JP2019043085A - Soft-printing front-printed laminate and soft-packing bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent blocking even if an excessive winding pressure is applied during winding in a manufacturing process, and to improve the appearance defect of a pattern due to rubbing between packaging bags in the case of a packaging bag. Offer. A base material layer in which two or more base materials 2 and 4 are laminated and a printing layer 1 laminated on one side of the base material layer are provided, and the printing layer 1 has a binder resin and a melting point of 50. The substrate layer contains a hydrocarbon-based wax having a temperature of ° C. or higher, and the wetness index of the surface in contact with the print layer 1 is larger than the wetness index of the surface not in contact with the print layer 1, and the difference is 3 yne / cm or more. Front printing laminate for flexible packaging. A front-print laminate for flexible packaging in which the binder resin contains a polyurethane resin and / or a polyamide resin in a total amount of 30% by mass or more in the total mass of the binder resin. [Selection diagram] Fig. 1

Description

The present invention relates to a flexible packaging surface printing laminate and a flexible packaging bag.

  When a film substrate such as an OPP film, a PET film, a NY film, a metallized film or the like is used for a packaging material, printing using a printing ink is usually applied for decoration or surface protection of the substrate. The printed substrate is then passed through a slitting process to a laminating process, and finally it becomes a soft packaging package for food packaging, cosmetic packaging and all other uses.

Such a soft packaging package comprises a laminate in which a film substrate, a printing layer, and an adhesive layer are optionally combined and laminated (laminated), in which the printing layer constitutes a pattern. Laminates for soft packaging are roughly classified into two types: those having a reverse printing layer and those having a front printing layer. The laminate having the reverse printing layer has a laminate structure in which the printing layer is sandwiched by the film substrate, and the pattern can be confirmed through the transparent substrate. On the other hand, in the laminate having the front printing layer, the printing layer is the outermost layer of the laminate. There is a separate request for each of these because the texture when looking at the pattern is different.

In the method of manufacturing a laminate having a front printing layer, printing is often performed using a laminate prepared in advance as a printing material. The laminate is difficult to print cleanly if it is not printed under a strong tension (referred to as printing tension) as compared to printing on a single-layer plastic substrate, so the internal pressure of the wound product rises, and the printing layer Require high blocking resistance.
Thereafter, the front printing laminate is cut to the size of the package, and the edges are heat-sealed (referred to as a heat sealing step) to form a packaging bag. Since the corners of the bag in which the laminate is heat-sealed are hard and stiff, they may rub against the printed layer of other front-printed laminates to cause a defect in the appearance of the printed layer.

For example, Patent Document 1 discloses a front-printed laminate having a polyurethane resin in the print layer, and a print layer having a fatty acid amide is proposed for the purpose of improving the blocking resistance. However, it is still difficult to obtain a flexible packaging surface printing laminate having a good appearance, since fatty acid amide can also be a factor that penetrates the substrate to cause adhesion inhibition.

Moreover, in patent document 2, invention regarding the laminated body for a shaping | molding process which has a surface printing printing layer is described, and it is proposed to apply | coat with a resin film for printing layer protection. As described above, the front-printed printing layer is required to be easily scratched and improved in resistance to rubbing, but in particular, the laminate for soft packaging is bent, wrinkled, bent, etc. This was difficult to achieve due to the large load.

JP 2003-136652 A Japanese Patent Application Laid-Open No. 7-330019

The present invention also relates to a flexible packaging surface printing laminate that does not block even if an excessive winding pressure is applied during winding of the laminate in the process of manufacturing the soft packaging surface printing laminate, and a packaging bag, It is an object of the present invention to provide a soft packaging surface printing laminate in which the appearance defect of the design due to rubbing of the packaging bags is improved.

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research with respect to the said subject, this inventor discovered that it solved by using the surface-printing laminated body for soft packaging described below, and completed this invention.

That is, the present invention has a base material layer in which two or more base materials are laminated, and a printing layer laminated on one side of the base material layer,
The printing layer contains a binder resin and a hydrocarbon wax having a melting point of 50 ° C. or higher,
The base layer has a wetting index of the surface in contact with the printing layer larger than the wetting index of the surface not in contact with the printing layer, and the difference thereof is 3 dyn / cm or more. .

Furthermore, the present invention relates to the surface printing laminate for soft packaging, wherein the binder resin contains a polyurethane resin and / or a polyamide resin in a total amount of 30% by mass or more in the total mass of the binder resin.

Furthermore, the present invention relates to the above-mentioned soft packaging surface printing laminate, wherein the above-mentioned hydrocarbon wax contains polyethylene wax.

Furthermore, the present invention relates to a flexible packaging bag comprising the above-mentioned flexible packaging surface printing laminate.

According to the present invention, in the case of using as a packaging bag a flexible packaging surface printing laminate that does not block even if excessive winding pressure is applied during winding of the laminate in the manufacturing process of the soft packaging surface printing laminate. It has become possible to provide a soft packaging surface printing laminate in which the appearance defect of the design due to rubbing of the packaging bags is improved.

