WO2018182026A1 - インモールド成形用ラベル及びラベル付き樹脂成形品 - Google Patents
インモールド成形用ラベル及びラベル付き樹脂成形品 Download PDFInfo
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- WO2018182026A1 WO2018182026A1 PCT/JP2018/014000 JP2018014000W WO2018182026A1 WO 2018182026 A1 WO2018182026 A1 WO 2018182026A1 JP 2018014000 W JP2018014000 W JP 2018014000W WO 2018182026 A1 WO2018182026 A1 WO 2018182026A1
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- molded product
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to a label for in-mold molding and a resin molded product with a label to which the label is attached.
- in-mold molding has been used as one of the methods for attaching labels to resin molded products.
- in-mold molding when a resin molded product is molded in a mold, a label is previously placed inside the mold, and the label is attached to the resin molded product simultaneously with the molding of the molten resin.
- a label used in in-mold molding is called an in-mold molding label, and a printing layer is formed by printing on the in-mold molding label from the viewpoint of decorativeness and design. .
- the resin constituting the resin molded product is brought into contact with the resin film constituting the label in a molten state. And after a label and a resin molded product adhere, it cools and solidifies and the container with a label which the label and the resin molded product adhered and integrated is shape
- Patent Document 1 discloses a method for in-mold molding in which a plurality of printed resin films are laminated via an ultraviolet curable and / or electron beam curable pseudo-adhesive resin layer.
- a label is disclosed.
- Patent Document 2 proposes an in-mold molding label that includes a base layer (A) containing a thermoplastic resin, a layer (B) that enables delamination, and a heat seal layer (C) in this order. Has been.
- the label can be peeled by the destruction of the layer (B) itself that enables delamination.
- a label such as a pseudo-adhesive resin layer or a layer that enables delamination is used.
- a layer for separating the part is required separately.
- Patent Document 2 a heat seal layer is required for adhesion between the label and the resin molded product. That is, in order to peel a part of the label or to bond the label and the resin molded product, a process for producing a layer or a heat seal layer for peeling a part of the label occurs. Therefore, the work process of manufacturing the label for in-mold molding becomes complicated, and the cost is increased accordingly.
- the present invention has been made in view of such background art. That is, in a label for in-mold molding, a part of the layer constituting the label can be peeled off without necessarily providing a peeling layer or a heat seal layer, and the adhesion between the label and the resin molded product can be improved.
- the object is to provide a label for in-mold molding that is maintained, and a resin-molded article with a label to which the label is attached.
- the present invention is not limited to the purpose described here, and is an operational effect derived from each configuration shown in the embodiment for carrying out the invention described later, and can also exhibit an operational effect that cannot be obtained by the conventional technology. It can be positioned as another purpose.
- a base material layer (A) containing a thermoplastic resin, an ink receiving layer (B) containing a polyethyleneimine polymer, and polyethylene The present inventors have found that the above problems can be solved by adopting an in-mold molding label having a printing layer (C) mainly composed of a resin in this order, and have completed the present invention.
- the thermoplastic resin is at least one thermoplastic resin selected from the group consisting of olefin resins, styrene resins, ester resins, amide resins, and polycarbonates. Label for molding.
- the polyethylene resin includes an ethylene / methacrylic acid copolymer.
- a second printed layer (c) and a second ink receiving layer (b) are provided on the surface of the base material layer (A) opposite to the side where the ink receiving layer (B) is provided.
- the in-mold molding label of the present invention has the above-described configuration, thereby ensuring an appropriate adhesive force between the ink receiving layer and the base material layer while maintaining the adhesiveness between the ink receiving layer and the printing layer ( It is possible to reduce the peel strength). That is, according to the present invention, the label is attached to the interface between the base material layer (A) and the ink receiving layer (B) or the ink receiving layer (B) and the printing layer (C) from the state where the label is adhered to the resin molded product. It is possible to provide an in-mold forming label that can be peeled off at the interface with the substrate.
- the label for in-mold molding of the present invention allows the base material layer to be peeled freely at any timing from container molding to disposal, and print information is printed on the base material layer and the surface of the print layer, respectively. It is possible to display, and the display area can be increased.
- the label for in-mold molding is peeled from the resin molded product with a label, the label is peeled off at the interface between the base material layer (A) and the ink receiving layer (B) or at the interface between the ink receiving layer (B) and the printing layer (C). Therefore, the printing layer (C) remains on the container surface side. For this reason, when the in-mold forming label is peeled off, the print information can be visually recognized on the surface of the container.
- the in-mold molding label of the present invention can display not only printing information provided on the base material layer but also different new printing information provided on the printing layer after the base material layer is peeled off. .
- the in-mold molding label of the present invention is difficult to re-attach the base material layer onto the ink receiving layer after the base material layer is peeled off, forgery prevention and reuse of the resin molded product with a label It can also be prevented.
- the base material layer peeled off from the in-mold molding label of the present invention can be secondarily used for coupons, application tickets, etc., and the print information on the print layer can be used only by the product purchaser. (For example, an ornamental code number, bar code, lottery, fortune telling, etc.) can also be used.
- FIG. 1 is a cross-sectional view of an embodiment of the in-mold label of the present invention.
- FIG. 2 is a cross-sectional view of one embodiment of the labeled resin molded product of the present invention obtained by attaching the in-mold molding label of FIG. 1 to a resin molded product.
- FIG. 3 is a cross-sectional view showing a state in which the labeled resin molded product of FIG. 2 is peeled off at the interface.
- FIG. 4 is a perspective view schematically showing a labeled resin molded product of the present invention.
- FIG. 5 is a cross-sectional view of another embodiment of the in-mold label of the present invention.
- FIG. 6 is a cross-sectional view of another embodiment of the labeled resin molded product of the present invention obtained by attaching the in-mold molding label shown in FIG. 5 to the resin molded product.
- FIG. 7 is a cross-sectional view of another embodiment of the in-mold label of the present invention.
- (meth) acrylic acid includes both acrylic acid and methacrylic acid.
- main component refers to a component having the highest content on a mass basis among the components contained in the target composition.
- the label for in-mold molding of the present invention includes a base material layer (A), an ink receiving layer (B), and a printing layer (C).
- FIG. 1 is a view showing an embodiment of an in-mold molding label according to the present invention.
- the in-mold molding label 1 includes a base material layer (A) 11, an ink receiving layer (B) 12, and a printing layer (C). 13 are laminated so as to have this order.
- peeling is possible at the interface between the base material layer (A) 11 and the ink receiving layer (B) 12. .
- the in-mold molding label 1 is formed by laminating a base material layer (A) 11, an ink receiving layer (B) 12, and a printing layer (C) 13 adjacent to each other in this order.
- A base material layer
- B ink receiving layer
- C printing layer
- the thickness of the entire in-mold molding label of the present invention is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more from the viewpoint of heat insulation for preventing heat received from the molten resin from escaping to the mold.
- the rigidity is too high, the base material layer and the ink receiving layer tend to be peeled off during normal transportation and use, so 160 ⁇ m or less is preferable, and 140 ⁇ m or less is more preferable.
- the base material layer (A) contains a thermoplastic resin.
- a printing layer (C) 13 is provided on a base material layer (A) 11 with an ink receiving layer (B) 12 interposed therebetween.
- the base material layer (A) 11 supports at least the printing layer (C) 13 and the ink receiving layer (B) 12, and has a rigidity (stiffness) that can be handled during printing or processing. It is a layer given to 1.
- the base layer (A) 11 is present on the outer surface of the labeled resin molded product 2 in a state where the printed layer (C) 13 is thermally fused to the resin molded product 21.
- the substrate layer (A) 11 itself may have a single layer structure or a multilayer structure of two or more layers. Moreover, when it is a multilayered structure of two or more layers, the layers may be composed of the same component or may be composed of different components.
- the base material layer (A) 11 contains a thermoplastic resin, and is usually made of a thermoplastic resin film sheet. This film may be unstretched or stretched, and may be a single layer or a multilayer.
- thermoplastic resin used for the base material layer (A) 11 is not particularly limited.
- high-density polyethylene high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, propylene-based copolymer resin, polymethyl-1-pentene, ethylene / cyclic olefin copolymer, and other olefin-based resins capable of film forming; atactic polystyrene, Styrene resins such as syndiotactic polystyrene and styrene-maleic acid copolymer; polyethylene terephthalate, polyethylene terephthalate isophthalate, polybutylene terephthalate, and ester resins such as polybutylene succinate, polybutylene adipate, and polylactic acid; ethylene Functional group-containing polyolefin resins such as vinyl acetate copolymer, ethylene / acrylic acid copolymer, maleic
- thermoplastic resins at least one kind of thermoplastic resin selected from the group consisting of olefin resins, styrene resins, ester resins, amide resins and polycarbonates is preferable from the viewpoint of excellent film processability.
- An olefin resin or a functional group-containing olefin resin is more preferable, and an olefin resin is particularly preferable.
- the olefin-based resin is composed solely of one type of olefin monomer such as ethylene, propylene, butylene, pentene, hexene, octene, butadiene, isoprene, chloroprene, methyl-1-pentene, and cyclic olefin.
