WO2022124082A1

WO2022124082A1 - Coating agent for paper substrates or plastic substrates, and paper substrates, plastic substrates, containers, and packaging materials that have coating layer of said coating agent

Info

Publication number: WO2022124082A1
Application number: PCT/JP2021/043095
Authority: WO
Inventors: 晃大門; 雅之寺川; 都詩中村; 敏生渡邊
Original assignee: Ｄｉｃグラフィックス株式会社
Priority date: 2020-12-08
Filing date: 2021-11-25
Publication date: 2022-06-16
Also published as: JP7174198B1; JPWO2022124082A1

Abstract

Provided is a coating agent for paper substrates or plastic substrates comprises a binder resin (A), an antimicrobial agent and/or antifungal agent (B), an anti-settling agent (C), and an organic solvent, wherein the anti-settling agent (C) is included in the amount of 0.1-50.0 mass% with respect to the antimicrobial agent and/or antifungal agent (B). Also provided are containers and packaging materials using these paper substrates or plastic substrates. The binder resin (A) comprises a cellulosic resin, polyamide resin, urethane resin, acrylic resin, or vinyl chloride resin.

Description

Coating agent for paper base material or plastic base material, and paper base material, plastic base material, container and packaging material having a coating layer of the coating agent.

The present invention relates to a coating agent for a paper base material or a plastic base material that can be used as a gravure ink for flexible packaging or a flexographic ink.

In recent years, it has been required to impart functionality to the surfaces of various base materials, and it is required to improve the surface properties of plastic materials, molded products, paper base materials, film base materials, packaging materials and the like. As a method of imparting these functions to the surface of a base material, a method of attaching a polymer film or the like having various functions to the surface is widely known. However, this method takes time and effort to attach the film, often has insufficient adhesion to the substrate and workability, and is expensive in terms of cost.
On the other hand, as a method of imparting functionality to the surface of these substrates, a method of expressing these functions by coating is also known. The coating method is highly convenient because it can be applied not only to the base material before molding or processing, but also to the base material after molding or processing, only to the desired part, but on the other hand, it is more functional than the film. In many cases, resistance is inferior.
As a base material, film base materials such as polyester film, nylon film, and polyolefin film, which are often used for food packaging and daily life coating consumer materials, are water repellent, oil repellent, antifouling, antistatic, antireflection, scratch prevention, etc. In addition to physical functionality, recently hygienic functions such as antibacterial, antifungal, antiviral, and deodorant functions are also desired.

On the other hand, as a compound having antibacterial, antifungal and deodorant functions, a compound in which zeolite particles, silica gel particles, alumina particles, phosphate particles and the like are used as carriers and a silver compound is supported on these carrier particles is known. .. For example, as an example of using silver-supported zeolite as an antibacterial agent, a coating agent for paper, a heat-sealing agent for paper (see, for example, Patent Documents 1 and 2), and an in-line coating agent used as an in-line coating during film production are known. (See, for example, Patent Document 2).

However, general-purpose silver-supported zeolite has a specific gravity of about 2 g / cm ³ or more, and when blended as a coating agent, it causes early precipitation and is difficult to handle, and when, for example, a gravure coating method is used as the coating method. Has a problem that the silver-supported zeolite itself is difficult to transfer to the substrate.

Japanese Unexamined Patent Publication No. 2009-203600 Japanese Unexamined Patent Publication No. 2017-040013 WO09 / 0626117

The present invention provides a coating agent for a paper base material or a plastic base material having antibacterial or antifungal properties using an antibacterial agent such as silver-supported zeolite or an antifungal agent, and has excellent coating suitability. There is something in it.

The present invention contains a binder resin (A), an antibacterial agent and / or an antifungal agent (B), an antisettling agent (C), and an organic solvent, and the antisettling agent (C) is used as the antibacterial agent and / or the antibacterial agent. Alternatively, the present invention provides a coating agent for a paper base material or a plastic base material containing a specific amount of the antifungal agent (B).

That is, the present invention contains a binder resin (A), an antibacterial agent and / or an antifungal agent (B), an antisettling agent (C), and an organic solvent, and the antisettling agent (C) is used as the antibacterial agent and / Or the coating agent for a paper base material or a plastic base material containing 0.1 to 50.0% by mass with respect to the antifungal agent (B).

The present invention also relates to a coating agent for a paper base material or a plastic base material in which the binder resin (A) contains a fibrous resin, a polyamide resin, a urethane resin, an acrylic resin, or a vinyl chloride resin. ..

Further, in the present invention, the binder resin is a urethane resin / vinyl chloride resin, a urethane resin / fiber element resin, a polyamide resin / fiber element resin, an acrylic resin / fiber element resin, or vinyl chloride. The present invention relates to a coating agent for a paper base material or a plastic base material, which is a combination selected from a based resin / a fibrous resin.

