry out image and handle, also can regard the hole area occupation ratio as base material film surface opening rate with image analysis apparatus to the image after the brushing.In addition,, be determined at the bond length in 20 holes of surperficial upper shed, as average opening directly its mean value that calculates according to the electron micrograph of observing simultaneously.In addition, so-called hole bond length can illustrate to be exactly length on the direction shown in Figure 1.

Resin stretched membrane of the present invention, with water system heat sealability resinous coat (E) is outermost layer, adopt common various mode of printing (so-called in this specification " printing " is meant the notion that comprises lettering and impression) printing back to use at its reverse side, also can be stacked in thermoplastic resin film, laminated paper, slurry paper, nonwoven, cloth etc. according to purposes and go up use.Lamination was made after the stack membrane structure can stretch each layer respectively, also can make in the lamination after-drawing.And, can behind the surface of these stack membranes and back up, use.These methods also can suitably make up.

Resin stretched membrane of the present invention prints the back and uses with label as mould internal shaping of the present invention on the face that is provided with water system heat sealability resinous coat (E).By printing on the face that is provided with water system heat sealability resinous coat (E), additional various information on the face of pasting on can be in the transparency of PET bottle, PP bottle, LD-PE bottle and so on the high container perhaps improve ornamental and improve the surcharge of container.This printing can be used known method, and what for example can list has hectographic printing, letterpress, intaglio printing, aniline printing, serigraphy, electrophotographic printing, ink jet printing, melting heat hectographic printing and a heat of sublimation hectographic printing etc.Resin stretched membrane of the present invention is to the film after water system heat sealability resinous coat (E) printing, because of the property heaved, label cementability good, see through the clear hollow container that posts the aftermentioned label, can be identified in the printing of implementing on water system heat sealability resinous coat (E) face clearly.

The resin stretched membrane that the present invention is provided with water system heat sealability resinous coat (E) preferably is stretched on axially at one at least, also can be stretched on axially two.

For example, is the content that includes inorganic attritive powder 0～40 weight %, be preferably the crystalline polyolefin resin film of 3～33 weight %, be lower than under the low temperature of this melting point resin, along direction stretch the single shaft that obtained to alignment films as substrate layer, at least on its single face is stacked as the melting resin of outermost resin combination, this resin combination is, by thermoplastic resin (A) 20～80 weight %, in the resin combination that surface treated inorganic attritive powder (B) 80～20 weight % and organic filler 0～50 weight % constitute, with respect to aforementioned thermoplastic resin (A), the amount that contains dispersant (C) in total 100 weight portions of inorganic attritive powder (B) and organic filler is 0.01～100 weight portion, subsequently, on the direction vertical, this stack membrane is stretched with aforementioned draw direction, obtain outermost layer at 1 axial orientation and substrate layer at the base material film of the laminated structure article of 2 directions orientations.

In addition, at this base material film outermost surface water system heat sealability resinous coat (E) is set and obtains resin stretched membrane of the present invention.

Preferable production process comprises unified stretching the behind substrate layer and the outermost layer lamination, the operation of water system heat sealability resinous coat (E) is set on gained film surface.The situation of lamination is compared with indivedual stretchings, easy and low cost of manufacture.

Stretching can be used known the whole bag of tricks.Be stretching in than carrying out under melting point resin low 5 ℃ or the low more temperature, and, using under the situation of 2 kinds or above resin, preferably carrying out under low 5 ℃ or the low more temperature than the fusing point of the resin of shared use level maximum.

As the concrete grammar that stretches, can list stretching between the roller that utilizes roller group linear differential, utilize tentering insulating box (テ Application タ one オ one Block Application) to carry out clamping stretching etc.If stretch between the employing roller, can regulate draw ratio arbitrarily, obtain to have the film of any rigidity, opacity, smoothness, glossiness easily, so be preferred.Draw ratio is not particularly limited, can be according to the present invention resin stretched membrane application target and used resin characteristic and determine.Be generally 2～11 times, preferably in 3～10 times of scopes, stretch.Wherein more preferably draw ratio is 4～7 times.

Under the situation of utilizing the clamping of tentering baking oven to stretch, draw ratio is preferably 4～11 times.The area multiple is generally 2～80 times, is preferably 3～60 times, more preferably 4～50 times.If 2 times of area multiple less thaies, the aperture opening ratio that can not obtain to stipulate on the resin stretched membrane surface can not obtain sufficient water imbibition, tends to be difficult to be provided with in its surface the water system heat sealability resinous coat (E) that has good bonding with container.If surpass 80 times, have tension failure and thick hole and become many tendencies.