- olefin monomer such as ethylene, propylene, butylene, pentene, hexene, octene, butadiene, isoprene, chloroprene, methyl-1-pentene, and cyclic olefin.
- examples thereof include a copolymer and a copolymer composed of two or more of the olefin monomers. Of these, polyethylene resins are preferred.
- examples of the functional group-containing olefin resin include a copolymer of at least one olefin monomer and at least one monomer copolymerizable with the olefin monomer.
- Examples of monomers copolymerizable with the olefin monomers include styrenes such as styrene and ⁇ -methylstyrene; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl stearate, Carboxylic acid vinyl esters such as vinyl benzoate, vinyl butylbenzoate, and vinyl cyclohexanecarboxylate; unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride, and acid anhydrides thereof; Methyl) methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid Monomethyl ester Uns
- the functional group-containing olefin-based resin is hydrolyzed with an acid or a base, and a functional group derived from a carboxylic acid vinyl ester, an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, or an unsaturated carboxylic acid amide is converted into a hydroxyl group or a carboxylic acid. It may be converted to an acid or carboxylic acid metal salt.
- the olefin resin or the functional group-containing olefin resin can be graft-modified.
- the graft modification include a method of reacting a peracid such as peracetic acid, persulfuric acid, potassium persulfate and the like and a metal salt thereof; an unsaturated carboxylic acid or a derivative thereof in the presence of an oxidizing agent such as ozone.
- the graft modification rate is usually 0.005 to 10% by mass, preferably 0.01 to 5% by mass, based on the olefin resin or the functional group-containing olefin resin.
- the film constituting the base material layer (A) 11 may contain a filler such as an inorganic powder or an organic powder.
- a filler such as an inorganic powder or an organic powder.
- the filler include heavy calcium carbonate, light calcium carbonate, calcined clay, silica, diatomaceous earth, talc, titanium oxide, barium sulfate, and alumina, and other inorganic powders, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and nylon.
- Organic powders such as -6, nylon-6,6, nylon-6, cyclic olefin, polystyrene, polymethacrylate, and the like.
- the transparency of the base material layer (A) 11 varies depending on the content of these fillers, and when it is not substantially contained, it is transparent, or the transparency decreases as the content increases.
- the printing information of the printing layer (C) 13 can be hidden, or adjusted to a semi-transparent or transparent state.
- the filler content is usually 5 to 60% by mass, preferably 20 to 50% by mass.
- the filler content of the base material layer (A) 11 is 3.0% by mass or less, preferably 1.0% by mass or less in terms of solid content with respect to the total amount of the base material layer (A) 11. Yes, more preferably 0.5% by mass or less, still more preferably 0.01% by mass.
- the filler content of the base material layer (A) 11 is in the above range, the base material layer (A) 11 becomes excellent in transparency, for example, printing without peeling off the base material layer (A) 11.
- the printed content of the layer (C) 13 can be clearly seen.
- the base layer (A) 11 can be peeled from the ink receiving layer (B) 12 while the printed layer (C) 13 is stuck to the resin molded product. Even when the base material layer (A) 11 contains a filler and the base material layer (A) 11 lacks transparency, the base material layer (A) 11 is replaced with the ink receiving layer (B) 12. It is possible to visually recognize the printed content of the printing layer (C) 13 by peeling between the two.
- the base material layer (A) 11 may contain a known additive as necessary in addition to the thermoplastic resin.
- the additive include a heat stabilizer, an antistatic agent, an antioxidant, an ultraviolet stabilizer, a dispersant, and a lubricant.
- the content of the additive in the base material layer (A) 11 is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0. 5 to 5 parts by mass.
- the thickness of the base material layer (A) 11 is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and still more preferably 40 to 100 ⁇ m.
- the thickness of the base material layer (A) 11 is equal to or greater than the lower limit of the above range, wrinkles are generated when the in-mold molding label 1 is imparted with appropriate rigidity and the printed layer (C) 13 is formed. And the label can be easily fixed at a desired position when inserted into the mold.
- the thickness of the base material layer (A) 11 is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in strength at the boundary portion of the in-mold molding label 1 in the obtained resin molded product, and the in-mold molding label It is possible to prevent damage from the end of the label 1 and to prevent the transparency of the in-mold molding label 1 from being lowered.
- molding observes a cross section with a microscope, and multiplies the ratio of the whole thickness of the label 1 for in-mold shaping
- the ink receiving layer (B) 12 is interposed between the printing layer (C) 13 and the base material layer (A) 11 in the in-mold molding label 1, and the printing layer (C ) A layer that accepts 13 prints.
- the printing layer (C) 13 is melted, the affinity between the printing layer (C) 13 and the ink receiving layer (B) 12 is improved, and the adhesion between the layers is enhanced.
- the printing layer (C) 13 is not provided on the entire surface of the ink receiving layer (B) 12, that is, provided only on a part of the ink receiving layer (B) 12.
- the molten resin constituting the resin molded product 21 and the portion of the ink receiving layer (B) 12 not covered with the printing layer (C) 13 come into contact with each other during in-mold molding.
- the ink receiving layer (B) melted by the heat of the molten resin is formed between the printing layers (C) 13 provided partially or intermittently by the pressure during in-mold molding.
- the resin is pseudo-bonded to the molten resin so as to fill the gap, and is cured after cooling, thereby contributing to pseudo-bonding between the resin molded product 21 and the in-mold molding label 1. That is, it is preferable that the ink receiving layer (B) 12 and the printing layer (C) 13 are in direct contact.
- the ink receiving layer (B) 12 itself may have a single layer structure or a multilayer structure of two or more layers. Moreover, when it is a multilayered structure of two or more layers, the layers may be composed of the same component or may be composed of different components.
- the peel strength between the base layer (A) 11 and the ink receiving layer (B) 12 is set to the printing layer (C) 13 and the resin molded product 21. It can be set lower than the peel strength. Further, the peel strength between the ink receiving layer (B) 12 and the print layer (C) 13 can be set lower than the peel strength between the print layer (C) 13 and the resin molded product 21.
- the printing layer (C) 13 is transferred from the label 1 side to the resin molded product 21 side when the label is peeled off.
- the polyethyleneimine polymer is a water-soluble polymer obtained by polymerizing ethyleneimine, not a complete linear polymer, but a polymer having a branched structure containing primary, secondary, and tertiary amines in the molecular skeleton. .
- both ends of the molecular chain are primary amines, and the other nitrogen atoms constitute secondary amines.
- a modifier or a crosslinking agent is allowed to act on polyethyleneimine, a secondary amine mainly reacts to produce a tertiary amine.
- the polyethylenimine resin is rich in reactivity.
- Functional groups that react with primary to tertiary amines of polyethyleneimine include aldehyde compounds, alkyl halide compounds, isocyanate compounds, epoxy compounds such as epichlorohydrin, cyanamide compounds, guanidine compounds, urea, carboxylic acid compounds, cyclic acid anhydride compounds, acyl halides. Compounds and the like.
- a compound having one of these functional groups in the molecule can be used as a modifier, and a compound having a plurality of functional groups in the molecule can be used as a cross-linking agent, respectively, and water resistance and solvent resistance can be imparted to the polyethyleneimine resin. Adjustment of peeling strength with (A) or the printing layer (C) becomes possible.
- Polyethyleneimine polymers include polyethyleneimine, alkyl-modified polyethyleneimine having 1 to 12 carbon atoms, poly (ethyleneimine-urea), poly (ethyleneimine-urea) ethyleneimine adduct, polyamine polyamide, polyamine Examples thereof include polyethyleneimine-based polymers such as polyamide ethyleneimine adducts and polyamine polyamide epichlorohydrin adducts.
- the polyethyleneimine polymer is a primary amino acid based on the total amount of amino groups from the viewpoint of adjusting the expiration date, reactivity, and peel strength with the base layer (A) or the printing layer (C) of the prepared coating liquid.
- the molar ratio of the group is preferably 0.01 to 0.1%
- the molar ratio of the secondary amino group is 1 to 99.5%
- the molar ratio of the tertiary amino group is preferably 0.1 to 10%.
- the molar ratio is the ratio of the number of moles of each amino group to the total number of moles of primary amino groups, secondary amino groups, and tertiary amino groups of polyethyleneimine.
- the number average molecular weight of the polyethyleneimine polymer is usually 200 to 100,000, preferably 300 to 70,000.
- the viscosity (mPa ⁇ s ⁇ 25 ° C.) is usually 200 to 150,000, preferably 10,000 to 100,000, and is appropriately adjusted to a viscosity that is diluted with water and easy to handle.
- the polyethyleneimine polymer those having properties such as water solubility, organic solvent availability and water dispersibility can be used.
- a commercially available product can be used as the polyethyleneimine polymer.
- Epomin registered trademark, manufactured by Nippon Shokubai Co., Ltd., product numbers SP-003, SP-006, SP-012, SP-018, SP-200).
- HM-2000, P-1000 and the like.
- a ring-opening polymerized ethylene imine as a raw material by a conventionally known method.
- ethyleneimine is reacted with a base amine such as ethylenediamine, diethylenetriamine, or monoethanolamine under an acid catalyst such as hydrochloric acid, sulfuric acid, or paratoluenesulfonic acid.