The present invention also relates to a coating agent for a paper base material or a plastic base material in which the antibacterial agent and / or the fungicide (B) is a silver-supported zeolite.

The present invention also relates to a coating agent for a paper base material or a plastic base material in which the antisettling agent (C) is fatty acid amide.

The present invention also relates to a coating agent for a paper base material or a plastic base material containing an isocyanate compound (E).

The present invention also relates to a paper base material or a plastic base material obtained by coating the coating agent on a paper base material and a film.

The present invention also relates to a paper base material or a plastic base material in which the paper base material or the plastic base material further has a printing ink layer.

The present invention also relates to a container and a packaging material using a paper base material or a plastic base material.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an antibacterial and antifungal coating agent which uses an antibacterial agent such as silver-supported zeolite or an antifungal agent and has excellent coating suitability.

(Definition of words)
In the present invention, "parts" means "parts by mass", "total amount of coating agent" means the total amount of ink containing all volatile components such as organic solvent, and "total amount of coating agent solid content" means. , Shows the total amount of non-volatile components only, without volatile components.

(Binder resin (A))
Examples of the binder resin (A) used for the coating agent for the paper base material or the plastic base material of the present invention include nitrified cotton, cellulose acetate propionate (CAP), cellulose acetate butironate (CAB), and other cellulose-based resins. Fiber element resin, polyamide resin, urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl chloride resin, etc. Examples thereof include vinyl chloride resin, polyester resin, alkyd resin, rosin resin, rosin modified maleic acid resin, ketone resin, cyclized rubber, rubber chloride, butyral, and petroleum resin.

(Fibrin resin)
Examples of the fiber-based resin include cellulose acetate propionate, cellulose acetate butyrate and other cellulose ester resins, nitrocellulose (also referred to as vitrified cotton), hydroxyalkyl cellulose, and carboxyalkyl cellulose. The cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group and the like, and further, an alkyl group. May have a substituent.
Of the above, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable as the cellulosic resin. Particularly preferred is nitrocellulose. The molecular weight preferably has a weight average molecular weight of 5,000 to 200,000, and more preferably 10,000 to 50,000. Further, it is preferable that the glass transition temperature is 120 ° C to 180 ° C. The combined use of the polyurethane resin (A) of the present invention is expected to improve blocking resistance, scratch resistance and other ink film physical properties.
Nitrocellulose (nitrated cotton) is obtained as a nitric acid ester obtained by reacting natural cellulose with nitric acid and substituting three hydroxyl groups in the 6-membered ring of anhydrous glucopyranose groups in the natural cellulose with nitric acid groups. preferable.

Since high dispersibility in pigments can be obtained by using nitrocellulose (nitrated cotton), it is preferable to use it as a coating agent for front printing because it can improve the strength of the printing ink coating film. .. The nitrocellulose (nitrated cotton) preferably has a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 30 to 500, and more preferably has a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 45 to 290. ..

The amount of nitrocellulose (nitrated cotton) added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of ink.

(Polyamide resin)
The polyamide resin is, for example, a thermoplastic polyamide that is soluble in an organic solvent and can be obtained by polycondensing a polybasic acid and a polyvalent amine. In particular, a polyamide resin containing a reaction product of an acid component containing a polymerized fatty acid and / or dimer acid and an aliphatic and / or aromatic polyamine, and further containing a part of primary and secondary monoamines. Is preferable.
The polybasic acid used as a raw material for a polyamide resin is not limited to the following, but is limited to adipic acid, sebacic acid, azelaic acid, phthalic acid anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, and pimerin. Acids, oxalic acids, malonic acids, succinic acids, maleic acids, terephthalic acids, 1,4-cyclohexyldicarboxylic acids, trimellitic acids, dimer acids, hydrogenated dimer acids, polymerized fatty acids, etc., among which dimer acids or polymerizations A polyamide resin containing a main component (50% by mass or more in the polyamide resin) of a structure derived from a fatty acid is preferable. Here, the polymerized fatty acid is obtained by a cyclization reaction of an unsaturated fatty acid fatty acid or the like, and includes a monobasic fatty acid, a dimeric acid fatty acid, a trimerized fatty acid and the like. As the fatty acid constituting dimer acid or polymerized fatty acid, those derived from natural oil such as soybean oil, palm oil and rice bran oil can be preferably mentioned, and those obtained from oleic acid and linoleic acid are preferable.
A monocarboxylic acid can also be used in combination with the polybasic acid. Examples of the monocarboxylic acid used in combination include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, cyclohexanecarboxylic acid and the like.