It is a schematic cross section which showed an example of the structure of the surface-printing laminated body for soft packaging of this invention.

  The embodiment of the present invention will be described in detail below, but the explanation of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not limited to the content.

The present invention has a substrate layer in which two or more substrates are laminated, and a printing layer laminated on one side of the substrate layer,
The printing layer contains a binder resin and a hydrocarbon wax having a melting point of 50 ° C. or higher,
The base layer is a surface-printing laminate for soft packaging characterized in that the wetting index of the surface in contact with the printing layer is larger than the wetting index of the surface not in contact with the printing layer, and the difference is 3 dyn / cm or more. is there.

<Printing layer>
The print layer is a layer that constitutes a pattern. The printing layer may be a printing layer in which multiple colors are printed in an overlapping manner, or only one color may be printed. The film thickness is preferably 1 to 10 μm. In addition, the printing layer is preferably a printing layer obtained from a gravure ink or flexo ink because the appearance is good. The printing layer contains a binder resin and a hydrocarbon wax having a melting point of 50 ° C. or higher. The mass ratio of the binder resin to the hydrocarbon wax is preferably 99: 1 to 90: 10.

<Binder resin>
In the present invention, the binder resin means a thermoplastic resin soluble in an organic solvent, and it is preferable to contain a polyurethane resin and / or a polyamide resin in a total amount of 30% by mass or more. Other binder resins include, for example, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, acrylic resins, polyester resins, rosin resins, rosin modified maleic acid resins, polystyrene resins, styrene-acrylic resins, styrene-maleic resins An acid resin and its modified resin etc. are mentioned. Several of these may be used in combination. In addition, as a binder resin, a cellulose resin and / or a vinyl chloride-vinyl acetate copolymer resin is preferable.

The polyurethane resin or polyamide resin preferably has a glass transition temperature of -70 to 70 ° C. Here, the glass transition temperature refers to the temperature at the peak top of the temperature-Tan δ value curve in the dynamic viscoelasticity measurement. The dynamic viscoelasticity measurement can be performed using, for example, DDV 01-GP manufactured by A & D Co., and the like. The measuring method may be a tensile measuring method or a shear measuring method.

The binder resin preferably has a weight average molecular weight of 2,000 to 100,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).

The binder resin preferably contains a polyurethane resin and / or a polyamide resin in a total amount of 30% by mass or more, and more preferably 40% by mass or more. Furthermore, it is preferable to contain a cellulose resin and / or a vinyl chloride-vinyl acetate copolymer resin, and a polyurethane resin or a polyamide resin and a cellulose resin and / or a vinyl chloride-vinyl acetate copolymer resin may be used. It is preferable to contain by mass ratio -95/5, and 40/60-95/5 are more preferable. It is preferable to contain these in 70 mass% or more in a binder resin in total.

<Polyurethane resin>
It is preferable that the said polyurethane resin is a polyurethane resin which consists of a polyol and polyisocyanate, for example. These have a structural unit consisting of a urethane bond and a polyol and a structural unit consisting of a polyisocyanate. Furthermore, it may be chain-extended by a urea bond with an amine compound such as diamine or triamine. From the viewpoint of adhesion to the substrate layer, the polyurethane resin preferably has a hydroxyl group and / or an amino group. The hydroxyl value is preferably 1 to 30 mg KOH / g, more preferably 1 to 20 mg KOH / g. The amine value is preferably 1 to 30 mg KOH / g, more preferably 1 to 20 mg KOH / g. The hydroxyl value is a value obtained according to JIS K 0070 (1992), and the amine value is a value obtained according to JIS K 1557-7 (2011). Moreover, it is preferable that a weight average molecular weight is 10000-100000, and, as for a polyurethane resin, it is more preferable that it is 10000-70000. The glass transition temperature is preferably -50 to 0 ° C.

As a polyol, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol etc. are mentioned, for example, It is preferable to contain polyester polyol. The polyester polyol preferably has a structure consisting of a condensate of sebacic acid or adipic acid and a diol. The diol preferably has 2 to 15 carbon atoms, and preferably contains a branched diol having at least one hydrogen of the diol substituted by an alkyl group. As the diol having a branched structure, for example, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol and the like are preferable. It is preferable that these polyols have a number average molecular weight of 200 to 3,000.

Examples of the polyisocyanate include aliphatic polyisocyanates and aromatic polyisocyanates. Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. The diisocyanate may, for example, be toluene diisocyanate, xylylene diisocyanate or diphenylmethane diisocyanate. The bonding position of the isocyanate group to the aromatic group may be ortho, meta or para.

In the production of the polyurethane resin, the reaction ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol is preferably adjusted appropriately in the range of 0.8 to 2.5.

When performing chain extension reaction by urea bond using an amine compound, it is preferable to use diamine compounds such as isophorone diamine, hexamethylene diamine, methylene diamine and the like.