- a base amine such as ethylenediamine, diethylenetriamine, or monoethanolamine
- an acid catalyst such as hydrochloric acid, sulfuric acid, or paratoluenesulfonic acid.
- the resulting product commonly referred to as polyethyleneimine, can produce ethylenediamine derived from base amine, DETA, or a copolymer of monoethanolamine and ethyleneimine.
- the ink receiving layer (B) 12 may also contain additives known in the art.
- the additive contained in the ink receiving layer (B) 12 include an antistatic agent, a plasticizer, an antioxidant, and an ultraviolet absorber.
- the content of the additive in the ink receiving layer (B) 12 is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, based on the total amount of the ink receiving layer (B). Part by mass.
- the thickness of the ink receiving layer (B) 12 is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.03 to 5 ⁇ m, still more preferably 0.05 to 3 ⁇ m, and particularly preferably 0.1 to 1 ⁇ m. It is.
- the ink receiving layer (B) 12 is not less than the lower limit of the above range, the ink receiving layer (B) 12 is heated together with the printing layer (C) 13 by the heat of the molten resin of the resin molded product 21 during in-mold molding. When melted, the resin molded product 21 and the in-mold molding label 1 are easily fused, and sufficient adhesiveness tends to be obtained.
- the thickness of the ink receiving layer (B) is not more than the upper limit of the above range, the curling of the in-mold molding label 1 is prevented, and the printing layer (C) 13 on the ink receiving layer (B) 12 is prevented. And fixing to a mold becomes easy.
- the peel strength is obtained by cutting the labeled resin molded product 2 into a width (MD direction) of 15 mm and a length (TD direction) of 110 mm in accordance with JIS K6854-3: 1999, for example.
- a tester manufactured by Shimadzu Corporation, device name: Autograph AGS-D type
- it can be determined by T-peeling at a tensile speed of 300 mm / min.
- the peel strength between the base material layer (A) 11 and the ink receiving layer (B) 12 is equal to or higher than the peel strength between the in-mold molding label and the resin molded product, and is usually 0.5 to 10 N / 15 mm. It is preferably 1 to 5 N / 15 mm.
- the method for forming the base material layer (A) 11 is not particularly limited, and various known methods can be used. Specific examples include cast molding in which molten resin is extruded into a sheet using a single-layer or multilayer T-die or I-die connected to a screw-type extruder, and the molten resin is extruded into a tube using a circular die. Inflation molding in which the air pressure is expanded, calender molding in which a kneaded material is rolled with a plurality of hot rolls and processed into a sheet, and rolling molding are exemplified.
- the base material layer (A) 11 itself may have a single-layer structure or a multilayer structure of two or more layers.
- the ink receiving layer (B) 12 can also be formed by a method similar to the method for forming the substrate layer (A) 11 described above.
- the base material layer (A) 11 and the ink receiving layer (B) 12 for example, coextrusion molding in which both molten resins are laminated in a die, the base material layer (A) 11 and the ink receiving layer ( B) At least one of 12 in advance is formed into a film, extruded laminate for extruding and laminating a heat-melted resin constituting the other layer, and a base material layer (A) 11 obtained by film formation in advance
- Examples include dry laminate molding or wet laminate molding in which the ink receiving layer (B) 12 is laminated via an adhesive layer.
- the thickness of the obtained ink receiving layer (B) 12 is preferably 3 to 30 ⁇ m.
- the resin constituting the ink receiving layer (B) 12 can be applied as a paint to the base material layer (A) 11 by a method described later, and dried as necessary.
- This paint can be prepared by dissolving the resin constituting the ink receiving layer (B) 12 in a solvent or dispersing it in a solvent.
- a solvent For example, water, toluene, acetone, methyl ethyl ketone, methanol, ethanol etc. can be used conveniently.
- the coating method is not particularly limited.
- the thickness of the obtained ink receiving layer (B) 12 is preferably 0.1 to 10 ⁇ m.
- the molten resin of the base material layer (A) 11 and the ink receiving layer (B) 12 is laminated in the die and extruded into a sheet shape.
- a method of simultaneously laminating and forming both layers by coextrusion cast molding is preferable. This method is simple in terms of process, and the base layer (A) 11 and the ink receiving layer (B) 12 are not easily separated in post-processing steps such as formation or cutting of the printing layer (C) 13. It is preferable because it can be obtained as a coextruded film having an adhesive strength of
- the base material layer (A) 11 and the ink receiving layer (B) 12 may be non-stretched (unstretched) films that are not stretched, or may be stretched films by stretching in at least a uniaxial direction.
- the unstretched film is further excellent in transparency and shape followability to a molded product.
- the stretched film is more excellent in transparency, lightness, and thickness uniformity due to thinning.
- biaxial stretching may be superposed by uniaxial stretching.
- the in-mold forming label 1 of the present embodiment may be subjected to surface oxidation treatment on the ink receiving layer (B) 12 as necessary.
- the surface of the film after molding has a relatively low surface free energy, and the surface free energy of the surface of the film can be improved by subjecting the surface of the film to surface oxidation treatment.
- the transferability of the toner composition is improved, thereby improving the adhesion between the printing layer (C) 13 and the ink receiving layer (B) 12.
- the transferability of the toner composition may be improved by controlling the water contact angle on the surface of the ink receiving layer (B) 12.
- Examples of the surface oxidation treatment include corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, and ozone treatment.
- the ink receiving layer (B) may be subjected to frame processing.
- the in-mold molding label 1 may be formed with a surface coating layer on the ink receiving layer (B) 12 for the same purpose as the surface oxidation treatment described above.
- Print layer (C) The print layer (C) 13 is in contact with the molten resin constituting the resin molded product 21 in a molding machine (for example, a mold) during in-mold molding.
- the printed layer (C) 13 is melted by the heat of the molten resin so as to be fused with the molten resin, and further cured after cooling, so that the wall surface of the resin molded product 21 and the in-mold molding label 1 are adhered. Contribute to.
- the printing layer (C) 13 is a resin film layer mainly composed of a polyethylene resin.
- the printed layer (C) 13 may be provided over the entire surface of the ink receiving layer (B) 12 as shown in FIG. 1, and the ink receiving layer as shown in FIG. (B) 12 may be provided partially or intermittently.
- the printing layer (C) 13 is partially or intermittently provided on the ink receiving layer (B)
- the printing layer (C) 13 is provided so as to constitute a character or a pattern. It is done.
- the printing layer (C) 13 is provided in patterns, such as a dot form, stripe form, and a check form, is mentioned.
- the printing layer (C) 13 may be provided so that a position, a shape, and a size may be arranged at random with a gap between adjacent printing layers (C) 13.
- the printing layer (C) 13 itself may have a single layer structure or a multilayer structure of two or more layers. Moreover, when it is a multilayered structure of two or more layers, the layers may be composed of the same component or may be composed of different components.
- Examples of printing methods for forming the printing layer (C) 13 include offset printing, letterpress printing, flexographic printing, gravure printing, screen printing, and inkjet printing. Further, the type of ink attached to the printing layer (C) 13 may be appropriately selected according to the printing method, and is not particularly limited. From the viewpoint of transferability and adhesion of the ink to the ink receiving layer (B) 12, liquid electrostatic ink (typically, Hewlett-Packard electro-ink) is preferably used as the toner composition.
- liquid electrostatic ink typically, Hewlett-Packard electro-ink
- the printing layer (C) 13 of the present embodiment is preferably a toner printing layer formed of a liquid ink containing thermoplastic toner particles in which a coloring material is blended in a binder of a thermoplastic resin containing an ethylene copolymer. It is. More preferably, the thermoplastic toner particles are charged. More preferably, printing is performed by transferring thermoplastic toner particles to the printing layer (C) 13 by electrophotography. Particularly preferably, it is formed using a liquid electro-ink containing the thermoplastic toner particles.
- the printing method is preferably offset printing, more preferably digital offset printing, from the viewpoints of handling a small lot and productivity.
- the printing layer (C) 13 is formed by offset printing.
- the printing layer (C) 13 is a layer mainly composed of a polyethylene-based resin. It may be formed using another printing method or a toner composition.
- the toner composition contains a polyethylene resin. Further, it usually contains a coloring material.
- the toner composition preferably further contains a liquid carrier and a charge control compound.
- the toner composition is more preferably charged.
- the toner composition may further contain a dispersion stabilizer that stabilizes the electrical properties of the charge control compound.
- the printing layer (C) 13 contains 50 mass% or more of polyethylene resin, it is more preferable to contain 60 mass% or more, and it is still more preferable to contain 70 mass% or more.
- the content is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and still more preferably 99.0% by mass or less.
- the liquid carrier dissolves, disperses or emulsifies the polyethylene resin and the color material in the toner composition.
- the liquid carrier is not particularly limited, but a nonpolar liquid having a low dielectric constant is preferably used.
- the nonpolar liquid preferably has an electrical resistivity of at least 10 9 ⁇ ⁇ cm and a dielectric constant of less than 3.0.
- Examples of the nonpolar liquid include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, light mineral oils, and the like.