Examples of the polyvalent amine include polyamines, primary or secondary monoamines, and the like. Examples of the polyamine used for the polyamide resin include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and methylaminopropylamine, and aliphatic polyamines such as diethylenetriamine and triethylenetetramine. Examples of the alicyclic polyamines include aliphatic polyamines. , Cyclohexylenediamine, isophoronediamine and the like. Further, examples of the aromatic aliphatic polyamine include xylylenediamine, and examples of the aromatic polyamine include phenylenediamine and diaminodiphenylmethane. Further, examples of the primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine and the like.
The amount of the polyamide resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the ink.

(Urethane resin)
The urethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol with a polyisocyanate. As the polyol, for example, various known polyols generally used for producing a polyurethane resin can be used, and one kind or two or more kinds may be used in combination. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3-propanediol, 1,3-butanediol. , 1,4-Butanediol, Neopentyl Glycol, Pentandiol, 3-Methyl-1,5 Pentandiol, Hexadiol, Octanediol, 1,4-Butindiol, 1,4-butylenediol, Diethylene Glycol, Triethylene Glycol , Dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaeslitol and other saturated or unsaturated low molecular weight polyols. (1), these low-molecular-weight polyols (1), sebacic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, and pimelli acid. , Polyvalent carboxylic acids such as spellic acid, azelaic acid, trimellitic acid, pyromellitic acid or polyester polyols obtained by dehydration condensation or polymerization of these anhydrides (2); cyclic ester compounds such as polycaprolactone. Polyester polyols (3) obtained by ring-opening polymerization of lactones such as polyvalerolactone and poly (β-methyl-γ-valerolactone); the low molecular weight polyols (1) and the like, for example, dimethyl carbonate, etc. Polycarbonate polyols (4) obtained by reaction with diphenyl carbonate, ethylene carbonate, phosgen, etc .; polybutadiene glycols (5); glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A; glycols (6); 1 molecule Acrylic obtained by copolymerizing one or more hydroxyethyl, hydroxypropurate acrylate, acrylic hydroxybutyl, etc., or their corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or an ester thereof. Examples thereof include polyol (7).

Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates generally used for producing polyurethane resins. For example, 1,3-phenylenedis isocyanate, 1,4-phenylenedi isocyanate, 1-methyl-2,4-phenylenedi isocyanate, 1-methyl-2,6-phenylenediisocyanate, 1-methyl-2,5-phenylenediisocyanate, 1 -Methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylenedi isocyanate, 1-ethyl-2,4-phenylenedi isocyanate, 1-isopropyl-2,4-phenylenediisocyanate, 1,3-dimethyl-2 , 4-Hexamethylene diisocyanate, 1,3-dimethyl-4,6-phenylenediisocyanis, 1,4-dimethyl-2,5-phenylenediisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene diisocyanate, 3-Methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl -Naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4 , 4'-Diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate and other aromatic polyisocyanes Texamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexamethylene diisocyanate, 1,4-cyclohexamethylene diisocyanate, 1,3-di (isocyanis). Methyl) cyclohexane, 1,4-di (hexamethylene) cyclohexane, lysine diisocyanis, isophoron diisocyanis, 4,4'-dicyclohexamethylene diisocyanate, 2,4'-dicyclohexammethane diisocyanate, 2,2'-dicyclohexammethane diisocyanis, 3, 3'-dimethyl-4,4'-dicyclohexamethylene Aliphatic compounds such as diisocyanate or alicyclic polyisocyanates can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, these diisocyanate compounds can be used alone or in combination of two or more.

It is also possible to use a chain extender. Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, etc., as well as 2-hydroxyethylethylenediamine and 2-hydroxyethylpropyldiamine. , 2-Hydroxyethyl propylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrropyrethylenediamine, di-2-hydroxypyrropyrethylenediamine, di- Amines having a hydroxyl group in the molecule, such as 2-hydroxypropylethylenediamine, can also be used. These chain extenders can be used alone or in admixture of two or more.

Further, a monovalent active hydrogen compound can also be used as a terminal blocking agent for the purpose of stopping the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine and alcohols such as ethanol and isopropyl alcohol. Further, especially when it is desired to introduce a carboxyl group into the polyurethane resin, amino acids such as glycine and L-alanine can be used as a reaction terminator. These terminal blockers can be used alone or in admixture of two or more.
The weight average molecular weight of the urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 80,000.

The urethane resin is particularly preferably a urethane obtained by reacting a polyester polyol having a polycarboxylic acid having 7 or more carbon atoms and having two or more carboxyl groups and a compound having two or more hydroxyl groups as reaction raw materials with the polyisocyanate. It is a resin (A).