Preferably on the base material film after the stretching, heat-treat.Heat treated temperature is preferably being selected to the temperature range that is higher than 30 ℃ of draft temperatures from draft temperature.By heat treatment, the percent thermal shrinkage of draw direction reduces, the minimizings such as discounting that flanging when making the goods keeping or the contraction during because of heat and molten disconnected the sealing cause.Heat-treating methods generally can adopt roller and oven heat to handle, and also they combinations can be handled.These are handled from obtaining better thermal effectiveness, and it is preferred heat-treating under the state of the maintenance of the film after stretching anxiety.

In addition, implement oxidation processes such as surface corona processing and plasma treatment after the heat treatment.By oxidation processes, when being set, improves water system heat sealability resinous coat (E) surperficial wettable, improve the solvent infiltration rate of water system heat sealability resin dispersion, help the littler resin in size ratio opening footpath and enter rapidly and more, so be desirable.

The opacity of the base material film after the stretching be 70% or more than, be preferably 75～100%, more preferably 80～100%.

In addition, also help improving adherence with water system heat sealability resin.

The resin stretched membrane integral thickness that is provided with water system heat sealability resinous coat (E) does not have particular determination, preferably in 40～400 μ m, more preferably 50～350 μ m, the scope of preferred 60～300 μ m further.If consider the absorption of contained water solvent in the water system heat sealability resin dispersion, then the outermost layer thickness of the base material film that joins with water system heat sealability resinous coat (E) is preferably 3～100 μ m, more preferably 5～80 μ m.According to application target, the thickness of water system heat sealability resinous coat (E) is preferably 0.05～40 μ m, more preferably 0.1～30 μ m.

[container that has label]

Mould internal shaping of the present invention can adhere on the container according to common mould internal shaping method with label.When carrying out the mould internal shaping, can touch container by water system heat sealability resinous coat (E) side that is arranged so that label of the present invention.Specifically, mould internal shaping order can be with reference to embodiment described later.

By mould internal shaping of the present invention is sticked on the transparent vessel with label, just can obtain the film internal shaping container that the present invention has label.The mould internal shaping container that the present invention has label has the so-called printing that transparent vessel energy Visual Confirmation is implemented that sees through on the label bonding plane.For this reason, the mould internal shaping container that has label of the present invention can improve the informedness of container, and enlarges the form of utilizing significantly.For example, if on the label bonding plane printing word and graphical information, just can transmit its information to the user through transparent vessel.In addition, if printing has the style of taste on label stickup face, see through transparent vessel and these information can be conveyed to the user.Fig. 4 expresses the example at (the left figure) that pasted the mould internal shaping container that has label that is printed with chevron patterns down label (right figure) on bonding plane.Label paste position and size do not have particular determination.

The printing of implementing on the label bonding plane, also can be in transparent vessel in the filling during content clearly Visual Confirmation and after taking out content Visual Confirmation clearly.The opaque content of filling or can realize this form in transparent vessel for example with the homochromy content of printing.On the contrary, the printing of also can be in transparent vessel being implemented on also can Visual Confirmation label bonding plane during content in the filling.For example, the transparent content thing just can constitute this form in the filling.Therefore, carry out suitable selection combination, just can utilize characteristics of the present invention with various forms by printing and the content that will implement on the label bonding plane.

By kind, the phase transition temperature of suitable selection water system heat sealability resin, mould internal shaping of the present invention just can be used for the plastic holding device that various materials are made with label.For example, the container that constitutes by high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene, polyester, polystyrene, polyvinyl chloride and Merlon etc. be can be used for, high density polyethylene (HDPE), polypropylene, polyester, polystyrene wherein more are applicable to.These plastic holding devices adopt differential pressure shaping, hollow forming, injection moulding, foaming and molding, draw blow molding or compression molding manufacturing.Wherein, more suitable differential pressure shaping, hollow forming, injection moulding, draw blow molding.Also have in addition to enlarge and use with having a few on the special container of label shaping difficulty of the prior art.