The polyurethane resin is preferably synthesized in an organic solvent, and the organic solvent may be an aromatic organic solvent such as toluene, a ketone organic solvent such as methyl ethyl ketone, or an ester organic solvent such as ethyl acetate or n-propyl acetate Alcohol-based organic solvents such as isopropanol and ethanol, and mixed organic solvents thereof are preferred.

The said polyurethane resin can be suitably manufactured by a well-known manufacturing method. As a manufacturing method, the method as described in Unexamined-Japanese-Patent No. 2017-025256, 2017-039896, etc. can be mentioned, for example.

<Polyamide resin>
The polyamide resin refers to a thermoplastic polyamide soluble in an organic solvent which can be obtained by polycondensation of a polybasic acid and a polyvalent amine. Particularly preferred is a polyamide resin containing a reactant of an aliphatic and / or aromatic polyamine with an acid component containing a polymerized fatty acid and / or a dimer acid, and further containing a part of primary and secondary monoamines. Is preferred.

Examples of polybasic acids used as raw materials of polyamide resins include, but are not limited to: adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, pimeline Acids, oxalic acid, malonic acid, succinic acid, maleic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acids, hydrogenated dimer acids, polymerized fatty acids, and among them, dimer acids, water Preferred are dimeric dimer acids and polymeric fatty acids. Here, the polymerized fatty acid is a dry or semi-dry fatty acid or a fatty acid obtained by ester polymerization, transesterification or the like, and includes monobasic fatty acid, dimerized polymerized fatty acid, trimerized polymerized fatty acid and the like.
A monocarboxylic acid can also be used together with the polybasic acid. Examples of the monocarboxylic acid used in combination include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, cyclohexanecarboxylic acid and the like.

Examples of polyvalent amines include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and methylaminopropylamine, and aliphatic polyamines such as diethylenetriamine and triethylenetetramine. Cycloaliphatic polyamines include cyclohexylene. Diamine, isophorone diamine, etc. can be mentioned. Moreover, xylylene diamine may be mentioned as the araliphatic polyamine, and phenylenediamine, diaminodiphenylmethane etc. may be mentioned as the aromatic polyamine.
Primary and secondary monoamines can be used in combination with polyhydric amines. Examples of primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine and the like.

The polyamide resin can be produced by a conventional polyamide resin synthesis method. The reaction temperature is preferably 180 to 230 ° C., and the reaction is preferably performed in an inert gas. Since dehydration reaction is performed, it is preferable to use a distillation apparatus. Furthermore, the reaction may be carried out under reduced pressure. The equivalent ratio of carboxyl group to amino group of the reaction component is preferably 0.9: 1.0 to 1.0: 0.9.

The polyamide resin preferably has a softening point of 80 to 140 ° C. and a weight average molecular weight of 2,000 to 70,000. When the softening point is 80 ° C. or more, surface tack breakage of the ink film of the printed matter becomes good, and blocking is prevented. When the softening point is 140 ° C. or less, the ink film becomes flexible and the adhesion to the substrate is improved. When the weight average molecular weight is in the range of 2,000 or more, the film strength of the ink becomes good, and the abrasion resistance, heat resistance and high speed printability are improved. When the molecular weight is 70,000 or less, the viscosity of the ink can be lowered, and the storage stability becomes good. In addition, a softening point represents the value measured by JISK2207 (ring and ball method).

<Vinyl chloride-vinyl acetate copolymer resin>
The vinyl chloride-vinyl acetate copolymer resin is a resin comprising a copolymer of vinyl chloride and vinyl acetate as a main component. The weight average molecular weight thereof is preferably 5,000 to 100,000, and more preferably 20,000 to 70,000. The content of the structural unit derived from the vinyl acetate monomer is preferably 1 to 30% by mass in 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer resin, and the content of the structural unit derived from the vinyl chloride monomer is 70 to 95 mass % Is preferred. In this case, the solubility in the organic solvent is improved, and the adhesion to the substrate, the physical properties of the film, the laminate strength and the like are further improved.
Further, in order to improve the solubility in organic solvents, those containing hydroxyl groups derived from vinyl alcohol by saponification reaction or copolymerization are more preferable, and the hydroxyl value is preferably 20 to 200 mg KOH / g. Moreover, it is preferable that a glass transition temperature is 50 degreeC-90 degreeC.

<Cellulose resin>
Examples of the cellulose-based resin include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, and carboxyalkyl cellulose. Examples of the alkyl group optionally contained in the cellulose resin include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group and a hexyl group. The alkyl group may have a substituent. Among them, cellulose acetate propionate, cellulose acetate butyrate and nitrocellulose are preferable. The weight average molecular weight is preferably 5,000 to 100,000, and more preferably 10,000 to 200,000. Moreover, it is preferable that a glass transition temperature is 100 degreeC-160 degreeC.