- aliphatic hydrocarbons branched chain aliphatic hydrocarbons are preferable, and for example, Isopar (registered trademark) series isoparaffin hydrocarbons (manufactured by ExxonMobil) are preferably used.
- the content of the liquid carrier is not particularly limited, but is preferably 10 to 99% by mass, more preferably 30 to 90% by mass, and further preferably 50 to 80% by mass with respect to the total amount of the toner composition.
- polyethylene resin examples of the polyethylene resin contained in the printing layer (C) 13 as a main component include a low density to medium density high pressure polyethylene having a density of 0.900 to 0.935 g / cm 3 , and a density of 0.880 to 0. 940 g / cm 3 linear linear polyethylene, ethylene copolymer and the like. Of these, linear linear polyethylene or ethylene-based copolymer is preferable.
- Ethylene copolymers contained in the printing layer (C) 13 include ethylene and vinyl esters such as vinyl acetate and vinyl propionate; (meth) acrylic acid; methyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as ethyl and butyl (meth) acrylate; carbon numbers such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 4-methyl-1-pentene Examples thereof include, but are not particularly limited to, a copolymer with one or more comonomers selected from 3 to 10 ⁇ -olefins; terephthalic acid; and alkyl terephthalates such as butyl terephthalate.
- an ethylene / vinyl acetate copolymer and an ethylene / methacrylic acid copolymer are preferable, and an ethylene / methacrylic acid copolymer is preferable. More preferred.
- the content of ethylene units in the ethylene copolymer is not particularly limited, but is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 60 to 85% by mass.
- the content of the ethylene copolymer is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 40% by mass with respect to the total amount of the toner composition. is there.
- the printing layer (C) 13 preferably contains an ethylene copolymer having a melting point of 135 ° C. or lower.
- the melting point of the ethylene-based copolymer contained in the printing layer (C) 13 is preferably 65 ° C to 135 ° C, more preferably 75 ° C to 130 ° C, still more preferably 85 ° C to 125 ° C or less, Particularly preferred is 90 ° C to 120 ° C.
- the melting point of the ethylene copolymer constituting the printing layer (C) 13 exceeds the lower limit of the above range, stickiness can be suppressed at room temperature and blocking can be prevented. Further, when the melting point of the ethylene copolymer constituting the printing layer (C) 13 is lower than the upper limit of the above range, the adhesion between the printing layer (C) 13 and the ink receiving layer (B) 12, and printing The adhesion between the layer (C) 13 and the resin molded product 21 tends to be improved.
- the adhesion between the printing layer (C) 13 and the resin molded product 21 can be enhanced.
- the adhesiveness between the printed layer (C) 13 and the resin molded product 21 can be adjusted to be low by partially providing the printed layer (C) 13 on the surface of the ink receiving layer (B) 12.
- the printing layer (C) 13 As a form of the printing layer (C) 13 when the printing layer (C) 13 is partially provided on the surface of the ink receiving layer (B) 12, there are a halftone dot shape, a mesh shape, a line shape with equal intervals, and the like. It is preferable that the printing layer (C) 13 is formed of a regular pattern having a uniform and fine size.
- the printing layer (C) 13 By configuring the printing layer (C) 13 with the pattern as described above, it is possible to reduce unevenness of the adhesive strength generated between the printing layer (C) 13 and the resin molded product 21, and to form a resin molded product. The touch when the label is peeled from 21 is also smooth.
- fusing point of resin means the value calculated
- the melting point of the ethylene copolymer constituting the printing layer (C) 13 is preferably 5 ° C. or more lower than the melting point of the thermoplastic resin constituting the resin molded article 21, and more preferably 10 ° C. or more lower. Thereby, there exists a tendency for the adhesiveness of the printing layer (C) 13 and the resin molded product 21 to improve.
- the color material a known dye or pigment used for printing ink can be used.
- the pigment may be an organic pigment or an inorganic pigment.
- the dye include azo dyes, anthraquinone dyes, indigo dyes, cyanine dyes, quinoline dyes, benzoquinone dyes, naphthoquinone dyes, and phthalocyanine dyes, but are not particularly limited thereto.
- the organic pigment include, but are not limited to, quinacridone pigments such as quindagenta, azo pigments such as toluidine red, phthalocyanine pigments such as monastral blue, monastral green, and the like.
- the inorganic pigment examples include carbon black, metal oxides such as Fe, Co, Ni, and Ti, ferrites and alloys of metals such as Zn, Cd, Ba, and Mg, but are not particularly limited thereto.
- a pigment is preferable, and an organic pigment and an inorganic pigment are more preferable.
- the content of the color material is not particularly limited, but is preferably 0.1 to 35% by mass, more preferably 1 to 30% by mass, and still more preferably 5% for the dye and the organic pigment with respect to the total amount of the toner composition. To 25% by mass.
- the content is preferably 0.1 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 30 to 50% by mass.
- the charge control compound is used to control the charge polarity and charge amount of the thermoplastic toner particles.
- an anionic, cationic, amphoteric or nonionic surfactant compound is used.
- One of these charge control compounds may be used alone, or two or more thereof may be used in combination.
- metal soap such as barium petroleum acid, phospholipid such as lecithin, metal salt compound of organic acid, organic phosphate compound, organic sulfonic acid compound, quaternary ammonium salt compound, etc. Although it is mentioned, it is not specifically limited to these.
- the content of the charge control compound is not particularly limited, but is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 4% by mass, and still more preferably based on the total amount of the toner composition. 1% by mass to 3% by mass.
- Dispersion stabilizer A dispersion stabilizer is used to help stabilize the charge control compound.
- the dispersant include, but are not limited to, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, and polyethylene glycol.
- the toner composition can be prepared by mixing a polyethylene resin and a coloring material while heating to form thermoplastic toner particles in a liquid carrier, and adding a charge control compound as necessary. Note that wax may be mixed together with the colorant when preparing the toner composition. When the toner composition contains a wax, the adhesion between the printed layer (C) 13 and the resin molded article 21 is improved.
- Formation of the printing layer (C) can be performed, for example, by performing offset printing using liquid electro-ink. First, a cylindrical image forming plate is charged by corona discharge, and then this image forming plate is exposed to form an electrostatic image. Next, the electrostatic image is developed by supplying a toner composition to the image plate on which the electrostatic image is formed. Further, the electrostatic toner image formed by the toner composition is transferred from the image forming plate to a cylindrical blanket. The toner composition transferred to the blanket is heated by the blanket to fuse or aggregate the thermoplastic toner particles contained in the toner composition.
- thermoplastic toner particles form a polymer film, and a polymer film image containing a colorant in the polymer film is formed on the blanket.
- the polymer film image thus formed is transferred from the blanket to the ink receiving layer (B) 12, and further cooled and cured, whereby the printed layer (C) 13 is formed.
- the ink density indicates the ratio of the area of the printing layer (C) 13 to the area of the ink receiving layer (B) 12.
- the printing layer (C) 13 is a collection of dot-like inks formed on the ink receiving layer (B) 12. It is configured as (halftone dot).
- the ink density can be represented by a halftone dot area ratio indicating a ratio of an area occupied by a halftone dot portion on the ink receiving layer (B) 12.
- the dot area ratio occupied by the printed layer (C) 13 is preferably 5 to 100%, more preferably 10 to 90%, still more preferably 15 to 80%, and particularly preferably 20 to 70%.
- the ink concentration of the in-mold molding label 1 is within the above range, sufficient adhesion between the in-mold molding label 1 on which the printing layer (C) 13 is formed and the resin molded product 21 tends to be exhibited. It is in.
- the halftone dot area ratio is a ratio of the area of the halftone dot portion that is printed by taking an image on the printed layer (C) 13 side of the in-mold label 1 using, for example, a CCD camera. Is a value calculated by obtaining image data by image processing.
- the thickness of the printing layer (C) 13 is appropriately changed according to the printing method and the toner composition, and is not particularly limited, but is preferably 0.5 to 20 ⁇ m, more preferably 0.8 to 10 ⁇ m, still more preferably 1. 0 to 5 ⁇ m.
- the printing layer (C) 13 is within the above range, the ink density is sufficiently maintained, visibility can be improved, and sufficient adhesiveness tends to be maintained.
- the ratio between the thickness of the ink receiving layer (B) 12 and the thickness of the printing layer (C) 13 is usually 1:20 to 2: 1, preferably 1:15 to 1: 1, more preferably. 1:12 to 1: 5.
- the ratio of the thickness of the ink receiving layer (B) 12 and the thickness of the printing layer (C) 13 is in the above range, when the printing layer (C) 13 is melted by the heat of the molten resin in in-mold molding, The heat of the molten resin is also transmitted to the ink receiving layer (B) 12 and the ink receiving layer (B) 12 is also partially melted, so that the ink receiving layer (B) 12 contributes to the adhesion with the resin molded product 21. It will be.
- the base material layer (A) 11, the ink receiving layer (B) 12, and the printing layer (C) 13 are preferably thickest in the base material layer (A) 11, and the ink receiving layer (B) 12. Is the thinnest, and the printing layer (C) has an intermediate thickness between the base material layer (A) 11 and the ink receiving layer (B) 12.