Coating process as the heat sealability resin, adopt Wiper blade type, rod-type, line bar type, sliding hopper formula, curtain formula, molding type, air-blade type, roll-type, elder brother horse (コ Application マ) formula, size press formula, recessed formula, fall general coating process such as recessed formula, the method that also can use these general coating processes of appropriate combination to be coated with.

Drying means after the coating can adopt known drying mode, but must be to carry out drying under the condition of the phase transition temperature of the heat sealability resin that is no more than use in the dry run.

Embodiment

Hereinafter, be example to modulate example, Production Example, embodiment, comparative example and test example, be described more specifically the present invention.Material shown in following examples, use amount, ratio, contents processing, processing sequence etc. are only otherwise breaking away from the scope of the invention then can suitably change.Therefore, scope of the present invention is not limited to the explanation of following described instantiation.

The modulation of (modulation example 1) surface conditioning agent (D)

In the reactor that has circulation cooler, thermometer, dropping funel, agitator and gas introduction tube, put into diallyl amine hydrochlorate (concentration is the aqueous solution of 60 weight %), 13 weight portion acrylamides (concentration is the aqueous solution of 40 weight %) and 40 weight parts waters of 500 weight portions, the limit makes nitrogen flow into the limit temperature in the system is elevated to 80 ℃.Stir down, with dropping funel with 4 hours dropping polymerization initiators and ammonium persulfate (concentration is the aqueous solution of 25 weight %) 30 weight portions.Drip and finish back continuation reaction 1 hour, obtain the faint yellow aqueous thing of thickness.The acetone of getting this liquid material 50g injection 500ml produces white precipitate.Filter to isolate sediment, use 100ml acetone rinsing secondary more respectively after, vacuum drying obtains white solid shaped polymer (water-soluble cationic polymer), the weight average molecular weight that resulting polymers is obtained with GPC is 55,000.

The modulation of (modulation example 2) surface treatment powdered whiting

(average grain diameter is 8 μ m the powdered whiting of 40 weight %, the dry type of Japan adhesive society system is pulverized product) and the water of 60 weight % fully stir into pulpous state, in the powdered whiting of per 100 weight portions, add surface conditioning agent (D) 0.06 weight portion of making in the modulation example 1, dilatory with desk-top Ah according to special (ア ト ラ イ タ one) type medium mixer (diameter is 1.5mm bead, pack completeness 170%, linear velocity 10m/sec) case of wet attrition.

Subsequently, to add carbon number be that 14 alkane sulfonic acid sodium and carbon number are 50 parts of stirrings of mixture (concentration is the aqueous solution of 2 weight %) of 16 alkane sulfonic acid sodium to principal component.Afterwards, by 350 mesh sieve classifications, passing through 350 purpose slurries media flow drying machine ((strain) nara machinery is made the MSD-200 of manufacturing) drying.Measuring the calcium carbonate average grain diameter that is obtained with microdetermination instrument (a day machine dress (strain) is made) is 1.5 μ m.

Production Example

Satisfy used base material film (Production Example 9～15) in the base material film (Production Example 1～8) of condition of the present invention and the comparative example according to the following order manufacturing.

Employed material write up is in table 1." MFR " refers to molten flow rate in the table.Employed material category and consumption (weight %), stretching condition, each layer thickness and opacity during the various base material films of record are made in the table 2.The material number of record is corresponding with the material number of record in the table 1 in the table 2.In addition, the dispersant addition of table 2 is used with respect to the weight portion of total addition 100 weight portions of material 1～3 and is represented.

In Production Example 1～6,9,10, the complex [A] of table 2 record is melting mixing in being set at 250 ℃ extruder, behind the extrusion molding, is cooled to 70 ℃ in cooling device, and obtaining individual layer does not have stretched sheet.

After this no stretched sheet being heated to draft temperature (1) heating of table 2 record, longitudinal stretching is 5 times between roller, obtains vertical monadic stretching membrane.Subsequently, the complex [B] of table 2 record melting mixing in being set at 250 ℃ extruder, and be stacked in the two sides of aforementioned vertical monadic stretching membrane.Draft temperature (2) heating of laminate in table 2 record, with 8 times of tentering stretching-machine cross directional stretch, under the temperature that is higher than (2) 20 ℃ of draft temperatures, heat-treat, obtain uniaxial tension/biaxial stretch-formed/3 layers of biaxial stretch-formed resin stretched membrane.