(Nitrocellulose)
Nitrocellulose is a nitrate ester of cellulose, and natural cellulose is reacted with nitric acid to obtain three hydroxyl groups in the six-membered ring of an anhydrous glucopyranose group in natural cellulose as a nitrate ester substituted with a nitrate group. Those having an average degree of polymerization of 35 to 480, more preferably 50 to 200 are preferable. When the average degree of polymerization is 50 or more, the strength of the ink film is improved, and the abrasion resistance and the rub resistance are improved, which is preferable. When the average degree of polymerization is 200 or less, the solubility in solvents, the low temperature stability of the ink, and the compatibility with the combined resin are improved, which is preferable. Moreover, it is preferable that a nitrogen content is 10.5-12.5 mass%.

<Hydrocarbon wax>
The printing layer contains a hydrocarbon wax having a melting point of 50 ° C. or higher. The melting point is preferably 70 ° C. or higher, and more preferably 90 to 130 ° C. In this case, the friction resistance and the blocking resistance of the print layer are improved, and the adhesion to the base layer is also excellent.
The content is preferably 0.1 to 17% by mass in the printing layer. More preferably, it is 0.3 to 15% by mass, still more preferably 0.5 to 12% by mass, and most preferably 0.8 to 12% by mass. In addition, in the gravure ink for comprising a printing layer, it is preferable to contain hydrocarbon-type wax 0.1-2.5 mass% in 100 mass% of inks.

The melting point means a value measured by differential scanning calorimetry (DSC method).

By using a hydrocarbon wax and a binder resin containing a polyurethane resin or a polyamide resin in combination, even when the soft packaging surface printing laminate is used as a soft packaging bag, when they are rubbed or overlapped with each other. It is possible to suppress the scratch caused by the generated friction. It is considered that this is because when the hydrocarbon-based wax has the above-mentioned melting point, the affinity with the above-mentioned binder resin becomes good and it becomes a uniform and tough printing layer.

As the above-mentioned hydrocarbon wax, for example, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, carnauba wax, paraffin wax, microstaline wax and the like are suitable, and two or more kinds may be used in combination. Among them, polyethylene wax and / or Fischer-Tropsch wax are preferable, and polyethylene wax is more preferable. As described above, these have high affinity with the polyurethane or polyamide resin, and are considered to have the effect of making the print layer tough.

The hydrocarbon-based wax preferably has a penetration (hardness) of 0.1 to 15 (unit: 10 ⁻¹ mm), and more preferably 0.5 to 15. Here, the degree of penetration refers to a value obtained according to JIS K 2207. Moreover, it is preferable that an acid value is 30 mgKOH / g or less from a viewpoint of water resistance.

In addition, the printing layer preferably further contains a fatty acid amide. The fatty acid amide is preferably a saturated or unsaturated hydrocarbon having 8 to 25 carbon atoms, such as oleic acid amide and palmitic acid amide.

<Pigment>
The printing layer preferably contains a pigment. The mass ratio of binder resin to pigment (binder resin / pigment) is preferably 99/1 to 10/90. More preferably, it is 80/20 to 20/80. This is because the adhesiveness to the base material layer is improved in the corresponding range.

Both organic and inorganic pigments can be used as the pigment, and the inorganic pigment may be used in combination with the organic pigment. Furthermore, it may contain an extender pigment such as barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate, silica and the like. Preferred are organic pigments and inorganic pigments.

Examples of the organic pigment include, but are not limited to, soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinoni, anthrapyrimidine, perylene, etc. Pigments such as perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone and carbon black Be Also, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophal yellow, chromophal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indance Ron Blue, Pyrimidine Yellow, Thioindigo Bordeaux, Thioindigo Magenta, Perylene Red, Perinone Orange, Isoindolinone Yellow, Aniline Black, Carbon Black, Diketopyrrolopyrrole Red, Daylight Fluorescent Pigment, etc. You can use the ones from time to time.

Inorganic pigments include zinc oxide, zinc sulfide, chromium oxide, aluminum particles, mica (mica), bronze powder, chromium vermillion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, bitumen, red iron oxide, iron oxide yellow, iron black Aluminum may be leafing type or non-leafing type.

Although titanium oxide is not particularly limited, it is preferable that the crystal structure is rutile type at least surface-treated with silica or alumina. Moreover, you may be processed by the other metal, For example, the metal single-piece which consists of elements of Si, Al, Zn, and Zr, the oxide of Al, Zn, etc. are mentioned. The above-mentioned "treated" means the state where the surface of titanium oxide particles is covered.

The titanium oxide preferably has an oil absorption of 14 to 35 ml / 100 g, and more preferably 17 to 32 ml / 100 g, according to the measurement method defined in JIS K 5101. Moreover, the average particle diameter (median particle diameter) measured by the transmission electron microscope is preferably 0.15 to 0.35 μm, and more preferably 0.2 to 0.3 μm. The total content of the titanium oxide pigment is preferably 10 to 60% by weight, and more preferably 10 to 45% by weight, in 100% by weight of the ink. Further, plural kinds of titanium oxide pigments may be used in combination. In the gravure ink of the present invention, in addition to the titanium oxide pigment, other inorganic pigments and organic pigments can be further used in combination.

