JP2014141601A - Method of manufacturing plastic film printed matter, ink and plastic film printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic film printed matter having high light emission intensity and a printed layer by a fluorescent ink excellent in fluorescence feeling (brightness of fluorescence) and its manufacturing method, and to provide a plastic film printed matter having the printed layer by a fluorescent ink which emits light even by ultraviolet light and its manufacturing method.SOLUTION: The method of manufacturing a plastic film printed matter includes forming a printed layer by applying an ink on at least a single-side of a plastic film and drying and solidifying, and the ink contains a resin, a fluorescent pigment, a sensitizer and a solvent.

Description

  The present invention relates to a method for producing a printed plastic film. The present invention also relates to printed matter of ink and plastic film. More specifically, the present invention relates to a method for producing a printed plastic film containing a fluorescent pigment, an ink containing a fluorescent pigment, and a printed plastic film having a printed layer containing the fluorescent pigment.

  Conventionally, a printing ink containing a fluorescent pigment, a film printed using the ink, and the like are known (for example, Patent Document 1).

JP 2004-2629 A

  However, when it is desired to increase the fluorescence intensity of the printing layer using a conventional ink containing a fluorescent pigment (hereinafter sometimes referred to as “fluorescent ink”), from the viewpoint of increasing the fluorescent pigment per unit area of the printing layer. It was necessary to increase the thickness of the printing layer. Therefore, there is a demand for fluorescent inks having higher emission intensity and strong fluorescent feeling, and printed matter printed using the fluorescent inks, even if the printed layer is thin.

  Also, many conventional fluorescent inks absorb visible light and emit light with a wavelength slightly longer than the absorbed visible light. For this reason, the said fluorescent ink needed to be used under visible light. Accordingly, there is a need for fluorescent inks that emit light even when light other than visible light such as ultraviolet rays, and printed matter printed using the fluorescent inks.

  That is, an object of the present invention is to provide a plastic film printed matter having a printed layer of fluorescent ink having high emission intensity and excellent fluorescence feeling (fluorescence brightness feeling) and a method for producing the same. Another object of the present invention is to provide a fluorescent ink having high emission intensity and excellent fluorescence. Another object of the present invention is to provide a printed matter of a plastic film having a printed layer of fluorescent ink that emits light even by ultraviolet light, and a method for producing the same. Another object of the present invention is to provide a fluorescent ink that emits light even by ultraviolet light.

  As a result of intensive studies to achieve the above object, the present inventors applied a fluorescent ink containing a resin, a fluorescent pigment, a sensitizer, and a solvent to at least one side of a plastic film, and dried and solidified the printed layer. As a result of the formation, it was found that the fluorescence emission intensity of the printing layer was improved, and a plastic film printed matter having a printing layer that was excellent in fluorescence feeling and also emitted by ultraviolet light was obtained, and the present invention was completed.

  That is, the present invention is a method for producing a printed plastic film product in which an ink is applied to at least one side of a plastic film and dried and solidified to form a printed layer, the ink comprising a resin, a fluorescent pigment, a sensitizer, and Provided is a method for producing a printed plastic film, comprising a solvent.

  Further, in the present invention, the content of the fluorescent pigment is 10 to 60% by weight with respect to 100% by weight of the total nonvolatile content of the ink, and the content of the sensitizer is the total weight of the fluorescent pigment. The manufacturing method of the said plastic film printed matter which is 3-25 weight part with respect to 100 weight part is provided.

  Furthermore, this invention provides the manufacturing method of the said plastic film printed matter whose absorption maximum wavelength of the said sensitizer exists in 300-400 nm.

  Furthermore, this invention provides the manufacturing method of the said plastic film printed matter whose said sensitizer is an anthracene type compound and / or a thioxanthone type compound.

  Furthermore, the present invention provides the method for producing a printed matter of the plastic film, wherein the fluorescent pigment has an absorption maximum wavelength of 300 to 600 nm and a fluorescence maximum wavelength of 400 to 700 nm.

  Further, the present invention is an ink containing a resin, a fluorescent pigment, a sensitizer, and a solvent, wherein the content of the fluorescent pigment is 10 to 60% by weight with respect to 100% by weight of the total nonvolatile content of the ink. The content of the sensitizer is 3 to 25 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment.

  Further, the present invention is a plastic film printed matter having a printed layer containing a resin, a fluorescent pigment, and a sensitizer on at least one side of the plastic film, wherein the content of the fluorescent pigment is a total weight of the printed layer. 10 to 60% by weight with respect to 100% by weight, and the content of the sensitizer is 3 to 25 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment. Provide film prints.

  Since the method for producing a printed plastic film according to the present invention has the above-described configuration, according to the producing method, a printed plastic film having a printed layer with improved light emission intensity and excellent fluorescence is obtained. Furthermore, when a sensitizer that absorbs ultraviolet light is used, a printed plastic film having a printed layer that emits light relatively strongly by ultraviolet light can be obtained.

  The method for producing a plastic film printed matter of the present invention is a method for producing a plastic film printed matter in which an ink is applied to at least one side of a plastic film and dried and solidified to form a printed layer, the ink comprising a resin, a fluorescent pigment, It contains a sensitizer and a solvent. In the present specification, the above ink (that is, an ink containing a resin, a fluorescent pigment, a sensitizer, and a solvent) may be referred to as “the ink of the present invention”. In addition, the above-mentioned printing layer, that is, a printing layer formed from the ink of the present invention may be referred to as “printing layer of the present invention”. Further, the method for producing a printed plastic film of the present invention may be referred to as “the production method of the present invention”. Furthermore, the plastic film printed matter having the printed layer of the present invention may be referred to as “the plastic film printed matter of the present invention”.

[Ink of the present invention]
The ink of the present invention is an essential ink used in the production method of the present invention. The ink of the present invention contains at least a resin, a fluorescent pigment, a sensitizer, and a solvent. In addition, the ink of the present invention may include components (other components) other than the resin, the fluorescent pigment, the sensitizer, and the solvent. Each of the resin, the fluorescent pigment, the sensitizer, the solvent, and the other components may be used alone or in combination of two or more.

(resin)
Although it does not specifically limit as said resin, For example, resin used as binder resin in well-known printing ink can be used. The resin is not particularly limited, and examples thereof include acrylic resins, urethane resins, polyester resins, polyamide resins, cellulose resins, urethane acrylic resins, and vinyl chloride-vinyl acetate copolymer resins. Among these, cellulose-based, urethane acrylic resins, urethane resins, and acrylic resins are preferable, and acrylic resins are particularly preferable.