Examples of the polycarboxylic acid having 7 or more carbon atoms and two or more carboxyl groups include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and anhydrides of these acids, pimelic acid, and sveric acid. , Azelaic acid, sebacic acid, dimer acid and other aliphatic dicarboxylic acids, trimellitic acid and its anhydrides and the like, benzenetetracarboxylic acids, benzenepentacarboxylic acids, benzenehexacarboxylic acids and anhydrides of these acids and the like. Can be used. These polybasic acids may be used alone or in combination of two or more. Among them, when sebacic acid and dimer acid are used, they are preferable in that adhesion to a wide variety of various film substrates can be obtained, and these may be used alone or in combination.

As the polyester polyol, other polyvalent carboxylic acids may be used if necessary, and various known polyvalent carboxylic acids generally used for producing polyester polyols can be used, and one or two kinds can be used. The above may be used together. Examples thereof include adipic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid and the like.

In addition, as global awareness of environmental issues has increased in recent years, attention has been focused on raw materials derived from biomass resources such as plants instead of petroleum-derived raw materials that affect global warming, and it is also possible to use these raw materials. It is possible. Examples of the polyvalent carboxylic acid derived from the biomass resource include succinic acid and anhydrous succinic acid.

Examples of the compound having two or more hydroxyl groups include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and tri. Glycols such as ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol; 2-methyl-1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propane Diol, neopentaneglycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3- Glycol having a branched structure such as hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol; glycerin, trimethylolpropane, trimethylolethane, penta Ellisritol, sorbitol and the like can be used. These compounds may be used alone or in combination of two or more.

Further, as with polyvalent carboxylic acids, it is also possible to use raw materials derived from biomass resources such as plants for compounds having two or more hydroxyl groups. Examples of the compound having two or more hydroxyl groups derived from biomass resources include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, and glycerin.

The number average molecular weight of the polyester polyol is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 7,000, and even more preferably in the range of 900 to 6,000. ..

Further, it is more preferable to contain a polyether polyol in the range of 1 to 40% by mass with respect to the polyurethane resin as a constituent component of the polyurethane resin (A). As the polyether polyol, various known ether polyols generally used for producing a polyurethane resin can be used, and one kind or two or more kinds may be used in combination. Examples thereof include polyether polyols of polymers such as ethylene oxide, propylene oxide and tetrahydrofuran, or copolymers. It is more preferable that the number average molecular weight of the polyether polyol is 100 to 3500.

As the combined polyol, polyisocyanate compound, chain extender, terminal sequestering agent and the like used as necessary for the polyurethane resin (A) used in the liquid ink composition of the present invention, the above-mentioned ones can be used as they are.
The weight average molecular weight of the polyurethane resin (A) is preferably in the range of 10,000 to 100,000, more preferably in the range of 15,000 to 95,000.

The amount of these urethane resins added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of ink.

(acrylic resin)
The acrylic resin is not particularly limited as long as it is a copolymer of a polymerizable monomer containing a (meth) acrylic acid ester as a main component. Examples of the polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n. -Octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, iso-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl ( Examples thereof include meth) acrylate, ethoxyethyl (meth) acrylate, and phenoxyethyl (meth) acrylate. The polymerization method is not particularly limited, and those obtained by known bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like can be used.
The weight average molecular weight of the acrylic resin is preferably 5,000 to 200,000, more preferably 10,000 to 100,000.
The amount of the acrylic resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the ink.

(Polyester resin)
The polyester resin is not particularly limited as long as it is a polyester resin obtained by reacting an alcohol and a carboxylic acid using a known esterification polymerization reaction.
Alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3 propanediol, and 1,3-butane. Diol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butinediol , 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaes Examples thereof include ritol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, spiroglycol, isosorbide and the like. These can be used alone or in admixture of two or more. Of these, polyfunctional alcohols are preferable.
The carboxylic acids include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, hepanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, linoleic acid, oxalic acid and malonic acid. , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid and the like. These can be used alone or in admixture of two or more. Of these, polyfunctional carboxylic acid is preferable.
The weight average molecular weight of the polyester resin is preferably 500 to 6000. It is more preferably 1400 to 5500, and the amount of the polyester resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the ink.

(Vinyl chloride-vinyl acetate copolymer resin)
As the vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin is generally used and preferable. The vinyl chloride-vinyl acetate copolymer resin is not particularly limited as long as it is a copolymer of vinyl chloride and vinyl acetate. The molecular weight preferably has a weight average molecular weight of 5,000 to 100,000, and more preferably 10,000 to 70,000. The structure derived from the vinyl acetate monomer is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass in the solid content of the vinyl chloride-vinyl acetate copolymer resin in an amount of 100% by mass. In this case, the solubility in an organic solvent is improved, and the adhesion to the substrate, the physical characteristics of the film, the scratch resistance and the like are improved.
Further, from the viewpoint of solubility in an organic solvent, those containing a hydroxyl group derived from a vinyl alcohol structure are also preferable. The hydroxyl value is preferably 20 to 200 mgKOH / g. The glass transition temperature is preferably 50 ° C to 90 ° C.
The amount of the vinyl chloride-vinyl acetate copolymer resin added is preferably 0.15 to 40% by mass, more preferably 1.0 to 35% by mass, based on the total amount of the ink.