In Production Example 7, the complex [A] of table 2 record and complex [B] melting mixing in being set at three extruders of 250 ℃ respectively, be squeezed into sheet with the mould lamination of feed capitiform formula, be cooled to 70 ℃ with cooling device, obtain 3 layers of no stretched sheet.This no stretched sheet is after draft temperature (1) heating of table 2 record, longitudinal stretching is 5 times between roller, subsequently, after draft temperature (2) heating, with 8 times of tentering stretching-machine cross directional stretch, heat-treat in the temperature that is higher than (2) 20 ℃ of draft temperatures, obtain biaxial stretch-formed/biaxial stretch-formed/3 layers of biaxial stretch-formed resin stretched membrane.

In Production Example 8, the complex [B] of table 2 record melting mixing in being set at 250 ℃ extruder, extrusion molding is cooled to 70 ℃ with cooling device, and obtaining individual layer does not have stretched sheet.This no stretched sheet is after draft temperature (1) heating of table 2 record, and longitudinal stretching is 5 times between roller, heat-treats in the temperature that is higher than (1) 20 ℃ of draft temperature, obtains the resin stretched membrane of vertical uniaxial tension.

In Production Example 11, use special 3 layers of resin stretched membrane opening uniaxial tension among the embodiment 3 that puts down in writing in the 2001-181423 communique/biaxial stretch-formed/uniaxial tension.

In Production Example 12, use special 3 layers of resin stretched membrane opening the uniaxial tension/biaxial stretch-formed/uniaxial tension among the embodiment 3 that puts down in writing in the 2001-226507 communique.

In Production Example 13, use special 3 layers of resin stretched membrane opening the uniaxial tension/biaxial stretch-formed/uniaxial tension among the embodiment 3 that puts down in writing in the 2001-164017 communique.

In Production Example 14, use special 3 layers of resin stretched membrane opening the uniaxial tension/biaxial stretch-formed/uniaxial tension among the embodiment 4 that puts down in writing in the 2001-151918 communique.

In Production Example 15, use special 3 layers of resin stretched membrane opening the uniaxial tension/biaxial stretch-formed/uniaxial tension among the embodiment 2 that puts down in writing in the flat 10-212367 communique.

On the individual layer that in Production Example 1～15, obtains and the two sides of 3 layers of resin stretched membrane, carry out the sided corona treatment that 40w/m2 divides, obtain base material film with discharge process machine (springtime motor (strain) manufacturing).The opacity of each base material film is that (institute's body (ス ガ) test machines (strain) are made: SM-5) measure, the result is illustrated in the table 2 standard with determinator with JIS P-8138.

Table 1

Material number	Title material	Content
			1	Noblen	The Noblen of MFR4g/10min (230 ℃, 2.16kg load-carrying), fusing point 164 ℃ (DSC peak temperatures) (make: trade name ノ バ テ Star Network PP " FY4 ") by Japanese polymeric chemical (strain)
2	Powdered whiting	The calcium carbonate that the dry type of average grain diameter 1.2 μ m is pulverized (make: trade name " ソ Off ト Application 1800 ") by shiraishi calcium (strain)
			3	The surface treatment powdered whiting	The surface treatment powdered whiting that modulation example 2 is enumerated through case of wet attrition and surface treatment gained
4	The polypropylene of maleic acid modification	Softening point is that (Sanyo changes into industry (strain) and makes: trade name Yemex1001 (maleic acid degree of modification 5%)) for the polypropylene of 154 ℃ maleic acid modification
			5	The polypropylene of maleic acid modification	Softening point is that (Sanyo changes into industry (strain) and makes: trade name Yemex1010 (maleic acid degree of modification 10%)) for the polypropylene of 145 ℃ maleic acid modification
6	The polypropylene of silanol modification	(Mitsubishi Chemical's (strain) makes the polypropylene of MFR11g/10min (190 ℃, 2.16kg load-carrying) silanol modification: trade name リ Application Network ロ Application PP " XPM800H ")

[table 2]

(embodiment 1～8, comparative example 1～7)

The adhesion of the dispersion of the heat sealability resin formation of table 3 record, table 3 record is prevented that agent and water from mixing in the mode that can form the solid component concentration of stipulating, is modulated into the water system paint of table 4 record.This water system paint being coated on the base material film table side of Production Example 1～15 with the slit die coating machine by on-line velocity 20m/min, pressing the baking temperature of table 4 record, is the stove drying of 10m with preseting length, forms the heat sealability resinous coat, acquisition mould internal shaping label film.The dried coating weight of the film that is obtained is documented in the table 4.