  The cellulose-based resin is not particularly limited, but is nitrocellulose (nitrified cotton); cellulose acetate butyrate (cellulose acetate butyrate: CAB), cellulose acetate (cellulose acetate), cellulose acetate propionate (cellulose acetate propionate: CAP). And cellulose resin esterified with a carboxylic acid such as). Examples of the carboxylic acid include acetic acid, butyric acid, propionic acid, acetic anhydride, and butyric anhydride. As the cellulose resin, a cellulose resin esterified with a carboxylic acid is preferable, and cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) are particularly preferable. Only 1 type may be used for the said cellulose resin, and 2 or more types may be used for it.

  Although the weight average molecular weight of the said cellulose resin is not specifically limited, 10000-150000 are preferable, More preferably, it is 15000-100000. When the weight average molecular weight is less than 10,000, blocking may occur and heat resistance may be reduced. On the other hand, when it exceeds 150,000, the solubility of the cellulose-based resin in the ink is deteriorated, and the ink is too high in viscosity and the applicability may be lowered.

  In addition, in this specification, although a weight average molecular weight (Mw) is not specifically limited, For example, it can measure by GPC.

  A commercial item can also be used for the said cellulose resin. For example, “CAB-381-20, CAB-381-0.5, CAB-381-0.1, CAB-551-0.1, CAB-551-0.01, CAP-504 manufactured by Eastman Chemical Co., Ltd. 0.2, CAP-482-0.5, etc. ", KOREA CNC" RS series "," SS series ", etc. are available on the market.

Although it does not specifically limit as said urethane acryl-type resin, It is a polymer (copolymer) comprised by making a urethane component and an acrylic component into essential structural components. In other words, the urethane acrylic resin is a polymer including a urethane component part having a urethane bond and an acrylic component part containing a structural unit (structural unit) derived from a monomer having a (meth) acryloyl group in the molecule. It is. The “(meth) acryloyl group” represents “acryloyl group [CH ₂ ═CHCO—]” and / or “methacryloyl group [CH ₂ ═C (CH ₃ ) CO—]”. A monomer having a (meth) acryloyl group has a structure of [CH ₂ ═CHCO—] and / or [CH ₂ ═C (CH ₃ ) CO—] in the molecule. “(Meth) acryl” means “acryl” and / or “methacryl” (any one or both of acryl and methacryl).

The acrylic component in the urethane acrylic resin includes a monomer (monomer) having a (meth) acryloyl group as an essential monomer component. That is, the acrylic component and the urethane acrylic resin have at least a structural unit derived from a monomer having a (meth) acryloyl group. Examples of the monomer having the (meth) acryloyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as isononyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate [preferably C _1-12 alkyl (meth) acrylate Esters etc.]; (Meth) acrylic acid; carboxyl groups such as carboxyethyl acrylate (Meth) acrylic acid ester; 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meta) ) Hydroxyl group-containing (meth) acrylic acid ester such as acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester etc.]; (Meth) acrylic acid cycloalkyl esters such as cyclohexyl acrylate; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-di (Meth) acrylic acid amide derivatives such as til (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dipropylamino And (meth) acrylic acid dialkylaminoalkyl esters such as propyl (meth) acrylate. As for the monomer which has the said (meth) acryloyl group, only 1 type may be used and 2 or more types may be used.

  The monomer component constituting the acrylic component other than the monomer having the (meth) acryloyl group is not particularly limited. For example, a carboxyl group-containing polymerizable unsaturated compound such as crotonic acid, itaconic acid, fumaric acid, maleic acid or the like Its anhydrides; Styrene compounds such as styrene, vinyltoluene and α-methylstyrene; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl halides such as vinyl chloride; Vinyl ethers such as methyl vinyl ether; (Meth) acrylonitrile And cyano group-containing vinyl compounds such as ethylene and propylene.

  Although the urethane component in the said urethane acrylic resin is not specifically limited, For example, a polyisocyanate compound and a polyol compound are comprised as a raw material component. That is, the urethane component has a structural unit derived from a polyisocyanate compound and a structural unit derived from a polyol compound. Especially, it is preferable that the said urethane component is comprised by using polyester polyol as an essential raw material component as a polyol compound. That is, it is preferable that the urethane component and the urethane acrylic resin have at least a structural unit derived from a polyester polyol.

  Examples of the polyisocyanate compound include known diisocyanates such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Examples of the diisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate. The diisocyanates may be used alone or in combination of two or more. If necessary, trifunctional or higher functional polyisocyanates and polyisocyanate adducts can be used in combination with the diisocyanates.

  The polyester polyol is a polyester compound having two or more hydroxyl groups in the molecule (in one molecule), and among them, a polyester diol having two hydroxyl groups in the molecule is preferable. The polyester polyol is not particularly limited, but is preferably a polymer composed of a dicarboxylic acid component and a diol component as essential components. That is, the polyester polyol preferably has at least a structural unit derived from a dicarboxylic acid and a structural unit derived from a diol.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2,5-dimethylterephthalic acid, 5-t-butylisophthalic acid, 4,4′-biphenyldicarboxylic acid, trans-3,3′-stilbene dicarboxylic acid, Trans-4,4′-stilbene dicarboxylic acid, 4,4′-dibenzyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,2,6,6-tetramethylbiphenyl-4,4′-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindene-4,5-dicarboxylic acid 1,2-diphenoxyethane-4,4′-dicarboxylic acid, diphenyl ether dicarboxylic acid, 2,5-ant Aromatic dicarboxylic acids such as sendicarboxylic acid, 2,5-pyridinedicarboxylic acid, and substituted products thereof; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, docosanedioic acid, 1,12-dodecanedioic acid, and Aliphatic dicarboxylic acids such as these substitutes; 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid , Trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedi Carboxylic acid, and include alicyclic dicarboxylic acids such as substituted versions thereof. Of these, aromatic dicarboxylic acids are preferable, and terephthalic acid (TPA) and isophthalic acid (IPA) are more preferable. The said dicarboxylic acid may use only 1 type and may use 2 or more types.

  Examples of the diol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2,4-dimethyl-1,3-hexanediol, 1,10-decanediol, polyethylene glycol, polypropylene Aliphatic diols such as glycol; 1,2-cyclohexanedimethanol, 1,3-cyclohexane Cycloaliphatic diols such as sandimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 2,2-bis (4-β-hydroxyethoxyphenyl) propane And ethylene oxide adducts of bisphenol compounds such as bis (4-β-hydroxyethoxyphenyl) sulfone, and aromatic diols such as xylylene glycol. Of these, aliphatic diols are preferable, and neopentyl glycol (NPG) and ethylene glycol (EG) are more preferable. Only 1 type may be used for the said diol, and 2 or more types may be used for it.