(Rosin resin)
The rosin-based resin is not particularly limited as long as it is a resin having a rosin skeleton, but rosin-modified maleic acid resin, rosin ester, rosin phenol, polymerized rosin and the like are preferable. The softening point (according to the ring-and-ball method) is preferably 90 to 200 ° C.
Of these, fibrin-based resins, polyamide-based resins, urethane-based resins, acrylic-based resins, and vinyl chloride-based resins are preferable. In particular, it is preferable that the binder resin contains at least two kinds of resins.
Preferably, it is selected from urethane resin / vinyl chloride resin, urethane resin / fiber element resin, polyamide resin / fiber element resin, acrylic resin / fiber element resin, vinyl chloride resin / fiber element resin. The total amount of the two resins is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, out of 100% by mass of the binder resin (A).

Further, urethane-based resin / vinyl chloride-based resin, urethane-based resin / fibrous-based resin, polyamide-based resin / fibrous-based resin, acrylic resin / fibrous-based resin, vinyl chloride-based resin / fibrous-based resin, The mass ratio is preferably 95/5 to 20/80, respectively. More preferably, the mass ratio is 90/10 to 50/50. This combination is excellent in abrasion resistance, blocking resistance, heat resistance, oil resistance and the like, which are the basic performances desired for a coating agent.

(Hardener)
Further, a curing agent may be used in combination with the binder resin (A). As the curing agent, a general-purpose curing agent may be used for organic solvent-based gravure ink, but the most commonly used is an isocyanate-based curing agent.
The amount of the isocyanate compound added is preferably in the range of 0.3% by mass to 10.0% by mass, preferably 1.0% by mass to 7.0% by mass, based on the solid content of the liquid printing ink from the viewpoint of curing efficiency. More preferred.
The binder resin (A) is preferably in the range of 0.15 to 50% by mass, preferably in the range of 1 to 40% by mass, based on the coating agent for paper or plastic base materials of the present invention. Is the most preferable.

(Antibacterial agent and / or antifungal agent (B))
The type of antibacterial agent and / or antifungal agent used in the present invention is not particularly limited, but it is preferable to use a silver-based antibacterial agent and / or silver-based antifungal agent because it is excellent in antibacterial and antifungal properties.
Examples of the silver-based antibacterial agent include silver-supported antibacterial agents in which zeolite particles, silica gel particles, alumina particles, phosphate particles and the like are used as carriers and a silver compound is supported on these carrier particles, as well as silver carbonate and the like. Of these, silver-supported zeolite is preferable. One type of antibacterial agent may be used alone, or two or more types may be used in combination. In addition, many of these silver-supported antibacterial agents also have an antifungal effect, and can be preferably used as an antifungal agent. Examples of such antibacterial agents and / or antifungal agents include "Zeomic" (manufactured by Sinanen Zeomic Co., Ltd.), "Bactekiller" (manufactured by Fuji Chemical Co., Ltd.), and "Novalon" (manufactured by Toagosei Co., Ltd.). Will be.

Further, in addition to the silver-based antibacterial agent and / or the silver-based antifungal agent, an organic / inorganic hybrid type antibacterial agent and / or an antifungal agent obtained by carrying an organic antibacterial agent and / or an antifungal agent in an inorganic compound. Agents can be used. This hybrid type antibacterial agent and / or antifungal agent has both the immediate effect of the organic component and the heat resistance and durability of the inorganic component. In addition, since the fungi / mold species that exert their effects differ by supporting a plurality of active ingredients, antibacterial / antifungal performance in a wide range of fields can be expected. Examples of such antibacterial agents and / or antifungal agents are "Essenguard" (manufactured by Sinanen Zeomic Co., Ltd.), "Lasap" (manufactured by Rasa Industries, Ltd.), "Cabinon" (manufactured by Toagosei Co., Ltd.), and " "Hybrid Ion Pure" (Ishizuka Glass Co., Ltd.) and the like.

The content of the antibacterial agent and / or the antifungal agent (B) in the coating agent of the present invention is not particularly limited, but if it is too small, it is difficult to develop antibacterial or antifungal properties, and if it is excessive, the coating agent The viscosity increases, and lumps of the antibacterial agent or antifungal agent are likely to occur in the coating agent, making it difficult to apply the coating agent uniformly to the film surface. Therefore, the content of the antibacterial agent and / or the antifungal agent (B) is preferably in the range of 1.0% by mass to 20.0% by mass, and 5.0% by mass to 10.0 with respect to the solid content of the coating agent. More preferably, it is by mass%.