Carry out ink jet printing and intaglio printing being provided with on resin-coated of the heat sealability of gained film by following condition, after having made the inner face decorative pattern, stamping-out growth 70mm, wide 60mm make mould internal shaping label.

＜ink jet printing 〉

Printing machine: the BJF-850C of Canon (CANON) (6 looks, dye ink)

Lettering style: Japanese Standards Association SCID grape wine and food containers " A4 "

Lettering is set: common paper pattern, the color revisal that does not cause because of driver

Environment for use: Windows (login trade mark) ME Pentium (Pentium) 41.8GHz, RAM512MB I/F in parallel

Use software: Adobe Photoshop 5.0J

＜intaglio printing 〉

The 10 look machines that printing machine: DNK makes

Printing style: Japanese Standards Association SCID grape wine and food containers " A4 "

China ink: the CSUP (yellow, blue, red 3 looks) that the industry (strain) of refining big day is made

Version roller: 175 lines

(test example)

Inorganic attritive powder dispersiveness, surface opening rate, surface opening footpath, liquid absorption coefficient are estimated in each base material film surface that Production Example is made.The detailed content of each test is described below.

1) dispersiveness of inorganic attritive powder

Each base material film of Production Example 1～15 manufacturing is cut into the piece of long 500mm * wide 500mm, per relatively 20 ° of angle reverberation numbers go out 0.1mm or above inorganic attritive powder agglutinator (surface protuberances) on its surface (face of complex [B]), number in the counting per unit area divides following 3 grades to estimate.

Zero: 3/m of less than ²

△: more than or equal to 3/m ², 10/m of less than ²

*: more than or equal to 10/m ²

2) surface opening rate, opening footpath

Each base material film that Production Example 1～15 is made cuts arbitrary part, be attached on the observation sample platform, go up gold evaporation at its sightingpiston (surface of complex [B]), (Hitachi (strain) makes, and S-2400) amplifies 2000 times to surperficial photography photo with scan microscope.Describing to describe hole and brushing on the film, (Nikon (ニ レ コ) (strain) is made: this (Le one ゼ Star Network ス) IID of model western Shandong storehouse) figure to brushing carries out the image processing, determines the surface opening rate of resin molding with image analysis apparatus.

On surface picture, select arbitrarily 20 in hole again, calculate bond length by the center, hole, with its mean value as the surface opening footpath.

3) liquid absorption coefficient

To the liquid absorption coefficient of each base material film of Production Example 1～15 manufacturing, press BRISTOW method (JAPAN TAPPI No.51-87), and (Xiong Gu reason machine industry (strain) is made: BRISTOW testing machine II type) measure to use the dynamic absorbent test machine of liquid.Water suction curves by back 20 microsecond to 40 microseconds under the drips of solution obtains straight line with least square method, tries to achieve the liquid absorption coefficient by its slope.Measuring solution uses mix the mixed liquor that the stamping ink (redness) (its Hart of going into business (シ ヤ チ Ha タ) (strain) manufacturing) as 2 weight % of illuminating colour forms in the distilled water of 98 weight %.The liquid absorption coefficient is big or small with following 4 grades of evaluations.△ refers to that practicality has problem, * referring to can not be practical.

◎: more than or equal to 15ml/ (m ²Ms ^1/2)

Zero: more than or equal to 5ml/ (m ²Ms ^1/2), not enough 15ml/ (m ²Ms ^1/2)

△: more than or equal to 1ml/ (m ²Ms ^1/2), not enough 5ml/ (m ²Ms ^1/2)

*: not enough 1ml/ (m ²Ms ^1/2)

The resin-coated base material film of heat sealability that is provided with that is obtained in embodiment, the comparative example is estimated coating surface form, in-mold labels applicability (label dress subsides property, the property heaved, adherence).The detailed description of each evaluation test is described below.

4) coating surface form

(Hitachi (strain) makes, and S-2400) observes for 2000 times being provided with the amplification of the resin-coated base material film coating surface of heat sealability 10 places in embodiment 1～8, the comparative example 1～7 with flying-spot microscope.Observe the whether remaining used dispersion particle form that has, divide following 3 grades to carry out estimating judgement.