  In addition to the above, the polyester polyol includes oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid; monocarboxylic acids such as benzoic acid and benzoylbenzoic acid; polyvalent carboxylic acids such as trimellitic acid; It may contain a structural unit derived from a monohydric alcohol such as polyalkylene glycol monomethyl ether; a polyhydric alcohol such as glycerin, pentaerythritol or trimethylolpropane.

  The polyol compound in the urethane component may contain a polyol compound other than the polyester polyol. Although it does not specifically limit as polyol compounds other than said polyester polyol, For example, ethylene glycol, diethylene glycol, 1,3-propanediol, propylene glycol (1,2-propanediol), butanediol (1,3-butanediol) , 1,4-butanediol, etc.), 1,6-hexanediol, low molecular weight glycols such as cyclohexanedimethanol; known diols such as polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, A trifunctional or higher functional polyol compound (polyether polyol, etc.) can be used.

  The weight average molecular weight (Mw) of the urethane acrylic resin is not particularly limited, but is preferably 20000 to 100,000 from the viewpoint of improvement in shrinkage followability (followability of the printed layer against shrinkage deformation during shrink processing) and prevention of blocking. More preferably, it is 25000-80000, More preferably, it is 30000-60000.

  Although the acid value of the said urethane acrylic resin is not specifically limited, From a viewpoint of the storage stability of printing ink, 0-20 mgKOH / g is preferable, More preferably, it is 0.3-5 mgKOH / g. In addition, in this specification, an acid value is calculated | required based on JISK5601-2-1 (titration method).

  A commercially available product can be used as the urethane acrylic resin. For example, “Acryt 8UA-140” and “Acryt 8UA-357” manufactured by Taisei Fine Chemical Co., Ltd. are available on the market.

  It does not specifically limit as said urethane type resin, The well-known thru | or usual polyurethane resin for printing ink can be used, For example, resin obtained by making a polyisocyanate compound and a polyol compound react is mentioned.

  Examples of the polyisocyanate compound include one or a mixture of two or more known diisocyanates of aromatic, aliphatic and alicyclic groups. Examples of the diisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate. If necessary, tri- or higher functional polyisocyanates and polyisocyanate adducts can be mixed with the diisocyanates.

  Examples of the polyol compound include ethylene glycol, diethylene glycol, 1,3-propanediol, propylene glycol (1,2-propanediol), butanediol (1,3-butanediol, 1,4-butanediol, etc.), 1, Low molecular weight glycols such as 6-hexanediol and cyclohexanedimethanol; polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene glycol-polycaprolactone copolymer; propylene glycol, butanediol, hexanediol Polyesters obtained from dibasic acids such as adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid and fumaric acid; Kutonjioru, polyvalerolactone diol, a known diols such as lactone diol, lactone block copolymer diols can be used. Moreover, said diols and trifunctional or more than polyol compounds (polyether polyol, polyester polyol, etc.) can also be mixed and used as needed.

  Among the above, polyester diol-based polyurethane (polyurethane obtained by using polyester diol as a polyol compound) is preferable.

  The weight average molecular weight (Mw) of the urethane resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and still more preferably 30,000 to 30,000, from the viewpoint of adhesion to a plastic film and scratch resistance. 70000.

  A commercial item can also be used for the said urethane-type resin. For example, “Samprene IB series, LQ series” manufactured by Sanyo Chemical Industries, Ltd. is available on the market.

Although it does not specifically limit as said acrylic resin, Resin which comprised acrylic monomer as an essential monomer component, ie, resin which contains at least the structural unit (structural unit) derived from an acrylic monomer Is mentioned. Examples of the monomer component constituting the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester having a linear or branched alkyl group such as isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate [preferably having 1 to 12 carbon atoms] (Meth) acrylic acid alkyl ester ((meth) acrylic acid C _1-1 having a linear or branched alkyl group ₂ alkyl ester) etc.]; (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and other carboxyl group-containing polymerizable unsaturated compounds or anhydrides thereof; 2-hydroxymethyl (meth) acrylate, 2- Hydroxyl group-containing (meth) acrylic acid such as hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate _Examples thereof include esters [preferably (meth) acrylic acid hydroxy C _1-8 alkyl ester and the like]. “(Meth) acryl” means “acryl” and / or “methacryl”.

  In addition to the above, as required, (meth) acrylic acid cycloalkyl esters such as cyclohexyl (meth) acrylate; N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylic acid amide derivatives such as (meth) acrylamide, N, N-diethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, dimethylamino (Meth) acrylic acid dialkylaminoalkyl esters such as propyl (meth) acrylate and dipropylaminopropyl (meth) acrylate; styrene compounds such as styrene, vinyltoluene and α-methylstyrene; vinyl acetate, Vinyl esters such as vinyl pionate; Vinyl halides such as vinyl chloride; Vinyl ethers such as methyl vinyl ether; Cyano group-containing vinyl compounds such as (meth) acrylonitrile; Polymerizability of olefins such as ethylene and propylene, and dienes Unsaturated compounds can also be used as monomer components. As for the monomer component which comprises the said acrylic resin, only 1 type may be used and 2 or more types may be used.

  A commercial item can also be used for the said acrylic resin. For example, “ARUFON series” manufactured by Toagosei Co., Ltd. and “Dianar series” manufactured by Mitsubishi Rayon Co., Ltd. are available on the market.

(Fluorescent pigment)
The fluorescent pigment is not particularly limited, but is a pigment that emits fluorescence, preferably a pigment that emits fluorescence in the visible range. For example, fluorescent pigments used in known printing inks, paints, plastic products, paints, and writing instruments. Can be used. Although it does not specifically limit as said fluorescent pigment, An inorganic fluorescent pigment and an organic fluorescent pigment are mentioned. More specifically, examples of the fluorescent pigment include a pigment formed by impregnating and / or applying a fluorescent material to particles such as melamine resin beads and acrylic resin beads. The fluorescent color of the fluorescent pigment is not particularly limited, and fluorescent pigments of various fluorescent colors such as yellow, vermilion, pink and purple can be used. Only 1 type may be used for the said fluorescent pigment, and 2 or more types may be used for it.

  The average particle diameter of the fluorescent pigment is not particularly limited, but is preferably 0.01 to 1 μm, more preferably 0.1 to 0.5 μm, from the viewpoint of light resistance and color developability.

  Although the said fluorescent pigment is not specifically limited, From a viewpoint of a combination with a sensitizer, it is preferable that an absorption maximum wavelength exists in 300-600 nm, More preferably, it is 330-590 nm, More preferably, it is 350-580 nm. The absorption maximum wavelength can be measured by fluorescence spectroscopy. Although it does not specifically limit as a measuring instrument of fluorescence spectrometry, For example, the fluorescence spectrophotometer "F-4500" (made by Hitachi, Ltd.) etc. can be used.