The average diameter of the antibacterial agent and / or the antifungal agent (B) is not particularly limited, but the average diameter measured according to the JIS H 7804 method using a scanning electron microscope is 0.5 μm or more and 4 μm or less. It is preferable, and more preferably 1 μm or more and 3 μm. If the average particle size of the antibacterial agent and / or the antifungal agent (B) is too small, the antibacterial agent or the antifungal agent does not appear on the surface of the cured film of the coating agent, and sufficient antibacterial and antifungal properties can be obtained. Not preferred as it may not be. If the average particle size of the antibacterial agent and / or the antifungal agent (B) is too large, coating with a gravure plate tends to be difficult. Further, if the average particle size of the antibacterial agent and / or the antifungal agent (B) is too large, the antibacterial agent and / or the antifungal agent tend to settle easily in the coating agent.

(Anti-precipitation agent (C))
In the present invention, it is essential to use the antisettling agent (C) for the purpose of preventing the sedimentation of the silver-supported antibacterial agent used as the antibacterial agent and / or the antifungal agent (B). As the anti-precipitation agent (C), fatty acid amide is preferable, and specifically, palmitic acid amide, stearic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid amide and the like can be used. These fatty acid amides may be used alone or in combination of two or more. The fatty acid amide is characterized by containing 0.1 to 10.0% by mass with respect to the solid content of the coating agent. Of these, 0.1 to 5.0% by mass is preferable, and 0.5 to 2.0% by mass is most preferable.
Further, the fatty acid amide is preferably contained in an amount of 0.1 to 50.0% by mass with respect to the antibacterial agent and / or the antifungal agent (B). Of these, 1.0 to 30.0% by mass is preferable, and 10.0 to 20.0% by mass is most preferable.

By using the silver-supporting antibacterial agent used as the antibacterial agent and / or the antifungal agent (B) in combination with the anti-precipitation agent (C), the silver-supporting antibacterial agent in the coating agent can be efficiently applied during coating. It can be transferred to the substrate. This effect is particularly remarkable in the coating method using a plate such as the gravure coating method. Although the reason for this is not clear, since the coating agent containing the anti-settling agent (C) has viscosity, even a silver-supported antibacterial agent having a heavy specific gravity can be suitably transferred to the substrate, but the anti-settling agent (C) ) Is not contained, the fluidity of the coating agent behaves close to that of Neutonian, and it is presumed that the silver-supported antibacterial agent having a heavy specific gravity remains on the plate. Alternatively, it is presumed that the silver-supported antibacterial agent can be uniformly and stably present in the coating agent containing the anti-precipitation agent (C), and it is presumed that the silver-supported antibacterial agent is transferred to the substrate at a uniform ratio.

(Organic solvent)
The organic solvent used in the coating agent for a paper substrate or a plastic substrate of the present invention is not particularly limited, but for example, an aromatic hydrocarbon-based organic solvent such as toluene, xylene, Solbesso # 100, Solbesso # 150, etc. Hydrocarbon-based organic solvents such as hexane, methylcyclohexane, heptane, octane, and decane, and ester-based solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. Examples include various organic solvents. Further, as a water-mixable organic solvent, alcohol-based substances such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketone-based substances such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) Examples thereof include various glycol ether-based organic solvents such as di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. These can be used alone or in combination of two or more.

In terms of both work hygiene during printing and the harmfulness of packaging materials, use ethyl acetate, propyl acetate, isopropanol, normal propanol, etc., and do not use aromatic solvents such as toluene or ketone solvents such as methyl ethyl ketone. Is more preferable.

Of these, a mixture of isopropyl alcohol / ethyl acetate / methoxypropanol is more preferable from the viewpoint of solubility in polyurethane resin and nitrocellulose. Further, glycol ethers can be added as long as it is less than 10% by mass of the total amount of ink for drying adjustment.
The coating agent for a paper base material or a plastic base material of the present invention also has a wax, a chelate cross-linking agent, an extender pigment, a leveling agent, a defoaming agent, for the purpose of imparting the desired basic physical properties to the coating agent. It can also contain plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like.

(Manufacturing method of coating agent for paper base material or plastic base material)
The coating agent for a paper base material or a plastic base material of the present invention is produced by dissolving and / or dispersing the binder resin (A), the antibacterial agent and / or the fungicide (B) in an organic solvent. be able to. As the disperser, generally used, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill and the like can be used.