<Other ingredients>
The print layer may further contain an additive component. The additives include pigment dispersants, leveling agents, trapping agents, antifoaming agents, chelating agents, antiblocking agents, lubricants, viscosity modifiers and the like.

<Base material layer> A base material layer is laminated so that two or more bases may constitute the outermost surface of a base material layer, and a base material which constitutes a field which contacts a printing layer among the outermost surfaces. An adhesive layer or another base may be provided between the base 1 and the base 2 constituting the surface not in contact with the print layer.
The substrate constituting the substrate layer is preferably a film-like plastic substrate, for example, polyethylene, polyolefin such as polypropylene, polyethylene terephthalate, polycarbonate, polyester such as polylactic acid, polystyrene, AS resin, ABS resin, etc. Film substrates such as polystyrene resins of the following, nylons, polyamides, polyvinyl chlorides, polyvinylidene chlorides, cellophanes, and film composites made of these composite materials. The plastic substrate may be deposited with a metal or metal oxide such as silica, alumina, or aluminum, and the deposition surface may be further coated with a paint such as polyvinyl alcohol. In general, the substrate surface to be printed may be subjected to surface treatment such as corona treatment. Furthermore, as to these plastic substrates, films obtained by processing plastic films such as application of antifogging agents, kneading, surface coating of matting agents, kneading and the like in advance can also be used.

The antifogging agent is preferably a surfactant, for example, ionic surfactant such as polyvalent alcohol fatty acid ester such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerin fatty acid ester or ethylene oxide adduct One or more agents may be used.

In the base material layer, the wetting index of the surface in contact with the printing layer (hereinafter abbreviated as surface) is larger than the wetting index of the surface not in contact with the printing layer (hereinafter abbreviated as back surface). The difference is 3 dyn / cm or more, preferably 5 to 20 dyn / cm. In addition, a wetting index (wetting tension) means the value measured by the method of JISK6768 using a wetting index standard liquid. When the difference in the wetting index is in the above-mentioned range, the adhesion between the surface and the print layer is excellent, and blocking of the back surface and the print layer when the laminate is taken up as a printing material by printing is suppressed Can.

The surface of the substrate layer is constituted by the substrate 1, and the wetting index of the surface is preferably 30 to 60 dyn / cm, and more preferably 35 to 55 dyn / cm. The base material 1 is preferably a plastic base material stretched uniaxially or biaxially, and preferably has an easy-adhesion surface subjected to easy-adhesion treatment such that the wetting index is in the above-mentioned range. Examples of the easy adhesion treatment include corona discharge treatment, ultraviolet light / ozone treatment, plasma treatment, oxygen plasma treatment, primer treatment and the like. For example, in the corona discharge treatment, a hydroxyl group, a carboxyl group, a carbonyl group or the like is expressed on the substrate. The binder resin preferably has a functional group such as a hydroxyl group or an amino group because hydrogen bonds can be used.

It is preferable that the back surface of a base material layer is comprised by the base material 2, and the wetting index of a back surface is 25-45 dyn / cm. The base material 2 is preferably a base material that is thermoplastic in order to form a soft packaging bag by heat-sealing the back surfaces of the front-printed laminate. As the thermoplastic substrate, unstretched polyethylene, unstretched polypropylene and other unstretched plastic substrates are preferable.

<Adhesive layer>
The base layer preferably has an adhesive layer between the base 1 and the base 2. The lamination method is representative of extrusion lamination, dry lamination, non-solvent lamination, and further includes wet lamination method, thermal lamination method, hot melt lamination method and the like.
Examples of the adhesive layer include layers made of an anchor coating agent, a urethane-based laminating adhesive, a molten resin and the like, and these may be used in combination.
It is preferable to use an anchor coating agent (AC agent) in the extrusion laminate, and examples of the AC agent include an imine AC agent, an isocyanate AC agent, a polybutadiene AC agent, and a titanium AC agent. Polyethylene is representative for the molten resin, and one melting at 280 to 360 ° C. can be appropriately used.
The urethane-based laminating adhesive includes, for example, polyether urethane-based laminating adhesive, polyester urethane-based laminating adhesive and the like, and examples thereof include those composed of two solutions of a resin having a hydroxyl group and a resin having an isocyanate group. Those containing an organic solvent are dry laminating adhesives, and those having no solvent are solventless laminating adhesives. In addition, it is preferable to use a polyester urethane type lamination adhesive for the soft packaging application which requires processes, such as retort.