  Although the said fluorescent pigment is not specifically limited, From a viewpoint of light-emitting visible light, it is preferable that a fluorescence maximum wavelength exists in 400-700 nm, More preferably, it is 420-690 nm, More preferably, it is 440-680 nm. In addition, although it does not specifically limit, it is preferable that the maximum fluorescence maximum wavelength exists in the said range. The fluorescence maximum wavelength can be measured by fluorescence spectroscopy. Although it does not specifically limit as a measuring instrument of fluorescence spectrometry, For example, the fluorescence spectrophotometer "F-4500" (made by Hitachi, Ltd.) etc. can be used.

  A commercial item can also be used for the said fluorescent pigment. For example, “SX-100 series”, “FZ-2000 series”, “SW-10 series”, “SP-10 series”, etc. manufactured by Sinloihi Co., Ltd. are available on the market.

(Sensitizer)
The sensitizer (photosensitizer) is not particularly limited, but thioxanthone compounds such as diethylthioxanthone and isopropylthioxanthone; anthracene compounds such as 9-butoxyanthracene and 9,10-dibutoxyanthracene; 2,4 -Benzophenone compounds such as dihydroxybenzophenone; Anthraquinone compounds such as benzanthrone and 2-phenoxyanthraquinone; Naphthalene compounds such as 1,4-diacryloxynaphthalene; Nitrogen such as aliphatic amine, aromatic amine and piperidine Amines such as amines; urea compounds such as allyl urea compounds and o-tolylthiourea; sulfur compounds such as sodium diethyldithiophosphate; nitriles such as N, N-disubstituted p-aminobenzonitrile compounds system Compound; phosphorus compound such as tri-n-butylphosphine; nitrogen compound such as N-nitrosohydroxylamine derivative and oxazolidine compound; chlorine compound such as carbon tetrachloride; naphtho [2,3-d] thiazole-4 , 9-dione derivatives and the like. Of these, thioxanthone compounds and anthracene compounds (thioxanthone compounds and / or anthracene compounds) are preferable from the viewpoint of the sensitizing effect. Only 1 type may be used for the said sensitizer and 2 or more types may be used for it.

  The thioxanthone compound (thioxanthone compound) is not particularly limited, and examples thereof include thioxanthone and thioxanthone derivatives. The thioxanthone-based compound is not particularly limited. For example, isopropylthioxanthone, thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone and the like can be mentioned. Of these, isopropylthioxanthone and 2,4-diethylthioxanthone are preferable. Only 1 type may be used for the said thioxanthone type compound, and 2 or more types may be used for it.

  Although it does not specifically limit as said anthracene type compound (anthracene compound), Anthracene, an anthracene derivative, etc. are mentioned. Among these, 9,10-disubstituted anthracene compounds are preferable, and 9,10-dialkoxyanthracene compounds are more preferable. Although it does not specifically limit as said anthracene type compound, For example, 9,10- dibutoxyanthracene, 9,10- dipropoxyanthracene, 9,10-diethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 9,10-diglycidyloxyanthracene, 9,10-bis (2-hydroxypropoxy) anthracene, 2-ethyl-9,10-dihydroxyanthracene and the like can be mentioned. Of these, 9,10-dibutoxyanthracene is preferable. The said anthracene type compound may use only 1 type, and may use 2 or more types.

  The sensitizer is not particularly limited, but preferably has an absorption maximum wavelength of 600 nm or less (for example, 300 to 600 nm), more preferably 500 nm or less (for example, 330 to 500 nm), and still more preferably 450 nm or less ( For example, 340 to 450 nm). It is particularly preferably 300 to 400 nm. When the absorption maximum wavelength is 400 nm or less, it is particularly preferable because the fluorescent pigment can emit light relatively strongly using ultraviolet rays. Further, although not particularly limited, it is preferable that the maximum absorption wavelength of the fluorescent pigment and the sensitizer are different from the viewpoint of being able to absorb ultraviolet rays or visible light having different wavelengths.

  Commercially available products can be used as the sensitizer. For example, “ANTHRACURE UVS-1331” (9,10-dibutoxyanthracene) manufactured by Kawasaki Chemical Industry Co., Ltd. is available on the market.

(solvent)
Although it does not specifically limit as said solvent, The organic solvent etc. which are normally used for printing ink can be used. Although it does not specifically limit as said solvent, Acetic ester, such as ethyl acetate, propyl acetate, butyl acetate; Alcohol, such as methanol, ethanol, isopropyl alcohol, propanol, butanol; Ketone, such as methyl ethyl ketone and methyl isobutyl ketone; Toluene, xylene, etc. Aromatic hydrocarbons such as hexane and octane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Glycols such as ethylene glycol and propylene glycol; Glycol ethers such as propylene glycol monomethyl ether and propylene glycol monobutyl ether A glycol ether ester such as propylene glycol monomethyl ether acetate; Of these, acetates and alcohols are preferred from the viewpoints of solubility and safety. As for the said solvent, only 1 type may be used and 2 or more types may be used. The solvent can be removed by drying after applying the ink to the plastic film.

(Other ingredients)
The ink of the present invention may contain components (other components) other than the resin, the fluorescent pigment, the sensitizer, and the solvent as long as the effects of the present invention are not impaired. Examples of the other components include, but are not limited to, plasticizers, lubricants, anti-settling agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, anti-coloring agents, and fragrances. And deodorant.

  The content of the solvent in the ink of the present invention is not particularly limited, but is preferably 30 to 80% by weight, more preferably 35 to 60% by weight with respect to 100% by weight of the total weight of the ink of the present invention. . When the content is less than 30% by weight, the viscosity of the ink is increased, the coatability is lowered, the solubility of the resin is lowered, and the aggregation of the fluorescent pigment may occur. On the other hand, if it exceeds 80% by weight, the viscosity of the ink becomes too low, the coatability is lowered, the fluorescence feeling is lowered, the solvent is not easily removed by drying, the productivity is lowered, and the printed layer is difficult to thicken. There is a case.

  The total non-volatile content in the ink of the present invention (total amount of all non-volatile content) is not particularly limited, but is 20 to 70% by weight with respect to 100% by weight of the total weight of the ink of the present invention. Is more preferable, and 40 to 65% by weight is more preferable.

  Although content of the said resin in the total non volatile matter of the ink of this invention is not specifically limited, It is 20-85 weight with respect to 100 weight% of total weight (weight of total non volatile matter) of the ink of this invention. % Is preferable, and more preferably 30 to 70% by weight. When the content is less than 20% by weight, the ink coating film becomes brittle and the scratch resistance may deteriorate. On the other hand, if it exceeds 85% by weight, the fluorescence may be lowered.