◎: be particle shape entirely.

Zero: can see between a part of particle and dissolve, but practical no problem.

*: can't see particle shape fully, become membranaceous.

5) in-mold labels employment and suitability test (E ﹠ ST)

Being provided with the resin-coated base material film stamping-out of heat sealability growth 70mm, wide 60mm in embodiment 1～8, the comparative example 1～7, make label.As shown in Figure 2, attract hole (5) decompression to attract and load fixingly by vacuum decompression, make to contact with 25 ℃ metal pattern (2) inwall (2-a) of being set to of the printing surface (1-a) of face (1-b) opposition side that has been coated with the heat sealability resin and hollow container manufacturing forming machine.Subsequently, the high density polyethylene (HDPE) of heating and melting to 180 ℃ (HDPE, Japanese polymeric chemical (strain) is made, trade name HB-330) injection cycle is carried out hollow forming in 12 seconds, obtain to have the hollow container of label.

Equally, use the high impact polystyrene (HIPS, big Japanese prepared Chinese ink chemical industry (strain) is made, trade name Di Kusi (デ イ Network ス) styrene IB-100) of heating and melting to 210 ℃ to obtain to have the hollow container of label.

In addition, as shown in Figure 3, attract hole (14) decompression to attract and load fixingly by vacuum decompression, make that (approximately very 25 ℃ metal pattern (12) inwall (12-a) of being set to of (ヨ-キ) industry (Co., Ltd.) is made: " trade name PET-2W type ") contacts with the printing surface (11-a) of face (11-b) opposition side that has been coated with the heat sealability resin and drawing blow molding machine.Subsequently, the PETG (PEP that is configured as the preform (13) of small containers shape in advance with injection machine, the excellent Ni Hante of Japan (ユ ニ ペ Star ト) (strain) makes: the famous-brand and high-quality Ni Hante of commodity (ユ ニ ペ Star ト) RT543) be heated to 95 ℃ with infrared heater, 30 seconds hollow formings that stretch of injection cycle, acquisition has the hollow container of label.

Adopt following method to estimate to label dress subsides property in these shapings and the hollow container that has that is obtained.

5-1) label dress subsides property

The dress situation of pasting to label in the hollow forming of 100 injections has carried out estimating judgement by following benchmark.

Zero: whole appointment place no problem ground dress pastes.

△: label nowhere, but as seen skew on the label assigned address has problems in practicality.

*: dress pastes markers and signs, as seen skew on the label assigned address.

5-2) the property heaved

The situation of pasting by labelled dress of 20 each gained containers is judged by following benchmark.

5 points: whole the generation heaved.

4 points: generation is heaved and is accounted for label area less than 10%.

3 points: produce heave account for the label area more than or equal to 10%, less than 20%.

2 points: produce heave account for the label area more than or equal to 20%, less than 50%.

4 points: generation is heaved and is accounted for the label area more than or equal to 50%.

Estimate (working to the last minute is 100 points) with always counting of 20 containers

Zero: 100 point

△: 80～99 points

*: 79 or following

5-3) label adherence

Label segment on the container that has label is cut at 4 becomes 15mm wide, a peeling label end part, (Ao Liaientike (オ リ エ Application テ Star Network) (strain) makes: the RTM type) press the velocity determination peel strength (g) that 200mm/ divides, calculate its mean value and judge by benchmark shown below with cupping machine.

Zero: more than or equal to 200g

△: 100～not enough 200g

*: not enough 100g

6) the printing applicability of heat sealability resinous coat face

Mould internal shaping label to embodiment 1, comparative example 1,7 has carried out following test.

As shown in Figure 2, attract hole (5) decompression attraction and load fixing by vacuum decompression, make to implement ink jet printing and intaglio printing and printing surface (1-a) face (1-b) opposition side that has been coated with the heat sealability resin that 25 ℃ metal pattern (2) inwall (2-a) of being set to of making forming machine with hollow container contacts.Subsequently, will be in low density polyethylene (LDPE) (LDPE, Japanese polymeric chemical (strain) manufacturing: trade name ZE41) carried out hollow forming in 12 seconds, obtain to have the hollow container of label of 160 ℃ of heating and meltings with injection cycle.