<Surface printing laminate for soft packaging>
The surface-printing laminate for soft packaging of the present invention (hereinafter sometimes abbreviated as a laminate) has a printing layer on one side of the above-mentioned base material layer.
As a manufacturing method of a layered product, a method of manufacturing a base material layer by which two or more base materials were laminated beforehand beforehand, and forming a printing layer on this base material layer is preferred. Moreover, the printed material which has a printing layer in the base material 1 may be prepared beforehand, and you may bond together with the other base materials containing the base material 2 (lamination).
As a method of laminating the substrate, for example, after applying an anchor coating agent to the substrate 1 in the case of extrusion lamination, further, a heat-melted polyethylene resin is dripped in a thin curtain shape from a narrow slit called T die. The substrate 2 is placed on a layer, and the substrate 2 is further pressed onto molten polyethylene. These are performed in a series of operations. As a manufacturing machine, a Co extrusion laminator manufactured by Musashi Shinokai Co., Ltd. can be mentioned.
In dry lamination, an adhesive such as urethane is coated and dried on the substrate 1 and a plastic film is laminated thereon. Since the laminating adhesive is often a two-component solution, it takes a certain time to cure, and it is preferable to cure in about 24 to 48 hours.
Non-solvent laminates are similar in process to dry lamination, but do not require a drying process because they do not contain a solvent. As a machine for producing these dry laminates and non-solvent laminates, dry laminators manufactured by Musa Shinokai can be mentioned. With respect to other laminating methods, they can be produced by any known method.

<Soft packaging bag>
The laminate, which can be manufactured above, is suitably cut into the size of the food package (called a slitting process). The cut laminate is formed into a bag shape, and the edge portion is heat-pressed (referred to as a heat sealing process) to form a soft packaging bag.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is merely an example of the invention embodiments, and the present invention is not limited to these examples. In the present invention, parts and% represent parts by weight and% by weight unless otherwise noted.

(Hydroxyl value)
It calculated | required according to JIS K0070.
(Amine value)
It calculated | required according to JIS K1557-7: 2011.

(Weight average molecular weight)
The weight average molecular weight was determined by measuring molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation), and determining polystyrene as a converted molecular weight using a standard substance. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh Corporation TSKgel SuperAW2500
Tosoh Corporation TSKgel SuperAW 3000
Tosoh Corporation TSKgel SuperAW 4000
Tosoh Corporation TSKgel guardcolumn SuperAWH
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: tetrahydrofuran flow rate: 1.0 mL / min

(Base material wetting index)
It was determined according to the method described in JIS K 6768 using a wetting index standard solution.

(Glass-transition temperature)
It measured and measured in the measurement temperature range -70-250 degreeC with the dynamic-viscoelasticity measuring machine (A and day company DDV01-GP).

(Melting point)
It was determined by differential scanning calorimetry (DSC method) at a heating rate of 10 ° C./min and a measurement temperature range of 25 to 180 ° C. The measuring instrument used was Shimadzu DSC-60 Plus.

[Preparation of base layer] (Composition: base 1 / adhesive layer / base 2)
In the following OPP, PET and alumina-deposited PET, a polyester urethane-based laminating adhesive (TM250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) is used as a 20% solids ethyl acetate solution, and the adhesive layer after drying is 2.0 g After coating and drying so as to be 1 / m ² , CPP corresponding to the base material 2 is attached to the adhesive layer and dry lamination is performed to form a base material layer J (OPP), K (PET), L (Alumina-deposited PET) were obtained respectively. The difference in the wetting index between the front surface and the back surface of the base layer is J (5 dyn / cm), K (15 dyn / cm), L (27 dyn / cm).
<Base 1>
・ OPP: Toyobo Co., Ltd. Biaxially oriented polypropylene substrate product name P 2261 film thickness 20 μm Wetting index of the surface mentioned above 38 dyn / cm
-PET: Unitika Biaxially Stretched Polyester Base Product Name PTM Film Thickness 12 μm Wetting Index of the Surface Above 48 dyn / cm
· Alumina-deposited PET: Alumina-deposited biaxially stretched polyester base product name TL-PETHS manufactured by Mitsui Chemicals Totoro Co., Ltd. Surface wetting index 60dyn / cm
<Base material 2>
・ CPP: Toray Industries Unstretched polypropylene substrate Product name 9405S Film thickness 60 μm Wetting index of the above-mentioned back side 33 dyn / cm

(Synthesis example 1) [polyurethane resin PU1]
80 parts of polyester polyol having a number average molecular weight of 1000, 20 parts of polypropylene glycol having a number average molecular weight of 1000, 24.9 parts of dicyclohexylmethane-4,4'-diisocyanate, and 208 parts of ethyl acetate, which is a condensate of neopentyl glycol and adipic acid Were reacted at 80.degree. C. for 4 hours under a nitrogen stream. Further, 208 parts of a mixed solvent of ethyl acetate: isopropanol (IPA) 1: 1 was added at a temperature of 40 ° C. to adjust the solid content to 30% to obtain a polyurethane resin solution PU1. PU1 was an amine value of 0.0 mgKOH / g, a hydroxyl value of 4.5 mgKOH / g, a weight average molecular weight of 38,000, and a glass transition temperature of -15 ° C.