  Although content of the said fluorescent pigment in the total non volatile matter of the ink of this invention is not specifically limited, It is 10-60 with respect to 100 weight% of total weight (weight of total non volatile matter) of the ink of this invention. % By weight is preferred, and more preferably 20 to 50% by weight. If the said content is less than 10 weight%, content of the fluorescent pigment in the printing layer formed from an ink may become low, and a fluorescence feeling may fall. On the other hand, if it exceeds 60% by weight, the ink coating film becomes brittle, and scratch resistance and rub resistance may decrease.

  The content of the sensitizer in the ink of the present invention is not particularly limited, but is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment. is there. When the content is less than 3 parts by weight, the sensitization effect is lowered, and the fluorescence may be lowered. On the other hand, if it exceeds 25 parts by weight, the ink coating film becomes brittle and the scratch resistance is lowered, and the target color may not be obtained.

  In the present specification, “nonvolatile content” means a nonvolatile component (nonvolatile material). Specifically, the nonvolatile content is, for example, a residue (nonvolatile residue) when 1 g (1 g ± 0.1 g) of a sample (the ink of the present invention) is heated at 150 ° C. for 2 hours. In addition, except for said heating conditions (150 degreeC x 2 hours) and sample amount (1g), it is a method (an apparatus, an instrument, a weighing method, a drying method, etc.) based on JISK5601-1-2, and the said non-volatile residue. It is preferable to obtain (heating residue).

  The ink of the present invention is produced by mixing the resin, the fluorescent pigment, the sensitizer, the solvent, and, if necessary, other components. Mixing can be performed by a known and common mixing method, and is not particularly limited. For example, a mixer such as a paint shaker, butterfly mixer, planetary mixer, pony mixer, dissolver, tank mixer, homomixer, homodisper, or roll mill , Sand mills, ball mills, bead mills, line mills, kneaders and the like are used. The mixing time (retention time) during mixing is not particularly limited, but is preferably 10 to 120 minutes.

  The viscosity (23 ± 2 ° C.) of the ink of the present invention is not particularly limited, but in the case of gravure printing and flexographic printing, for example, 10 to 1000 mPa · s is preferable, and 20 to 500 mPa · s is more preferable. When the viscosity exceeds 1000 mPa · s, for example, the printability is lowered, and “blur”, “plate fog”, etc. may occur, and printing may not be performed as desired. On the other hand, if it is less than 10 mPa · s, the storage stability may be reduced, or “spreading” may occur, resulting in uneven printing, and printing may not be performed as desired. The viscosity of the ink of the present invention can be controlled by the type and content of the resin and the solvent, the content of the fluorescent pigment and the sensitizer, the thickener, the thickener, and the like. In the present specification, the “viscosity” is not particularly limited, but for example, using an E-type viscometer (conical plate type rotational viscometer) under the conditions of 23 ± 2 ° C. and the rotational speed of the cylinder at 50 rpm. It can be measured according to 8803.

  The ink of the present invention can be used in addition to the production method of the present invention. For example, a paint that is applied to a place where ultraviolet rays are handled and is visible as visible light when the ultraviolet rays leak; a paint that is applied to a dark place and emits visible light when irradiated with ultraviolet rays Can be used for Accordingly, the present application includes an invention related to the ink of the present invention.

[Plastic film (base material)]
Although the said plastic film becomes a support body of the printing layer of this invention and is not specifically limited, For example, it has the main influence on the intensity | strength, rigidity, and shrinkage | contraction characteristic of the plastic film printed matter of this invention. The said plastic film is not specifically limited, A well-known plastic film can be used. The type of the plastic film can be appropriately selected according to the type and use of the printed plastic film of the present invention. For example, when the printed plastic film of the present invention is a shrink label (heat-shrinkable label) or the like, the plastic film may be a shrink film (heat-shrinkable film).

  The type of resin forming the plastic film can be appropriately selected according to the required physical properties, application, cost, etc., and is not particularly limited. For example, polyester resin, polyolefin resin, polystyrene resin, Examples thereof include polyvinyl chloride resins, polyamide resins, aramid resins, polyimide resins, polyphenylene sulfide resins, and acrylic resins. Only 1 type may be used for the said resin and 2 or more types may be used for it. Of these, polyester resins, polyolefin resins, and polystyrene resins are preferable. Examples of the polyester-based resin, the polyolefin-based resin, and the polystyrene-based resin include, for example, JP 2008-170822 A, JP 2008-170697 A, JP 2008-163215 A, and JP 2008-163231 A. And polyester resins, polyolefin resins, polystyrene resins and the like.

  Examples of the polyester resin used for the polyester film include polyethylene terephthalate (PET) resin, poly (ethylene-2,6-naphthalenedicarboxylate) (PEN), and polylactic acid (PLA). Among them, polyethylene terephthalate (PET) resin is preferable. As the PET resin, polyethylene terephthalate (PET) using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component; terephthalic acid as the dicarboxylic acid component, ethylene glycol as the diol component, Copolyester (CHDM copolymerized PET) using 4-cyclohexanedimethanol (CHDM) as a copolymerization component, terephthalic acid as a dicarboxylic acid component, ethylene glycol as a main component as a diol component, neopentyl glycol (NPG) as a main component Copolyester (NPG copolymerized PET) used as copolymer component, terephthalic acid as dicarboxylic acid component, ethylene glycol as main component as diol component, diethylene glycol as copolymer component Diol-modified PET such as copolyester; dicarboxylic acid such as copolyester using terephthalic acid as the main component, isophthalic acid and / or adipic acid as the co-polymerization component, and ethylene glycol as the diol component Examples thereof include modified PET.

  As a polystyrene-type resin used for the said polystyrene-type film, as a constituent monomer, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-isobutylstyrene, pt- Examples thereof include resins containing one or more styrene monomers such as butyl styrene and chloromethyl styrene. Specific examples include general polystyrene, styrene-butadiene copolymer (SBS), styrene-butadiene-isoprene copolymer (SBIS), and styrene-acrylic acid ester copolymer.

  Polyolefin resins used for the polyolefin film include polyethylene resins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and metallocene catalyst LLDPE (mLLDPE), polypropylene, and propylene-α-olefin. Examples include polypropylene resins such as copolymers, ethylene-vinyl acetate copolymers, and cyclic olefin resins. In particular, the polyolefin film is preferably one having a cyclic olefin resin as an outer layer. For example, it is preferable to use a cyclic olefin resin as an outer layer and a polyethylene resin or a polypropylene resin as an inner layer (center layer).