In addition, as shown in Figure 3, attract hole (15) decompression to attract and load fixingly by vacuum decompression, make 25 ℃ metal pattern (12) inwall (12-a) of being set to that implements ink jet printing and intaglio printing and printing surface (11-a) face (11-b) opposition side that has been coated with the heat sealability resin and drawing blow molding machine (approximately strange (ヨ one キ) industry (Co., Ltd.) is made: " trade name PET-2W type ") contact.Subsequently, the PETG (PEP that is configured as the preform (13) of small containers shape in advance with injection machine, the excellent Ni Hante of Japan (ユ ニ ペ Star ト) (strain) makes: the famous-brand and high-quality Ni Hante of commodity (ユ ニ ペ Star ト) RT543) be heated to 95 ℃ with infrared heater, 30 seconds hollow formings that stretch of injection cycle, acquisition has the hollow container of label.

These hollow containers that have label that obtain that are shaped are adopted said method evaluation property heaved and label adherence.Mould internal shaping label among the embodiment 1 is used for the hollow container of low density polyethylene (LDPE), any manufacturing of PETG, all has good property heaved and adherence.

In addition, see through the clear hollow container that has label, the printing state of implementing on visualization heat sealability resinous coat (E) face has carried out estimating judgement fully by following benchmark.

Zero: obviously observe the printing of implementing on heat sealability resinous coat (E) face.

*: the printing of implementing on heat sealability resinous coat (E) face is not obvious.

Table 4 and table 5 are expressed each result of the test.Even the mould internal shaping beyond the embodiment 1 also has the good results identical with embodiment 1 with label.

Table 3

Dispersion (1)	The ethylene methacrylic acid copolymer of 90 ℃ of phase transition temperatures, average grain diameter 0.7 μ m (central physics and chemistry industry (strain) is made, trade name ア Network ア テ Star Network ス AC-3100)
		Dispersion (2)	The ethylene vinyl acetate copolymer of 70 ℃ of phase transition temperatures, average grain diameter 1.2 μ m (central physics and chemistry industry (strain) is made, trade name ア Network ア テ Star Network ス EC-4800)
Dispersion (3)	The ethylene vinyl acetate copolymer of 80 ℃ of phase transition temperatures, average grain diameter 0.8 μ m (central physics and chemistry industry (strain) is made, trade name ア Network ア テ Star Network ス MC-3800)
		Dispersion (4)	The ethylene vinyl acetate copolymer of 60 ℃ of phase transition temperatures, average grain diameter 1.7 μ m (central physics and chemistry industry (strain) is made, trade name ア Network ア テ Star Network ス EC-1700)
Adhesion prevents agent	The ethylene methacrylic acid methyl terpolymer of 108 ℃ of phase transition temperatures, average grain diameter 0.7 μ m (central physics and chemistry industry (strain) is made, trade name リ カ ボ Application De ES-90)

Table 5

From above result obviously as can be seen, mould internal shaping label of the present invention can be brought into play good in-mold labels applicability, and the printing applicability of bonding plane is good (embodiment 1～8) also.In addition, usefulness also is, under situation about being attached on the transparent vessel, sees through the printing that transparent vessel can confirm obviously that the label bonding plane is implemented.Relative therewith, the mould internal shaping that does not possess condition of the present invention is low with the applicability of label, does not have practicality (comparative example 1～7).

Utilize possibility on the industry

Resin stretched membrane of the present invention has the good base material film of liquid-absorbent and water system heat sealability resinous coat, has good in-mold labels applicability. Resin stretched membrane of the present invention can be made with the coating weight that is less than prior art, because not needing to carry out the Surface Machining such as embossing that prior art is carried out for discharging air, can more effectively make. In addition, the heat sealability resinous coat that consists of resin stretched membrane of the present invention can be used widely material formation, and compared with prior art, has significantly reduced related coating and the restriction for the treatment of facility. Because having these characteristics, resin stretched membrane of the present invention can the utmost point usefully as the mould internal shaping label of the non-polyolefin-based resins containers such as polystyrene and polyester, say nothing of also and can be used as polyolefin-based resins container mould internal shaping label.

In addition, be pasted with the container of the tape label of mould internal shaping label of the present invention on the transparent vessel, have the advantages that to observe the printing of implementing on the label sticking face through container. Therefore, can improve the informedness with label container, can be used for various use states, from this point, greatly improve industry and utilized possibility.