The coating agent for a paper base material or a plastic base material of the present invention can be coated on a base material such as a plastic material, a molded product, a film base material, and a packaging material by a general coating method, specifically, gravure. Roll coating (gravure coater), flexo roll coating (flexo coater), reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. can be adopted. Above all, from an industrial point of view, it is preferable to use a gravure roll coating (gravure coater) and a flexo roll coating (flexo coater).

Further, a coating layer may be provided on the base material by impregnating the base material with the overcoating agent of the present invention.
When the coating agent of the present invention is coated using a gravure coater, the viscosity may be 12 to 30 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigo Co., Ltd., more preferably 15 to 20 seconds. be.
Further, when the coating agent of the present invention is coated using a flexo coater, the viscosity may be as long as it is 7 to 40 seconds at 25 ° C. using Zahn Cup # 4 manufactured by Rigo Co., Ltd., and more preferably 10 to 20. Seconds.

The thickness of the coating layer of the present invention can be appropriately adjusted depending on the intended use and the material of the base material, but for example, the range of 0.1 μm to 5 μm is preferable, the range of 0.3 μm to 3 μm is preferable, and the range of 0.5 to 2 μm is preferable. preferable.

Since the coating agent for a paper base material or a plastic base material of the present invention has excellent dispersibility, one of the antibacterial agent and / or the fungicide (B) in the coating layer formed by using the coating agent. The structure tends to expose the part. Therefore, the coating layer in the present invention can maximize the antibacterial or antifungal effect. The

(Coating agent for paper base material or plastic base material of the present invention)
The base material used in the present invention is a paper base material or a plastic base material.

(Paper base material)
The paper base material is manufactured by a known paper machine using natural fibers for paper making such as wood pulp, but the paper making conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp such as coniferous tree pulp and broadleaf tree pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, chemical pulp, gland pulp, chemi-grand pulp, thermomechanical pulp and the like obtained by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method and the like can be used.
Further, various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboards, paperboards and the like can also be used.

(Plastic base material)
The plastic base material may be any base material used for base materials such as plastic materials, molded products, film base materials, and packaging materials, and in particular, gravure roll coating (gravure coater) and flexorol coating (flexo coater). When using, the film base material usually used in the field of gravure / flexo printing can be used as it is.
Specifically, for example, polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, and polybutylene terephthalate. Polyester resins such as polybutylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polypropylene, polyethylene, etc. Examples thereof include films made of thermoplastic resins such as polyolefin resins, polyimide resins, polyarylate resins or mixtures thereof, and laminates thereof. Among them, films made of polyethylene terephthalate (PET), polyester, polyamide, polyethylene and polypropylene. Can be preferably used. In these base films, petroleum-derived raw materials or plant-derived raw materials are used as raw materials, but in the present invention, either of them may be used. Further, these base films may be unstretched films or stretched films, and the production method thereof is not limited. Further, the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 μm. Further, the base film is preferably subjected to a corona discharge treatment, and aluminum, silica, alumina or the like may be vapor-deposited.

The base material is a laminated body (sometimes referred to as a laminated film) having a laminated structure in which the paper base material or the film base material is laminated by a dry laminating method, a solvent-free laminating method, or an extrusion laminating method. It doesn't matter. Further, the structure of the laminate may include a metal foil, a metal vapor deposition film layer, an inorganic vapor deposition film layer, an oxygen absorption layer, an anchor coat layer, a printing layer, a varnish layer and the like. There are various types of such laminates depending on the application, but the most commonly used configurations for food packaging and daily necessities are the paper base material and film base material expressed as (F), and printing and varnish layers. Is expressed as (P), the metal or inorganic layer of the metal foil or vapor-deposited film layer is expressed as (M), the adhesive layer is expressed as (AD), and the hot melt adhesive, heat sealant or cold sealant is expressed as (AD2). ), The following configuration can be considered as a specific embodiment of the laminated film, but of course, the present invention is not limited to this.

(F) / (P) / (F)
(F) / (P) / (AD) / (F),
(F) / (P) / (AD) / (F) / (AD) / (F),
(F) / (P) / (AD) / (M) / (AD) / (F),
(F) / (P) / (AD) / (M),
(F) / (P) / (AD) / (F) / (AD) / (M) / (AD) / (F),
(F) / (P) / (AD) / (M) / (AD) / (F) / (AD) / (F),
(M) / (P) / (AD) / (M),
(M) / (P) / (AD) / (F) / (AD) / (M),
(P) / (F)
(P) / (F) / (P)
(P) / (F) / (AD) / (F),
(P) / (F) / (AD) / (F) / (AD) / (F)
(F) / (P) / (F) / (AD2)
(F) / (P) / (AD2)
(F) / (P) / (AD) / (M) / (AD2)

The single-layer paper base material or film base material, or the laminate having a laminated structure may be a functional film, a flexible packaging film, a shrink film, a film for daily necessities packaging, a film for pharmaceutical packaging, or a food product, depending on the industry and usage method. High-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper, etc. used for packaging of packaging films, cartons, posters, leaflets, CD jackets, direct mail, brochures, cosmetics and beverages, pharmaceuticals, toys, equipment, etc. Although various expressions such as paper and various synthetic papers are used, the coating agent for a paper base material or a plastic base material of the present invention can be used without particular limitation. At this time, it is preferable that the coating agent for a paper base material or a plastic base material of the present invention is coated on the surface that becomes the outermost layer when a container or packaging material using these is used.