  The plastic film may have a single-layer structure or a laminated structure. That is, the plastic film may be a single-layer film or a laminated film in which a plurality of film layers are laminated according to required physical properties, applications, and the like. In the case of a laminated film, film layers made of the same kind of resin may be laminated, or film layers made of different resins may be laminated. In the case of a laminated film, a laminated film having a polyester resin as an outer layer and a polyolefin resin or polystyrene resin as an inner layer, or a laminated film having a cyclic olefin resin as an outer layer and a polyethylene resin or a polypropylene resin as an inner layer is preferable.

  The plastic film may be a non-oriented film or an oriented film. Especially, when a plastic film is a shrink film, it is preferable that it is a film orientated uniaxially, biaxially or multiaxially from the viewpoint of exhibiting shrinkage characteristics (heat shrinkage characteristics). When the shrink film is a laminated film, it is preferable that at least one film layer in the laminated film is oriented. When all the film layers are non-oriented, sufficient shrink characteristics may not be exhibited. The plastic film (especially shrink film) is preferably a uniaxial or biaxially oriented film, and more preferably a film (substantially uniaxially stretched) that is strongly oriented in the uniaxial direction of the film. A film uniaxially stretched in the width direction is particularly preferable.

  The plastic film can be produced by a conventional method such as melt film formation or solution film formation. A commercially available plastic film (such as a shrink film) can also be used. The surface of the plastic film may be subjected to conventional surface treatment such as corona discharge treatment or primer treatment, if necessary. When producing a laminated plastic film, a conventional method such as a co-extrusion method or a dry laminating method can be used as a laminating method. Examples of methods for orienting the plastic film include 2 in the longitudinal direction (film production line direction; also referred to as the longitudinal direction or MD direction) and the width direction (direction orthogonal to the longitudinal direction; also referred to as lateral direction or TD direction). Axial stretching, uniaxial stretching in the longitudinal direction or width direction, and the like can be used. As the stretching method, for example, a roll method, a tenter method, a tube method, or the like can be used. For example, the stretching treatment of the film substantially uniaxially stretched in the width direction is performed at a temperature of about 70 to 100 ° C., if necessary, 1.01 to 1.5 times in the longitudinal direction, preferably 1.05 to After stretching to about 1.3 times, it can be carried out by stretching in the width direction 3 to 6 times, preferably about 4 to 5.5 times.

  When the plastic film is a shrink film, the heat shrinkage rate in the main orientation direction of the shrink film at 90 ° C. for 10 seconds (sometimes referred to as “heat shrinkage rate (90 ° C., 10 seconds)”) is particularly limited. Although not, 15 to 90% is preferable, and more preferably 20 to 85%. Although the thermal contraction rate (90 degreeC, 10 second) of the direction orthogonal to the main orientation direction of the said shrink film is not specifically limited, -3-10% is preferable. The above-mentioned “main orientation direction” is a direction mainly subjected to a stretching process (a direction having the largest thermal shrinkage), and is generally a longitudinal direction or a width direction, for example, substantially in the width direction. In the case of a uniaxially stretched film, it is the width direction.

  When the plastic film is a transparent film, the haze value (%) of the plastic film (based on JIS K 7105) is preferably less than 10%, more preferably less than 5.0%, and still more preferably less than 2.0%. . When the haze (haze) value is 10% or more, when printing is shown through a plastic film, the printing may become cloudy and the decorativeness may be lowered.

  Although the thickness of the said plastic film is not specifically limited, 10-100 micrometers is preferable, More preferably, it is 12-80 micrometers, More preferably, it is 15-60 micrometers.

  A commercial item can also be used for the plastic film (for example, shrink film). For example, commercially available shrink films include “Space Clean S7042” and “SV-808” manufactured by Toyobo Co., Ltd., “LX-10S”, “LX-18S” and “LX-61S” manufactured by Mitsubishi Plastics, Inc. “Polyester film”; “Bonnset” manufactured by CI Kasei Co., Ltd .; “GMLS” manufactured by Gunze Co., Ltd. (polystyrene film); “FL” manufactured by Gunze Co., Ltd. (polyolefin film); “Ecology” manufactured by Mitsubishi Plastics (polylactic acid film); “DL” manufactured by Mitsubishi Plastics, and “HGS” manufactured by Gunze Co., Ltd. (The surface layer is a polyester resin and the center layer is a polystyrene resin. Laminated film) and the like.

[Production Method of Printed Plastic Film of the Present Invention]
The method for producing a printed plastic film according to the present invention (the method for producing the present invention) includes at least a step of forming the printed layer of the present invention by applying the ink of the present invention to at least one side of the plastic film and drying and solidifying it. . In the present specification, the above “process for forming the printed layer of the present invention by applying the ink of the present invention to at least one side of the plastic film and drying and solidifying it” is referred to as the “printed layer forming process of the present invention”. There is. The production method of the present invention includes at least one printing layer forming step of the present invention, and may include two or more printing layer forming steps of the present invention. Moreover, the manufacturing method of this invention may also include processes (other processes) other than the printing layer formation process of this invention.

  The printed layer forming step of the present invention includes at least a step of applying the ink of the present invention to at least one side of the plastic film, and a step of drying and solidifying the ink of the present invention applied to at least one side of the plastic film. Including. In the present specification, “the step of applying the ink of the present invention to at least one side of a plastic film” may be referred to as “application step”. Further, the above-mentioned “stage for drying and solidifying the ink of the present invention applied on at least one side of the plastic film” may be referred to as “drying and solidification stage”. The printed layer forming process of the present invention includes at least one coating step and at least one drying and solidifying step. Two or more coating steps and two or more drying and solidification steps may be included. Furthermore, steps other than the coating step and the drying and solidifying step may be included. In the printed layer forming process of the present invention, the printed layer of the present invention is formed through the application step and the drying and solidifying step.

  The application in the application step can be performed using a known and commonly used ink application method and printing method. The application method is not particularly limited, and examples thereof include a gravure printing method, a flexographic printing method, and a screen printing method from the viewpoint of cost, productivity, printing decoration, and the like. Among these, a gravure printing method is particularly preferable from the viewpoint of decorativeness of printing. In the gravure printing method, the step of filling the intaglio indentation (cell) with ink, the step of removing the ink excluding the intaglio cell (for example, using a doctor blade), the intaglio and the film are brought into contact with the cell. And a step of transferring the ink stored in the film surface to the film surface, so that the thickness of the printing layer becomes relatively thin. Therefore, the printing layer of the present invention is particularly suitable for the gravure printing method because it can exhibit excellent fluorescence even when the thickness is small.