- the in-mold molding label 1 of the present invention has an ink receiving layer (B) of the base material layer (A) as shown in FIG. 7 separately from the ink receiving layer (B) 12 and the printing layer (C) 13.
- the second printed layer (c) and the second ink receiving layer (b) may be further provided in this order on the surface opposite to the side where the ink is provided. That is, the in-mold molding label 1 of the present invention includes a second printed layer (c) 41, a second ink receiving layer (b) 31, a base material layer (A) 11, an ink receiving layer (B) 12,
- the printed layer (C) 13 may be laminated so as to include this order.
- the second ink receiving layer (b) 31 and the second printing layer (c) 41 are the same as the ink receiving layer (B) 12 and the printing layer (C) 13, respectively.
- the optional layer includes a base layer (A) 11 and the ink receiving layer (B) 12 or a layer that adjusts the peel strength between the ink receiving layer (B) 12 and the printing layer (C) 13.
- Various layers are provided on the surface opposite to the side where the ink receiving layer (B) 12 and the printing layer (C) 13 are provided via the material layer (A) 11 as long as the effects of the present invention are not impaired. It may be provided.
- the in-mold label 1 of the present invention has the second ink receiving layer (b) 31 and the second printed layer (c) 41, that is, the base layer (A) 11 is interposed.
- the resin-molded article 2 with a label to which the label is attached can have various design properties as described below.
- the print information of the second print layer (c) 41 is visually recognized before the base material layer (A) 11 is peeled off.
- the printing information of the printing layer (C) 13 is now visually recognized.
- the second printing can be performed by irradiating blue light or the like even before the base material layer (A) 11 is peeled off. It is also possible to view the printing information of the layer (c) 41 and the printing information of the printing layer (C) 13 at the same time.
- the base material layer (A) 11 is transparent, before the base material layer (A) 11 is peeled off, the printing information of both the printing layer (C) 13 and the second printing layer (c) 41 is printed. Are simultaneously recognized, and when the base material layer (A) 11 is peeled off, only the printing information of the printing layer (C) 13 is visually recognized.
- the in-mold molding label 1 of the present invention may be provided with a heat seal layer at an arbitrary location.
- the heat seal layer is activated by heat during molding of the resin molded product and has a function of an adhesive.
- the heat seal layer can be formed, for example, by molding a resin composition containing a thermoplastic resin into a film shape.
- thermoplastic resin used for a heat seal layer A conventionally well-known thing can be used suitably as a thermoplastic resin used for a heat seal layer.
- the label and the resin molded product 21 are not provided with a heat seal layer. Adhesion can be sufficiently performed.
- the in-mold molding label 1 of the present invention is made of a resin film on the surface of the base layer (A) 11 in order to improve fastness such as light resistance, water resistance, gas resistance, and friction resistance.
- a protective layer may be provided.
- the resin which comprises a protective layer is not specifically limited, The thing similar to the thermoplastic resin used by the base material layer (A) 11 mentioned above can be used.
- the thickness of the protective layer is not particularly limited, but is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m. Various methods can be adopted as means for providing the protective layer, and are not particularly limited.
- the present invention also relates to a resin molded product 2 with a label in which the above-mentioned in-mold molding label 1 is bonded and integrated to a resin molded product by in-mold molding.
- the resin molded product 2 with a label according to the present invention is a resin molded product after the peeling progresses at the interface between the base material layer (A) 11 and the ink receiving layer (B) 12 and the in-mold molding label 1 is peeled off. It has an ink receiving layer (B) 12 and a printing layer (C) 13 on the surface of the product, or peeling progresses at the interface between the ink receiving layer (B) 12 and the printing layer (C) 13 for in-mold molding.
- the printed layer (C) 13 is provided on the surface of the resin molded product after the label 1 is peeled off.
- the in-mold molding label 1 of the present invention can be particularly suitably used as an in-mold molding label for blow molding.
- the resin molded product 2 with a label manufactured as described above since the label and the resin molded product are integrally molded after the label is fixed in the mold, there is no deformation of the label, and the molded product main body and the label.
- the adhesive has a strong adhesive strength, has no blisters, and has a good appearance decorated with a label.
- the in-mold molding label 1 of the present invention can also be used as an in-mold molding label for differential pressure molding.
- the label is fixed to the inner wall of the die by suction, and then the container molding material resin sheet
- the melt is guided to the upper part of the lower female mold, is subjected to differential pressure molding by a conventional method, and a resin molded product with a label in which the label is bonded and integrated to the outer wall of the molded product is molded.
- the differential pressure molding either a vacuum molding method or a pressure air molding method can be adopted, but a method using both of them and utilizing plug assist is preferable.
- the label for in-mold molding and the resin molded product are “attached and integrated” means that a part of the resin component constituting the resin molded product and the ink receiving layer (B) 12 of the label for in-mold molding. Or the state in which a part of resin component which comprises the printing layer (C) 13 is adhere
- sticking integration can be realized by forming the labeled resin molded product 2 by in-mold molding.
- the resin molding material is not particularly limited as long as it is a thermoplastic resin, but the viewpoint of adhesion to the ink receiving layer (B) 12 and the printing layer (C) 13 is not limited.
- thermoplastic resin such as polystyrene resin and polyethylene terephthalate resin.
- thermoplastic resins may be used alone or in combination. Of these, polyethylene resins and polystyrene resins are preferably used, and polyethylene resins are more preferably used.
- the labeled resin molded product 2 of the present invention includes, for example, household detergent, bathtub detergent, toilet bowl detergent, car wash detergent, facial cleanser, liquid soap, shampoo, rinse, deodorant, liquid bath agent, iron paste Containers for chemicals (bottles) used for chemicals, alcohol for sterilization, wax for polishing, insecticides, etc .; Containers for foods (bottles) used for soft drinks, liquor, soy sauce, oil, sauce, sauces, dressings, etc .; jam, margarine Squeeze containers used for spreads such as peanut butter, ketchup and mayonnaise; containers for ice cream, yogurt and the like; containers for laundry detergent, dishwashing detergent, wet tissue and the like.
- the base material layer (A) 11 of the in-mold molding label 1 is changed to a transparent or translucent one, the base material layer (A) functions as a barrier layer, thereby The durability of printing information can be improved.
- a resin-molded article 2 with a label having a design in which the printing information of the printing layer (C) 13 and the second ink receiving layer (b) 31 is superimposed may be used.
- the peel strength between the base material layer (A) and the ink receiving layer (B) is as follows.
- the resin molded product with label is 15 mm wide (MD direction) and length (TD direction) in accordance with JIS K6854-3: 1999.
- Table 1 shows the details of the materials used in the examples and comparative examples.
- Example 1> Manufacture of base material layer
- the base material layer material A1 was kneaded with an extruder set at 230 ° C. Then, it supplied to the die
- MD direction machine direction
- TD direction transverse direction
- the base layer of the biaxially stretched film was obtained by slitting the ears. At this time, the thickness of the base material layer was 80 ⁇ m.
- Corona discharge treatment was performed on one side of the base material layer produced in the previous step using a corona discharge treatment apparatus (manufactured by Kasuga Electric Co., Ltd., device name: HF400F).
- a corona discharge treatment apparatus manufactured by Kasuga Electric Co., Ltd., device name: HF400F.
- an aluminum discharge electrode having a length of 0.8 m and a silicone film roll as a treater roll were used.
- the gap between the discharge electrode and the treater roll was 5 mm
- the line processing speed was 15 m / min
- the applied energy density was 4,200 J / m 2 .
- the ink receiving layer material B1 was coated on the surface subjected to the corona discharge treatment so that the solid content after drying was 0.2 g / m 2 .
- a bar coater was used for coating.
- the ink receiving layer was formed by drying in an oven and wound up.
- the thickness of the ink receiving layer was about 0.2 ⁇ m.
- a printing layer was formed by printing on the ink receiving layer prepared in the above step.
- the printing layer material C1 shown in Table 1 was used as the printing layer material, and a wet electrophotographic printer (manufactured by Hewlett-Packard Inc., device name: HP Indigo WS6800) was used.
- the printing conditions were a room temperature of 23 ° C., a relative humidity of 50%, a blanket temperature of 105 ° C., and a transfer pressure of 200 kg.
- the dot area ratio was 100%.
- the base material layer is punched into a size of 70 mm in the MD direction and 90 mm in the TD direction, and a label for in-mold molding Got.
- a label was placed in the mold and fixed by suction so that the non-printed surface of the in-mold molding label was in contact with the cavity on a test piece molding mold having a cavity with a length of 130 mm, a width of 150 mm, and a thickness of 2 mm. .
- the mold was closed, and using an injection molding machine (manufactured by Niigata Steel Co., Ltd., equipment name: NV50ST), the resin molded product material D1 shown in Table 1 was resin temperature 230 ° C., injection pressure 74 N / m. Injection molding was performed under the conditions of 2 . Subsequently, after injection molding, the mold was sufficiently cooled for 20 seconds, and the mold was opened to obtain a resin molded product with a label.
- Example 2 ⁇ Examples 2, 3 and 6>
- the labels and the resin molded products with labels of Examples 2, 3 and 6 were obtained in the same manner as in Example 1. Obtained.