(Synthesis Example 2) [Polyurethane Resin PU2]
90 parts of a number average molecular weight 1000 polyester polyol, which is a condensation product of methyl pentanediol and adipic acid, 10 parts of a polypropylene glycol with a number average molecular weight 1000, 46.7 parts of isophorone diisocyanate, and 36.7 parts of ethyl acetate under a nitrogen stream The reaction was carried out at 80 ° C. for 4 hours, and the reaction solution was cooled to 40 ° C. Then, the reaction solution is mixed with a mixture comprising 13.7 parts of isophorone diamine, 5.0 parts of 2- (2-aminoethylamino) ethanol and 328.4 parts of a mixed solvent of ethyl acetate: isopropanol 1: 1, The mixture was gradually added at ° C and then reacted at 80 ° C for 1 hour to obtain a polyurethane resin solution PU2. PU2 had a solid content of 30%, an amine value of 5.5 mg KOH / g, a hydroxyl value of 16.3 mg KOH / g, a weight average molecular weight of 55000, and a glass transition temperature of -30 ° C.

(Production Example 1) [Production of Gravure Ink S1]
It mixed by the following composition, and it knead | mixed and disperse | distributed for 20 minutes with the sand mill, and obtained gravure ink S1.
-Polyurethane resin solution PU2 (solid content 30%): 36 parts-Vinyl chloride-vinyl acetate copolymer resin solution (Solvane TA3 solid content 30%): 4 parts In the table, it was abbreviated as "salt and vinyl acetate resin solution".
· Titanium oxide (CR-80 rutile crystal structure manufactured by Ishihara Sangyo Co., Ltd. Surface treatment with silica and alumina, average particle size 0.25 μm, oil absorption 20 (ml / 100 g)) 30 parts · Wax particles 1 (polyethylene (wax) particles Penetration degree 13 melting point 110 ° C): 0.2 parts mixed solvent (propyl acetate / IPA = 70/30) 29.8 parts

(Production Examples 2 to 15) [Production of Gravure Inks S2 to S15]
Gravure inks S2 to S15 were produced in the same manner as in Production Example 1 except that the following raw materials were used. The ink composition is shown in Table 1. In addition, the abbreviation of the raw material in Table 1 shows the following.
S-2800: Kao polyamide resin softening point 115 ° C. weight average molecular weight 3500
(Solid content 30% IPA / toluene = 30/70 solution)
-Solven TA3: Nisshin Chemical Co., Ltd. vinyl chloride-vinyl acetate copolymer resin vinyl chloride structure / vinyl acetate structure / hydroxy acrylic structure = 83/4/13 (ethyl acetate solution with solid content of 30%)
-DLX5-8: manufactured by ICI Novel enterprises Inc. Nitrocellulose 12.0% nitrogen content (30% solid solution in isopropanol)
· FG 7400 G: manufactured by Toyo Color Inc. Pigment Blue 15: 4 Phthalocyanine pigment · Wax particles 2: Polyethylene (wax) particles Penetration 7 Melting point 109 ° C
・ Wax particle 3: Fischer-Tropsch (wax) particle penetration 2 melting point 102 ° C
・ Wax particles 4: Paraffin (wax) particles Penetration degree 17 Melting point 53 ° C.

(Comparative Production Examples 1 to 7) [Preparation of Gravure Inks T1 to T7]
Gravure inks T1 to T7 were obtained from the raw materials and the composition as shown in Table 2 and in the same manner as the methods described in Production Examples 1 to 15 above.
Oleic acid amide: fatty acid amide melting point 70 ° C.
· Wax particles 5: paraffin (wax) particles Penetration degree 30 melting point 47 ° C

Example 1
<Formation of front printing laminate for soft packaging> (Gravure printing on substrate layers J, K, L)
Gravure ink S1 obtained above was diluted with mixed solvent (methyl ethyl ketone: N propyl acetate: isopropanol = 40: 40: 20) to a viscosity of 16 seconds (25 ° C, Zahn cup No. 3). , And printed at a printing speed of 100 m / min on the surface of the above base layers J, K and L using a corrosion 175-line solid plate (plate type compressed, 100% solid pattern), surface-printing laminates for soft packaging J1, K1, L1 was obtained respectively. The printing conditions were a temperature of 25 ° C. and a humidity of 60%.

(Examples 2 to 15)
In the same manner as in Example 1, the inks described in Table 1 were used to obtain soft printing surface printed laminates J2 to J15, K2 to K15, and L2 to L15, respectively.

(Comparative Examples 1 to 7)
In the same manner as in Example 1, the inks described in Table 2 were used to obtain soft printing surface-printed laminates JJ1 to JJ7, KK1 to KK7, and LL1 to LL7, respectively.

<Evaluation>
The following evaluation was performed in the laminated body of an Example and a comparative example. The results are shown in Table 3 and Table 4.