  In the application step, the ink of the present invention may be applied only to one side of the plastic film, or the ink of the present invention may be applied to both sides of the plastic film. In addition, the ink of the present invention may be applied to the entire surface of the surface on which the plastic film is applied, or the ink of the present invention may be applied to a part of the surface. Further, the printing ink of the present invention may be applied directly (without other layers) to the surface of the plastic film, or on the other layers of the plastic film provided with other layers. The printing ink of the present invention may be applied to the surface (that is, the printing ink of the present invention may be applied to the surface of the plastic film via another layer). By the coating step, a layer (coating layer) of the printing ink of the present invention is formed on the plastic film.

  In the drying and solidifying step, the volatile component (mainly solvent) is removed from the layer (coating layer) of the printing ink of the present invention formed in the printing step, and the non-volatile component remains and is solidified. Is obtained. The drying and solidification in the drying and solidifying step can be performed using a known and common method for drying and solidifying ink. Although it does not specifically limit as said dry solidification, Dry solidification by heating and dry solidification by infrared rays are preferable. For heat drying and solidification, for example, a general heating device capable of heating on a printing device can be preferably used. The apparatus used in the drying and solidification is not particularly limited, but a hot air heater is preferable from the viewpoint of safety.

  In the production method of the present invention, the process (other processes) other than the printed layer forming process of the present invention is not particularly limited, but a process of forming a protective coating layer, a slit process, a label processing process (tubularization or And the like).

[Printed plastic film of the present invention]
The printed plastic film of the present invention has the printed layer of the present invention on at least one side of the plastic film. The printed layer of the present invention may be provided on the plastic film without any other layer (a layer other than the plastic film and the printed layer of the present invention) or may be provided via another layer. Also good.

  Although it does not specifically limit as said other layer, Printing layers other than the printing layer of this invention, a protective coating layer, an easily bonding layer, etc. are mentioned.

  The layer structure of the printed plastic film of the present invention is not particularly limited, but the printed layer / plastic film of the present invention; the printed layer / plastic film / printed layer of the present invention; the printed layer / plastic film / present of the present invention. Examples include printing layers other than the printing layer of the invention; protective coating layer / printing layer / plastic film of the invention; protective coating layer / printing layer of the invention / plastic film / printing layer of the invention / protective coating layer. The printed matter of the plastic film of the present invention may be a so-called surface printing (a type showing printing from the printing layer side) or a back printing (a type showing printing through a plastic film). From the viewpoint of the beauty of fluorescent color development, a printed material with surface printing is preferred.

(Print layer of the present invention)
The printed layer of the present invention is a printed layer containing at least the resin, the fluorescent pigment, and the sensitizer. The printed layer of the present invention may contain components other than the resin, the fluorescent pigment, and the sensitizer (other components) within a range not impairing the effects of the present invention. Examples of the other components include, but are not limited to, plasticizers, lubricants, anti-settling agents, dispersants, stabilizers, fillers, antioxidants, ultraviolet absorbers, antistatic agents, anti-coloring agents, and fragrances. And deodorant. Each of the resin, the fluorescent pigment, the sensitizer and the other components may be used alone or in combination of two or more.

Although content of the said resin in the printing layer of this invention is not specifically limited, 20 to 85 weight% is preferable with respect to 100 weight% of total weight of the printing layer of this invention, More preferably, it is 30 to 70 weight% It is.
Although content of the said fluorescent pigment in the printing layer of this invention is not specifically limited, 10-60 weight% is preferable with respect to 100 weight% of total weight of the printing layer of this invention, More preferably, it is 20-50 weight %.
The content of the sensitizer in the printing layer of the present invention is not particularly limited, but is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment. It is.

  The weight of the printing layer of the present invention is generally equal to the total non-volatile content (total non-volatile content) of the ink of the present invention. In order to control the content of components such as resins, fluorescent pigments, and sensitizers in the printing layer of the present invention, the content of each component in the non-volatile content of the ink of the present invention is the printing of the present invention. What is necessary is just to prepare the ink of this invention so that it may become desired content in a layer. Although not particularly limited, the content (% by weight) of each component (nonvolatile content) in the total nonvolatile content of the ink of the present invention is equal to the content (% by weight) of each component in the printed layer of the present invention. Become.

  Although the thickness of the printing layer of this invention is not specifically limited, 0.1-10 micrometers is preferable, More preferably, it is 0.2-5 micrometers, More preferably, it is 0.3-3 micrometers. If the thickness is less than 0.1 μm, it may be difficult to see the fluorescent color or it may be difficult to provide a printed layer uniformly, and partial “fading” may occur, resulting in impaired decorativeness, Printing as designed may be difficult. On the other hand, if it exceeds 10 μm, a large amount of ink is consumed, which may increase the cost, make it difficult to apply uniformly, or make the printing layer brittle and easy to peel off. Moreover, when the plastic film is a shrink film, the rigidity of the print layer becomes high, and the print layer may hardly follow the shrinkage of the shrink film during shrink processing. The printed layer of the present invention is preferable because it can exhibit excellent fluorescence even when the thickness is relatively thin.

  Although the plastic film printed matter of the present invention is not particularly limited, for example, a plastic label such as a stretch label, a shrink label, a stretch shrink label, an in-mold label, a tack label, a roll label (a wrap-type glued label), a thermal label; Examples include pillow packaging bags; gusset packaging bags; spouted bags; shrink packaging bags; Among these, a shrink label, a stretch label, and a tack label are preferable, and a shrink label is particularly preferable.

  When the plastic film printed matter of the present invention is a plastic label (for example, a tack label), it is not particularly limited. For example, it can also be used as an indicator label that can visualize the intensity of ultraviolet rays emitted from sunlight.

  The ink of the present invention and the printed layer of the present invention contain a sensitizer in addition to the fluorescent pigment. Therefore, in the ink of the present invention and in the printing layer of the present invention, the fluorescent pigment is not absorbed by the fluorescent pigment in addition to the light having an absorption wavelength unique to the fluorescent pigment (or the absorption efficiency is low). Light (visible light or ultraviolet light) having an absorption wavelength of the sensitizer can also be used. For this reason, the ink of the present invention and the printing layer of the present invention have an increased emission intensity and can exhibit an excellent fluorescence feeling as compared with the conventional fluorescent ink and a printing layer comprising the same.