- Example 4 In Example 3, the label and the resin-molded article with a label of Example 4 were obtained in the same manner as in Example 3 except that the base material layer material A1 was changed to the base material layer material A2 shown in Table 1.
- Example 5 a label and a resin molded product with a label of Example 5 were obtained in the same manner as in Example 1 except that the dot area ratio 100% as the printing condition was changed to 50% dot-like printing.
- Example 1 ⁇ Comparative Examples 1 and 2>
- the labels of Comparative Examples 1 and 2 and the resin molded products with labels were obtained in the same manner as in Example 1.
- Example 3 In Example 1, when the ink receiving layer material B1 was changed to the ink receiving layer material B4 shown in Table 1, the ink was not fixed on the ink receiving layer and printing was not possible.
- Example 4 In Example 1, when the ink receiving layer (B) was not provided, the ink was not fixed on the base material layer (A) and printing was not possible.
- Example 1 ⁇ Comparative Examples 5 and 6>
- the printing layer material C1 was changed to the printing layer material shown in Table 1
- labels and comparative resin molded articles of Comparative Examples 5 and 6 were obtained in the same manner as in Example 1.
- Table 2 shows the configuration of resin molded products with labels for in-mold molding and the evaluation results.
- the printed layer (C) is transferred from the label (base material layer) side to the resin molded product side, and a resin molded product with a pattern having print information is obtained. It was.
- the peel strength was 1 to 10 N / 15 mm, indicating a practical value as an easily peelable label.
- the printing layer (C) is transferred from the label side to the resin molded product side.
- the peeling strength between the printing layer (C) and the resin molded product is that the printing layer (C) and the ink receiving layer (B).
- the peel strength between the printed layer (C) and the resin molded product is higher than the peel strength between the ink receiving layer (B) and the base material layer (A).
- Example 1 and Example 5 were compared, it was shown that the peel strength can be controlled by changing the dot area ratio.
- the printed layer (C) is not transferred to the resin-molded product when the label is peeled off. Some remained on the label side. Also, the peel strength is strong, and it exceeds the practical range as an easily peelable label.
- the ink receiving layer (B) of the label of Comparative Example 3 had poor ink receiving properties, and the printing layer (C) could not be provided. Since the resin-molded article with a label of Comparative Example 4 does not have the ink receiving layer (B), the ink could not be transferred to the label and the printing layer (C) could not be provided.
- the practically preferable peel strength could not be obtained with the resin molded products with labels of Comparative Examples 5 and 6 using a general oil-based ink or ultraviolet curable ink for offset printing.
- Examples 1 to 6 and Comparative Examples 1 to 4 show that it is preferable to use a polyethyleneimine resin as the material of the ink receiving layer (B).
- the material is not limited to polyethyleneimine (B1) as long as the material of the ink receiving layer (B) satisfies the relationship of the peel strength.
- the injection mold was used in the examples and comparative examples, the present invention is not limited to this, and can be used for hollow molding such as direct blow, stretch blow, injection blow, etc., pressure molding, and vacuum molding.
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Abstract
Description
[1]熱可塑性樹脂を含有する基材層(A)と、
ポリエチレンイミン系重合体を含むインク受容層(B)と、
ポリエチレン系樹脂を主成分とする印刷層(C)と
をこの順に有するインモールド成形用ラベル。
[2]前記熱可塑性樹脂が、オレフィン系樹脂、スチレン系樹脂、エステル系樹脂、アミド系樹脂およびポリカーボネートからなる群より選択される少なくとも1種類の熱可塑性樹脂である、[1]に記載のインモールド成形用ラベル。
[3]前記ポリエチレン系樹脂が、エチレン・メタクリル酸共重合体を含む、[1]または[2]に記載のインモールド成形用ラベル。
[4]前記基材層(A)のインク受容層(B)が設けられている方とは反対の面に、さらに第2の印刷層(c)、及び第2のインク受容層(b)をこの順に含む[1]~[3]のいずれかに記載のインモールド成形用ラベル。
[5]前記[1]~[4]のいずれかに記載のインモールド成形用ラベルをインモールド成形により樹脂成形品に貼着一体化したラベル付き樹脂成形品。
[6]前記樹脂成形品がポリエチレン系樹脂、ポリスチレン樹脂より選択される少なくとも1種の熱可塑性樹脂を含む、[5]に記載のラベル付き樹脂成形品。
[7]前記ラベル付き樹脂成形品から前記インモールド成形用ラベルを剥離すると基材層(A)とインク受容層(B)間の界面またはインク受容層(B)と印刷層(C)との界面で剥離し、インモールド成形用ラベルを剥離した後の樹脂成形品表面に少なくとも印刷層(C)を有する、[5]または[6]に記載のラベル付き樹脂成形品。
また、本明細書において、(メタ)アクリル酸とは、アクリル酸及びメタクリル酸の双方が含まれる。
また、本明細書において、「主成分」と表記するときは、対象とする組成物中に含まれる各成分の中で、質量基準で最も含有量が多い成分を指す。
本発明のインモールド成形用ラベルは、基材層(A)、インク受容層(B)及び印刷層(C)を含む。図1は本発明のインモールド成形用ラベルの一実施態様を示す図であり、インモールド成形用ラベル1は、基材層(A)11、インク受容層(B)12、印刷層(C)13をこの順に有するように積層したものである。また、図3に示されているように、本発明のインモールド成形用ラベル1においては、基材層(A)11とインク受容層(B)12との間の界面で剥離が可能である。