<Blocking resistance>
The blocking resistance was evaluated under the following conditions for the soft-printing front-printed laminates J1 to J15, K1 to K15 and L1 to L15 and JJ1 to JJ7, KK1 to KK7 and LL1 to LL7.
(Sample and pressure)
The printing layer of various soft packaging front printing laminates and the back surface of the above-mentioned CPP were overlapped, and a pressure of 6 kg / cm ² was applied.
(Standing conditions) 40 ° C.-80% RH for 48 hours (Evaluation method) Peel off the stacked laminates and visually judge the degree of peeling of the ink film from the printing surface.
Judgment criteria5. The printed layer does not peel at all and the peeling resistance is small (good)
4. Peeling area of printing layer is 1% or more and less than 5%, and peeling resistance is small (practical)
3. Peeling area of printing layer is 5% or more and less than 20% (slightly poor)
2. Peeling area of printing layer is 20% or more and less than 50% (defect)
1. Print layer peels off by 50% or more (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.

<Scratch resistance>
The surface of the printed layer was rubbed three times with a nail on the surface-printed laminates J1 to J15, K1 to K15 and L1 to L15 and JJ1 to JJ7, KK1 to KK7 and LL1 to LL7 for soft packaging, and the degree of damage of the printed layer was evaluated. .
Judgment criteria5. No damage on the print layer (good)
4. There is no scratching of the printed layer but slight marks of nails remain. (Practical use possible)
3. The print layer is scratched and the surface of the print layer is slightly curled. (Slightly poor)
2. The print layer is scratched and the substrate is slightly visible. (Defective)
1. The print layer is scratched and the substrate is clearly visible. (Very bad)
In addition, 5 and 4 are ranges which have no problem in practical use.

<Anti-friction>
Using the Gakushin-type friction tester (made by Daisho Scientific Seiki Mfg. Co., Ltd.), cut 20 mm × 250 mm into test pieces for the soft-printing front-printed laminates K1 to K15 and KK1 to KK7. The abrasion resistance of the printed layer was evaluated under the following conditions.
Load: 200 g (Kanakin No. 3) Number of frictions: 40 round trip Temperature: 25 ° C
Judgment criteria5. No peeling of the print layer (good)
4. Peeling area of printing layer is less than 10% (practical)
3. Peeling area of printing layer is 10% or more and less than 30% (slightly poor)
2. Peeling area of printing layer is 30% or more and less than 50% (defect)
1. Peeling all over (very poor)
In addition, 5 and 4 are ranges which have no problem in practical use.

(Comparative example 8)
[Preparation of base layer] (Composition: base 1 / adhesive layer / base 2)
In the following OPP, a polyester urethane-based laminating adhesive (TM250HV / CAT-RT86L-60 manufactured by Toyo Morton Co., Ltd.) is used as an ethyl acetate solution with a solid content of 20%, and the adhesive layer after drying is 2.0 g / m ² After coating and drying, a CPP corresponding to the substrate 2 was attached to the adhesive layer, and dry lamination was performed to obtain a substrate layer M (OPP).
<Base 1>
-OPP: Futamura Chemical Co., Ltd. Biaxially oriented polypropylene substrate product name FOA film thickness 20 μm The above-mentioned surface wetting index 28 dyn / cm
<Base material 2>
・ CPP: Toray Industries Unstretched polypropylene substrate Product name 9405S Film thickness 60 μm Wetting index of the above-mentioned back side 33 dyn / cm
Gravure ink S4 prepared in Example 1 was printed on the surface of the base material layer M in the same manner as in Example 16 to obtain a surface-printing laminate M1 for soft packaging. The above-mentioned performance evaluation about the obtained layered product was blocking resistance: 2, scratch resistance: 3, and abrasion resistance: 3.

According to the present invention, in the case of using as a packaging bag a flexible packaging surface printing laminate that does not block even if excessive winding pressure is applied during winding of the laminate in the manufacturing process of the soft packaging surface printing laminate. It has become possible to provide a flexible packaging front printing laminate in which the appearance defect of the design due to rubbing between the packaging bags is improved.

1 ··· Printing layer 2 · · · Base material 1
3 ··· Adhesive layer 4 ··· Base material 2

Claims (4)

It has a base material layer on which two or more base materials are laminated, and a printing layer laminated on one side of the base material layer,
The printing layer contains a binder resin and a hydrocarbon wax having a melting point of 50 ° C. or higher,
A surface layer for soft packaging characterized in that the base material layer has a wetting index of the surface in contact with the printing layer larger than the wetting index of the surface not in contact with the printing layer, and the difference is 3 dyn / cm or more. The surface printing laminate for soft packaging according to claim 1, wherein the binder resin contains a polyurethane resin and / or a polyamide resin in a total amount of 30% by mass or more in the total mass of the binder resin. The flexible packaging front printing laminate according to claim 1, wherein the hydrocarbon wax contains polyethylene wax. A flexible packaging bag comprising the flexible packaging front printing laminate according to claim 1 or 2.