  In the ink of the present invention and the printed layer of the present invention, when the sensitizer absorbs ultraviolet light (ultraviolet light) (particularly, ultraviolet light of 400 nm or less), the energy of the ultraviolet light is efficiently fluorescent by the sensitizer. Since it can be passed to the pigment, it is also possible to cause fluorescent color development only with ultraviolet light. The mechanism of energy transfer from the sensitizer to the fluorescent pigment is not clear, but it is estimated that energy transfer and light reabsorption occur. For this reason, the plastic film printed matter of the present invention can exhibit an excellent fluorescence feeling even under conditions with little visible light (for example, even with black light). For this reason, for example, by applying black light in a dark room or the like, it becomes a printed matter that can express a fluorescent feeling, and the decorating property of the printed matter is improved, which is preferable.

  EXAMPLES Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  Table 1 shows the components in the inks used in the examples and comparative examples, their blending composition (blending amount), the evaluation results of the obtained plastic labels, and the like.

Example 1
(ink)
As resin, acrylic resin (Mitsubishi Rayon Co., Ltd., trade name “Dianar BR-113”) 30 parts by weight, fluorescent pigment (Shinloihi Co., Ltd., trade name “SX-105”, absorption maximum wavelength: 440 nm , Fluorescence maximum wavelength: 502 nm) 23 parts by weight, sensitizer (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name “Anthracure UVS-1331”, absorption maximum wavelength: 385 nm) 3 parts by weight ethyl acetate 22 parts by weight, acetic acid The mixture was mixed with 22 parts by weight of n-propyl and dispersed using (trade name “TK Homodisper 2.5 type” (manufactured by Primics Co., Ltd.) to obtain an ink.

(Plastic label)
The ink obtained above is gravure-printed with a 175-line gravure plate on a PET-based shrink film (trade name “LX-18S” manufactured by Mitsubishi Plastics, Inc.), dried and solidified to obtain a printed layer (thickness) : 1.0 μm) to form a plastic label.

Comparative Example 1
As shown in Table 1, inks and plastic labels were produced in the same manner as in Example 1 except that no sensitizer was used and the blending amounts of ethyl acetate and n-propyl acetate were changed.

Example 2
As shown in Table 1, Examples were used except that the trade name “Kayacure DETX-S” (manufactured by Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone, absorption maximum wavelength: 386 nm) was used as a sensitizer. In the same manner as in Example 1, ink and plastic labels were prepared.

Example 3
As shown in Table 1, in the same manner as in Example 1, except that the trade name “SX-104” (manufactured by Sinloihi Co., Ltd., absorption maximum wavelength: 440 nm, fluorescence maximum wavelength: 590 nm) was used as the fluorescent pigment. Ink and plastic labels were prepared.

Comparative Example 2
As shown in Table 1, inks and plastic labels were produced in the same manner as in Example 3 except that no sensitizer was used and the blending amounts of ethyl acetate and n-propyl acetate were changed.

Example 4
As shown in Table 1, in the same manner as in Example 1 except that the trade name “SX-103” (manufactured by Sinloihi Co., Ltd., absorption maximum wavelength: 532 nm, fluorescence maximum wavelength: 595 nm) was used as the fluorescent pigment. Ink and plastic labels were prepared.

Comparative Example 3
As shown in Table 1, inks and plastic labels were produced in the same manner as in Example 4 except that no sensitizer was used and the blending amounts of ethyl acetate and n-propyl acetate were changed.

Example 5
As shown in Table 1, in the same manner as in Example 1 except that the trade name “SX-147” (manufactured by Sinloihi Co., Ltd., maximum wavelength: 570 nm, maximum wavelength: 615 nm) was used as the fluorescent pigment. Ink and plastic labels were prepared.

Comparative Example 4
As shown in Table 1, inks and plastic labels were produced in the same manner as in Example 5 except that no sensitizer was used and the blending amounts of ethyl acetate and n-propyl acetate were changed.

(Measurement method of fluorescence intensity)
From the plastic labels obtained in Examples and Comparative Examples, a label piece was cut into a measurable size and used as a measurement sample. Using the fluorescence spectrophotometer “F-4500” (manufactured by Hitachi, Ltd.), the obtained measurement sample is irradiated with light near the absorption maximum wavelength (386 nm) of the sensitizer, and the reflection spectrum is measured. did. From the obtained spectrum, the fluorescence intensity at the fluorescence maximum wavelength of each fluorescent pigment was read and used as the fluorescence intensity of the plastic label.

  As can be seen from the evaluation results, the plastic label (Examples 1 and 2) produced by the production method of the present invention has a wavelength of 502 nm as compared with the plastic label produced without using a sensitizer (Comparative Example 1). And had a high fluorescence intensity. In addition, the plastic label (Example 3) produced by the production method of the present invention has a higher fluorescence intensity at a wavelength of 590 nm than the plastic label (Comparative Example 2) produced without using a sensitizer. Was. In addition, the plastic label (Example 4) produced by the production method of the present invention has higher fluorescence intensity at a wavelength of 595 nm than the plastic label produced without using a sensitizer (Comparative Example 3). Was. In addition, the plastic label (Example 5) produced by the production method of the present invention has higher fluorescence intensity at a wavelength of 615 nm than the plastic label (Comparative Example 4) produced without using a sensitizer. Was.

Claims (7)

A method for producing a printed plastic film product, wherein ink is applied to at least one side of a plastic film, dried and solidified to form a printed layer,
The method for producing a printed matter of a plastic film, wherein the ink contains a resin, a fluorescent pigment, a sensitizer, and a solvent. The fluorescent pigment content is 10 to 60% by weight with respect to 100% by weight of the total nonvolatile content of the ink,
The method for producing a printed matter of a plastic film according to claim 1, wherein the content of the sensitizer is 3 to 25 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment.   The manufacturing method of the plastic film printed matter of Claim 1 or 2 with which the absorption maximum wavelength of the said sensitizer exists in 300-400 nm.   The method for producing a printed matter of a plastic film according to any one of claims 1 to 3, wherein the sensitizer is an anthracene compound and / or a thioxanthone compound.   The manufacturing method of the plastic film printed matter of any one of Claims 1-4 in which the absorption maximum wavelength of the said fluorescent pigment exists in 300-600 nm, and a fluorescence maximum wavelength exists in 400-700 nm. An ink containing a resin, a fluorescent pigment, a sensitizer, and a solvent,
The fluorescent pigment content is 10 to 60% by weight with respect to 100% by weight of the total nonvolatile content of the ink,
The ink according to claim 1, wherein the content of the sensitizer is 3 to 25 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment. A plastic film printed matter having a printed layer containing a resin, a fluorescent pigment, and a sensitizer on at least one side of the plastic film,
The content of the fluorescent pigment is 10 to 60% by weight with respect to 100% by weight of the total weight of the printed layer,
The plastic film printed matter, wherein the content of the sensitizer is 3 to 25 parts by weight with respect to 100 parts by weight of the total weight of the fluorescent pigment.