基材層(A)は熱可塑性樹脂を含む。図1に示すように、インモールド成形用ラベル1において、基材層(A)11上に、インク受容層(B)12を挟んで印刷層(C)13が設けられている。基材層(A)11は、少なくとも印刷層(C)13及びインク受容層(B)12を支持して、印刷又は加工の際にハンドリングができる程度の剛性(コシ)をインモールド成形用ラベル1に与える層である。また、図3、図4に示すように、印刷層(C)13が樹脂成形品21に熱融着した状態で、基材層(A)11はラベル付き樹脂成形品2の外表面に存在し、印刷層(C)13及びインク受容層(B)12の保護層としても機能する。なお、上述したように、基材層(A)11は、インク受容層(B)12との間の界面で剥離が可能であるため、剥離後は前記保護層としての機能は失われることになる。
基材層(A)11に用いる熱可塑性樹脂の種類は特に制限されない。例えば、フィルム成形が可能な高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、ポリプロピレン、プロピレン系共重合樹脂、ポリメチル-1-ペンテン、エチレン・環状オレフィン共重合体等のオレフィン系樹脂;アタクティックポリスチレン、シンジオタクティックポリスチレン、スチレン-マレイン酸共重合体等のスチレン系樹脂;ポリエチレンテレフタレート、ポリエチレンテレフタレートイソフタレート、ポリブチレンテレフタレート、およびポリブチレンサクシネート、ポリブチレンアジペート、ポリ乳酸等のエステル系樹脂;エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体、マレイン酸変性ポリエチレン、マレイン酸変性ポリプロピレン等の官能基含有ポリオレフィン樹脂;ナイロン-6、ナイロン-6,6等のアミド系樹脂;およびポリカーボネートが挙げられる。これらの樹脂の中から、1種類もしくは2種類以上を混合して使用することができる。
基材層(A)11は、前記の熱可塑性樹脂に加え、必要に応じて公知の添加剤を含んでもよい。添加剤としては、例えば、熱安定剤、帯電防止剤、酸化防止剤、紫外線安定剤、分散剤及び潤滑剤等が挙げられる。基材層(A)11における添加剤の含有量は、特に限定されないが、基材層(A)11の質量を100質量部として、好ましくは0.1~10質量部、より好ましくは0.5~5質量部である。
基材層(A)11の厚みは、特に制限されないが、好ましくは20~200μm、より好ましくは30~150μm、さらに好ましくは40~100μmである。基材層(A)11の厚みが前記範囲の下限値以上であることにより、インモールド成形用ラベル1に適度な剛性を付与して、印刷層(C)13を形成する際にシワの発生を防止できるとともに、金型内への挿入時に所望の位置にラベルを固定しやすくなる。また、基材層(A)11の厚みが前記範囲の上限値以下であることにより、得られる樹脂成形品におけるインモールド成形用ラベル1の境界部分の強度低下を防止でき、インモールド成形用ラベル1のラベル端部からの破損を防ぐことができるとともに、インモールド成形用ラベル1の透明性の低下を防ぐことができる。
図1に示すように、インク受容層(B)12は、インモールド成形用ラベル1において、印刷層(C)13と基材層(A)11との間に介在して、印刷層(C)13の印刷を受容する層である。印刷層(C)13が溶融することで、印刷層(C)13とインク受容層(B)12の親和性が向上し、互いの層の密着が強くなる。
インク受容層(B)12の厚みは、特に制限されないが、好ましくは0.01~10μm、より好ましくは0.03~5μm、さらに好ましくは0.05~3μm、特に好ましくは0.1~1μmである。インク受容層(B)12の厚みが前記範囲の下限値以上であることにより、インモールド成形時にインク受容層(B)12が樹脂成形品21の溶融樹脂の熱により印刷層(C)13とともに融解して、樹脂成形品21とインモールド成形用ラベル1が融着しやすく、十分な接着性が得られる傾向にある。また、インク受容層(B)の厚みが前記範囲の上限値以下であることにより、インモールド成形用ラベル1のカールの発生を防ぎ、インク受容層(B)12への印刷層(C)13の形成や、金型への固定が容易となる。
前記のように、インク受容層(B)12がポリエチレンイミン系重合体を含むことにより、基材層(A)11等とインク受容層(B)12との剥離強度を適度に低くすることができる。
基材層(A)11を成形する方法は特に限定されず、公知の種々の方法が使用できる。具体例としては、スクリュー型押出機に接続された単層又は多層のTダイやIダイを使用して溶融樹脂をシート状に押し出すキャスト成形、円形ダイを使用し溶融樹脂をチューブ状に押し出し内部の空気圧力で膨張させるインフレーション成形、混練された材料を複数の熱ロールで圧延しシート状に加工するカレンダー成形、圧延成形等が挙げられる。基材層(A)11自体は、単層構造であってもよく、2層以上の多層構造であってもよい。
インク受容層(B)12も前記の基材層(A)11の成形方法と同様の方法で成形することができる。
印刷層(C)13は、インモールド成形の際に、成形機(例えば金型)内において樹脂成形品21を構成する溶融樹脂と接触する。印刷層(C)13は、溶融樹脂の熱により溶融することで、この溶融樹脂と融着し、さらに冷却後に硬化して、樹脂成形品21の壁面とインモールド成形用ラベル1との貼着に寄与する。
トナー組成物は、ポリエチレン系樹脂を含有する。さらに、通常色材を含有する。また、トナー組成物は、液体担体と、電荷制御化合物とをさらに含有することが好ましい。トナー組成物は、帯電性を有することがより好ましい。トナー組成物は、電荷制御化合物の電気的性質を安定させる分散安定剤をさらに含有してもよい。このようなポリエチレン系樹脂及び色材を分散したトナー組成物を、インク受容層(B)12上に付着(或いは、転移、転写等)させることによって、印刷情報を有する印刷層(C)13を形成することができる。すなわち、印刷層(C)13は、ポリエチレン系樹脂を主成分として含有するポリマーフィルムであって、このポリマーフィルムに通常色材が含まれている。なお、印刷層(C)13は、ポリエチレン系樹脂を50質量%以上含有することが好ましく、60質量%以上含有することがより好ましく、70質量%以上含有することが更に好ましい。一方、99.9質量%以下含有することが好ましく、99.5質量%以下含有することがより好ましく、99.0質量%以下含有することが更に好ましい。
液体担体は、トナー組成物において、ポリエチレン系樹脂及び色材を溶解、分散、又は乳化させるものである。液体担体としては、特に限定されないが、低誘電率の無極性液体が好ましく用いられる。無極性液体は、少なくとも109Ω・cm以上の電気抵抗率と、3.0未満の誘電定数を持つことが好ましい。無極性液体としては、例えば、脂肪族炭化水素、芳香族炭化水素、及び軽質鉱油等が挙げられるが、これらに特に限定されない。脂肪族炭化水素の中でも、分枝鎖脂肪族炭化水素が好ましく、例えばIsopar(登録商標)系列のイソパラフィン炭化水素(エクソンモービル社製)が好適に用いられる。液体担体の含有量は、特に限定されないが、トナー組成物の総量に対して、好ましくは10~99質量%、より好ましくは30~90質量%、さらに好ましくは50~80質量%である。
印刷層(C)13が主成分として含有するポリエチレン系樹脂としては、例えば、密度が0.900~0.935g/cm3の低密度ないし中密度の高圧法ポリエチレン、密度が0.880~0.940g/cm3の直鎖線状ポリエチレン、およびエチレン系共重合体等が挙げられる。なかでも、直鎖線状ポリエチレンまたはエチレン系共重合体が好ましい。
印刷層(C)13に含有されるエチレン系共重合体としては、エチレンと、酢酸ビニル、プロピオン酸ビニル等のビニルエステル;(メタ)アクリル酸;(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル等の(メタ)アクリル酸エステル;プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、4-メチル-1-ペンテン等の炭素数3~10のα-オレフィン;テレフタル酸;ブチルテレフタレート等のアルキルテレフタレートから選ばれる1種又は2種以上のコモノマーとの共重合体が挙げられるが、これらに特に限定されない。
色材としては、印刷用のインクに使用される公知の染料又は顔料を用いることができる。また、顔料は、有機顔料、無機顔料のいずれであってもよい。染料としては、例えば、アゾ染料、アントラキノン染料、インジゴ染料、シアニン染料、キノリン染料、ベンゾキノン染料、ナフトキノン染料、フタロシアニン染料等が挙げられるが、これらに特に限定されない。有機顔料としては、クインドマゼンタ等のキナクリドン系顔料、トルイジンレッド等のアゾ系顔料、モナストラールブルー、モナストラールグリーン等のフタロシアニン系顔料等が挙げられるが、これらに特に限定されない。無機顔料としては、カーボンブラック、Fe、Co、Ni、Ti等の金属の酸化物、Zn、Cd、Ba、Mg等の金属のフェライト、合金等が挙げられるが、これらに特に限定されない。これらの中でも、顔料が好ましく、有機顔料、無機顔料がより好ましい。色材の含有量は、特に限定されないが、トナー組成物の総量に対して、染料及び有機顔料では、好ましくは0.1~35質量%、より好ましくは1~30質量%、さらに好ましくは5~25質量%である。無機顔料では、好ましくは0.1~80質量%、より好ましくは10~70質量%、さらに好ましくは30~50質量%である。
電荷制御化合物は、熱可塑性トナー粒子の帯電極性や帯電量を制御するために用いられる。電荷制御化合物としては、アニオン性、カチオン性、両性又は非イオン性の界面活性化合物が用いられる。これらの電荷制御化合物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。電荷制御化合物として、より具体的には、石油酸バリウム等の金属石鹸、レシチン等のリン脂質、有機酸の金属塩化合物、有機リン酸化合物、有機スルホン酸化合物、第四級アンモニウム塩化合物等が挙げられるが、これらに特に限定されない。帯電制御化合物の含有量は、特に限定されないが、トナー組成物の総量に対して、好ましくは0.1質量%~5質量%、より好ましくは0.5質量%~4質量%、さらに好ましくは1質量%~3質量%である。
分散安定剤は、電荷制御化合物の安定化を助長するために用いられる。分散剤としては、例えば、ポリビニルピロリドン、ポリビニルアルコール、ポリエチレングリコール、ポリエチレングリコールが挙げられるが、これらに特に限定されない。
トナー組成物は、ポリエチレン系樹脂及び色材を加熱しながら混合して熱可塑性トナー粒子を液体担体中で形成し、さらに必要に応じて電荷制御化合物を添加することにより調製することができる。なお、トナー組成物の調製の際に色材とともにワックスを混合してもよい。トナー組成物がワックスを含有することにより、印刷層(C)13と樹脂成形品21との接着性が向上する。