Claims (26)

1. mould internal shaping label is by being 5ml/m at the liquid absorption coefficient ²(ms) ^1/2Or above base material film is provided with the resin stretched membrane formation of water system heat sealability resinous coat (E), and on this water system heat sealability resinous coat (E), implemented printing, described base material film contains thermoplastic resin (A), at least carried out inorganic attritive powder of surface-treated (B) and dispersant (C) by a kind of surface conditioning agent (D), with respect to being 20 weight %～80 weight % with thermoplastic resin (A), inorganic attritive powder (B) is 80 weight %～20 weight %, organic filler is resin combination 100 weight portions that the ratio of 0 weight %～50 weight % cooperates, and the amount that described base material film contains dispersant (C) is 0.01～100 part of weight portion.

2. according to the mould internal shaping label of claim 1 record, the surface opening rate of described base material film be 7% or more than.

3. according to the mould internal shaping label of claim 1 record, the opacity of described base material film be 70% or more than.

4. according to the mould internal shaping label of claim 1 record, thermoplastic resin (A) is that crystalline polyolefin is a resin.

5. according to the mould internal shaping label of claim 1 record, dispersant (C) is acid modified polyolefin and/or silanol improved polyalkene.

6. according to the mould internal shaping label of claim 5 record, the sour degree of modification that it is characterized in that described acid modified polyolefin is 0.01%～20%.

7. according to the mould internal shaping label of claim 1 record, it is characterized in that hydrophilicity-imparting treatment is carried out with surface conditioning agent (D) in the surface of described inorganic attritive powder (B).

8. according to the mould internal shaping label of claim 7 record, described surface conditioning agent (D) is that water-soluble cationic polymer and/or water soluble anion are surfactant.

9. the mould internal shaping label of record according to Claim 8, described water-soluble cationic polymer serves as the formation unit with diallyl amine salt and/or cyclopolymers of alkyldiallylamine salt and nonionic hydrophilic ethylene base monomer.

10. according to the mould internal shaping label of claim 1 record, described base material film is stretched at 1 direction of principal axis at least, and area extension area multiple is 2～80 times.

11. according to the mould internal shaping label of claim 1 record, hectographic printing, letterpress, intaglio printing, aniline printing, serigraphy, electrophotographic printing, ink jet printing, melting heat hectographic printing or heat of sublimation hectographic printing are used in described printing.

12. according to the mould internal shaping label of claim 1 record, ink jet printing or intaglio printing are adopted in described printing.

13. according to the mould internal shaping label of claim 1 record, described water system heat sealability resinous coat (E) is to contain by coating to carry out drying behind the coating fluid of water system dispersion and be provided with.

14. according to the mould internal shaping label of claim 13 record, the average grain diameter of described dispersion is greater than the average opening footpath on described base material film surface.

15. according to the mould internal shaping label of claim 13 record, described dispersion is coated on the base material film surface with particle shape.

16. according to the mould internal shaping label of claim 1 record, the phase transition temperature of contained heat sealability resin is 50 ℃～140 ℃ in the described water system heat sealability resinous coat (E).

17. according to the mould internal shaping label of claim 1 record, described water system heat sealability resinous coat (E) is to adopt online coating and/or off-line to be coated with and to be provided with.

18., implement printing at water system heat sealability resinous coat (E) reverse side of described resin stretched membrane according to the mould internal shaping label of claim 1 record.

19. according to the mould internal shaping label of claim 1 record, described printing has informedness.

20. according to the mould internal shaping label of claim 1 record, described printing is to have informational literal or figure.

21. have the mould internal shaping container of label, it is stained with the label of claim 1 record on transparent mould internal shaping container.

22. according to the mould internal shaping container of claim 21 record, described mould internal shaping container is to adopt differential pressure shaping, hollow forming, injection moulding, foaming and molding, stretch-blow or compression molding to make.

23. according to the mould internal shaping container of claim 21 record, the material of mould internal shaping container is selected from high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene, polyester, polystyrene, polyvinyl chloride and Merlon.

24. have the mould internal shaping container of label, on transparent mould internal shaping container, be stained with the label of claim 2 record.

25. have the mould internal shaping container of label, on transparent mould internal shaping container, be stained with the label of claim 3 record.

26. have the mould internal shaping container of label, on transparent mould internal shaping container, be stained with the label of each record of claim 4～20.

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