印刷層(C)の形成は、例えば、液体エレクトロインキを用いたオフセット印刷を行うことにより行うことができる。まず、シリンダー状の画像形成プレートをコロナ放電により帯電させて、続いてこの画像形成プレートを露光することで静電画像を形成する。次に、静電画像が形成された画像プレートにトナー組成物を供給することで、静電画像を現像する。さらに、トナー組成物によって形成された静電トナー像を、画像形成プレートからシリンダー状のブランケットに転写する。ブランケットに転写されたトナー組成物を、ブランケットにより加熱して、トナー組成物に含まれる熱可塑性トナー粒子を融合又は凝集させる。融合又は凝集が進むにつれて、熱可塑性トナー粒子がポリマーフィルムを形成し、このポリマーフィルムに色材が含まれたポリマーフィルム画像がブランケット上に生じる。このようにして形成されたポリマーフィルム画像を、ブランケットからインク受容層(B)12に転写して、さらに冷却して硬化することで、印刷層(C)13が形成される。
インク濃度は、インク受容層(B)12の面積に対する印刷層(C)13の面積の割合を示すものである。インク受容層(B)12上に上述した手法により印刷層(C)13を形成する場合、印刷層(C)13は、インク受容層(B)12上に形成された点状のインクの集合(網点)として構成される。このため、インク濃度は、インク受容層(B)12上の網点部分が占める面積の割合を示す、網点面積率によって表すことができる。
印刷層(C)13の厚みは、印刷方式及びトナー組成物に応じて適宜変更され、特に制限されないが、好ましくは0.5~20μm、より好ましくは0.8~10μm、さらに好ましくは1.0~5μmである。印刷層(C)13が前記範囲内であることにより、インク濃度が十分に保たれて視認性を高めることができ、また十分な接着性を維持できる傾向にある。
(第2のインク受容層、及び第2の印刷層)
本発明のインモールド成形用ラベル1は、前記インク受容層(B)12、印刷層(C)13とは別に、図7に示すように、基材層(A)のインク受容層(B)が設けられている方とは反対の面に、さらに第2の印刷層(c)、及び第2のインク受容層(b)をこの順に有してもよい。すなわち、本発明のインモールド成形用ラベル1は、第2の印刷層(c)41、第2のインク受容層(b)31、基材層(A)11、インク受容層(B)12、印刷層(C)13をこの順に含むように積層したものとすることができる。前記ラベル1を樹脂成形品21に貼着した場合、最外層は第2の印刷層(c)41となり、印刷層(C)13が樹脂成形品21と接着することになる。
本発明のインモールド成形用ラベル1は、任意の箇所にヒートシール層を設けてもよい。ヒートシール層は樹脂成形品の成形時の熱により活性化して接着剤の働きを有するものである。ヒートシール層は例えば、熱可塑性樹脂を含む樹脂組成物をフィルム状に成形したものとすることができる。
本発明のインモールド成形用ラベル1には、耐光性、耐水性、耐ガス性、耐摩擦性等の堅牢性を向上させるために、基材層(A)11側の面に樹脂フィルムからなる保護層を設けてもよい。保護層を構成する樹脂は特に限定されないが、上述した基材層(A)11で用いられる熱可塑性樹脂と同様のものを使用することができる。保護層の厚みも特に限定されないが、好ましくは5~100μm、より好ましくは10~50μmである。保護層を設ける手段としては種々の方法を採用することができ、特に限定されない。基材層(A)11側の面にドライラミネート法や熱ラミネート法を用いて複層化する手段や、基材層(A)11及びインク受容層(B)12とともに押出ラミネートする方法、熱可塑性樹脂をコーティングする方法等の公知の手段から適宜選択して用いればよい。
本発明はまた、上述のインモールド成形用ラベル1をインモールド成形により樹脂成形品に貼着一体化したラベル付き樹脂成形品2に関するものでもある。そして、本発明のラベル付き樹脂成形品2は、基材層(A)11とインク受容層(B)12との界面で剥離が進行し、インモールド成形用ラベル1を剥離した後の樹脂成形品表面にインク受容層(B)12と印刷層(C)13とを有するか、またはインク受容層(B)12と印刷層(C)13との界面で剥離が進行し、インモールド成形用ラベル1を剥離した後の樹脂成形品表面に印刷層(C)13を有するものである。
各実施例、比較例で得られたインモールド成形用のラベル及びラベル付き樹脂成形品の評価は、以下の方法で行った。
○:良 (ラベルへのインク転移性が良好である)
△:可 (ラベルへのインク転移に一部欠けが見られる)
×:不可(ラベルへのインク転移性が悪い)
基材層(A)とインク受容層(B)との間の剥離強度は、JIS K6854-3:1999に準拠して、ラベル付き樹脂成形品を幅(MD方向)15mm、長さ(TD方向)110mmに切り取り、引張試験機((株)島津製作所製、機器名:オートグラフ AGS-D形)を用いて、300mm/minの引張速度でT形剥離することにより求めた。
樹脂成形品からラベルを剥離した際のインクの転写性について、以下の基準で判定した。
◎:優 (インクが樹脂成形品に完全に転写されている)
○:良 (インクの一部が欠けた状態で樹脂成形品に転写されている)
△:可 (印刷情報が樹脂成型品にほぼ転写されるが、ラベル側にも薄く残る)
×:不可(インクが樹脂成形品に全く転写されない)
(基材層の製造)
基材層材料A1を230℃に設定した押出機にて混練した。その後、250℃に設定したダイに供給し、シート状に押出した。押し出されたシートを冷却ロールにて約40℃まで冷却して、無延伸シートを得た。次に、無延伸シートを、150℃の温度に再加熱した後、ロール群の周速差を利用して縦方向(MD方向)に5倍延伸し、引き続きテンターオーブンを用いて155℃の温度まで再加熱して、テンターを用いて横方向(TD方向)に7.5倍延伸した。その後、165℃の温度でアニーリング処理し、60℃の温度にまで冷却した後、耳部をスリットすることで、2軸延伸フィルムの基材層を得た。このとき、基材層の厚みは80μmであった。
前工程で作製した基材層の片面に、コロナ放電処理装置(春日電機社(株)製、機器名:HF400F)を用いてコロナ放電処理を実施した。コロナ放電処理は、長さ0.8mのアルミニウム製放電電極と、トリーターロールにシリコーン被膜ロールとを用いた。また、放電電極とトリーターロールとのギャップを5mmとし、ライン処理速度を15m/分とし、印加エネルギー密度を4,200J/m2とした。
次にコロナ放電処理を実施した側の面に、インク受容層材料B1を乾燥後固形分として0.2g/m2となるように塗工した。塗工にはバーコーターを用いた。続いて、オーブンで乾燥させてインク受容層を形成し、巻き取った。インク受容層の厚みは約0.2μmであった。
前記工程で作製したインク受容層上に印刷することにより印刷層を形成した。印刷層材料として、表1に記載の印刷層材料C1を用い、湿式電子写真印刷機(Hewlett-Packard Inc.製、機器名:HP Indigo WS6800)を用いた。印刷の条件は、温度23℃、相対湿度50%の室内環境下、ブランケット温度105℃、転写圧200kgで実施した。また、網点面積率を100%とした。
次に打ち抜き機((株)ダンベル製、機器名:SD型レバー式試料裁断器SDL-100)で、基材層のMD方向に70mm、TD方向に90mmのサイズに打ち抜き、インモールド成形用ラベルを得た。
長さ130mm、幅150mm、厚み2mmのキャビティを有する試験片成形用金型にインモールド成形用ラベルの印刷していない面がキャビティに接する様に、金型内にラベルを配置し、吸引固定した。次いで、金型を閉じ、射出成型機((株)新潟鐵工所製、機器名:NV50ST)を用いて、表1に記載の樹脂成形品材料D1を樹脂温度230℃、射出圧力74N/m2の条件で射出成型した。続いて射出成型後、金型を20秒間十分に冷却し、金型を開放してラベル付き樹脂成形品を得た。
実施例1において、樹脂成形品材料D1をそれぞれ表1に記載の樹脂成形品材料に変更したこと以外は実施例1と同様にして実施例2、3および6のラベル及びラベル付き樹脂成形品を得た。
実施例3において、基材層材料A1を表1に記載の基材層材料A2に変更したこと以外は実施例3と同様にして実施例4のラベル及びラベル付き樹脂成形品を得た。
実施例1において、印刷条件としての網点面積率100%を50%のドット状印刷に変更したこと以外は実施例1と同様にして実施例5のラベル及びラベル付き樹脂成形品を得た。
実施例1において、インク受容層材料B1を表1に記載のインク受容層材料に変更したこと以外は実施例1と同様にして比較例1および2のラベル及びラベル付き樹脂成形品を得た。
実施例1において、インク受容層材料B1を表1に記載のインク受容層材料B4に変更したところ、インク受容層にインクが定着せず、印刷できなかった。
実施例1において、インク受容層(B)を設けなかったところ、基材層(A)にインクが定着せず、印刷できなかった。
実施例1において、印刷層材料C1を表1に記載の印刷層材料に変更したこと以外は実施例1と同様にして比較例5および6のラベル及びラベル付き樹脂成形品を得た。
表2に、インモールド成形用ラベル付き樹脂成形品の構成、及び評価結果を示す。
2 ラベル付き樹脂成形品
11 基材層(A)
12 インク受容層(B)
13 印刷層(C)
21 樹脂成形品
31 第2のインク受容層(b)
41 第2の印刷層(c)
Claims (7)
- 熱可塑性樹脂を含有する基材層(A)と、
ポリエチレンイミン系重合体を含むインク受容層(B)と、
ポリエチレン系樹脂を主成分とする印刷層(C)と
をこの順に有するインモールド成形用ラベル。 - 前記熱可塑性樹脂が、オレフィン系樹脂、スチレン系樹脂、エステル系樹脂、アミド系樹脂およびポリカーボネートからなる群より選択される少なくとも1種類の熱可塑性樹脂である、請求項1に記載のインモールド成形用ラベル。
- 前記ポリエチレン系樹脂が、エチレン・メタクリル酸共重合体を含む、請求項1または2に記載のインモールド成形用ラベル。
- 前記基材層(A)のインク受容層(B)が設けられている方とは反対の面に、さらに第2の印刷層(c)、及び第2のインク受容層(b)をこの順に含む請求項1~3のいずれか1項に記載のインモールド成形用ラベル。
- 請求項1~4のいずれか1項に記載のインモールド成形用ラベルをインモールド成形により樹脂成形品に貼着一体化したラベル付き樹脂成形品。
- 前記樹脂成形品がポリエチレン系樹脂、ポリスチレン樹脂より選択される少なくとも1種の熱可塑性樹脂を含む、請求項5に記載のラベル付き樹脂成形品。
- 前記ラベル付き樹脂成形品から前記インモールド成形用ラベルを剥離すると基材層(A)とインク受容層(B)間の界面またはインク受容層(B)と印刷層(C)との界面で剥離し、インモールド成形用ラベルを剥離した後の樹脂成形品表面に少なくとも印刷層(C)を有する、請求項5または6に記載のラベル付き樹脂成形品。
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