As described above, as a laminated body having a laminated structure, many laminated bodies have a printed layer on which a printed layer is applied to a paper base material or a film base material, but the coating for a paper base material or a plastic base material of the present invention is used. Of course, the agent can also be coated on the substrate having the printing ink layer, which is preferable.

The printing ink used for the printing ink layer is not particularly limited, and coating is possible on the printing layer such as offset flat plate ink, gravure printing ink, flexo printing ink, and inkjet printing ink. In particular, when using gravure roll coating (gravure coater) or flexo roll coating (flexo coater), in-line printing is possible, so it is industrially possible to combine it with gravure printing ink or flexo printing ink. Is preferable.
The gravure printing ink and the flexographic printing ink (hereinafter referred to as liquid printing ink) are formed of a printing ink composed of a binder resin, a pigment, a solvent, and if necessary, an additive.

(Liquid printing ink)
Liquid printing inks used as gravure printing inks and flexo printing inks are roughly classified into organic solvent type liquid printing inks having an organic solvent as a main solvent and water-based liquid printing inks having water as a main solvent.

(Organic solvent type liquid printing ink)
In the organic solvent type liquid printing ink, in addition to the modified pigment used in the present invention, a mixture containing a binder resin, an organic solvent medium, a dispersant, a defoaming agent, etc., which will be described later, is dispersed by a disperser to obtain a pigment dispersion. .. It is obtained by adding an additive such as a resin, an aqueous medium and, if necessary, a leveling agent to the obtained pigment dispersion and stirring and mixing. As the disperser, it is manufactured by using a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, etc., which are generally used for manufacturing gravure and flexographic printing inks.

The ink viscosity of the organic solvent type liquid printing ink is 10 mPa · s or more from the viewpoint of preventing the pigment from settling and appropriately dispersing it, regardless of whether it is used as a gravure ink or a flexographic ink. From the viewpoint of workability efficiency during ink production and printing, the range is preferably 1000 mPa · s or less. The viscosity is a viscosity measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

The viscosity of the ink can be adjusted by appropriately selecting the type and amount of raw materials used, the binder resin, the pigment, the organic solvent, and the like. Further, the viscosity of the ink can be adjusted by adjusting the particle size and the particle size distribution of the pigment in the ink.

(Creation of printed matter)
Organic solvent-type liquid printing inks have excellent adhesion to various substrates and can be used for printing on paper, synthetic paper, thermoplastic resin films, plastic products, steel plates, etc., and are electronically engraved indentations, etc. It is useful as an ink for gravure printing using a gravure printing plate with a resin plate or for flexographic printing using a flexographic printing plate with a resin plate or the like.

The film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the organic solvent type liquid printing ink of the present invention is, for example, 10 μm or less, preferably 5 μm or less.

(Binder resin)
The binder resin for organic solvent type liquid printing ink is not particularly limited, and is not particularly limited in general. Polyurethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride used for general liquid printing ink. -Acrylic copolymer resin, chlorinated polypropylene resin, cellulose resin, polyamide resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, styrene resin, dammar resin, styrene-maleic acid copolymer resin, polyester resin, Alkid resin, polyvinyl chloride resin, rosin resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, rubber chloride, butyral, polyacetal resin, petroleum resin, and modified resins thereof, etc. Can be mentioned. These resins can be used alone or in admixture of two or more.

Among the above, polyurethane resin, cellulose resin, polyamide resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, acrylic resin, styrene resin. , A binder resin containing at least one selected from the group consisting of a styrene-maleic acid copolymer resin, a dammar resin, a rosin-based resin, a rosin-modified maleic acid resin, a ketone resin and a cyclized rubber is preferable.
The content of the binder resin is in the range of 1 to 50% by mass in terms of solid content, more preferably 2 to 40% by mass in terms of solid content of the aqueous liquid printing ink of the present invention.

(Organic solvent)
The organic solvent for the organic solvent type liquid printing ink is not particularly limited, but for example, aromatic hydrocarbon-based organic solvents such as toluene, xylene, Solbesso # 100 and Solbesso # 150, hexane, methylcyclohexane, heptane, octane, etc. Examples thereof include aliphatic hydrocarbon-based organic solvents such as decane, and various ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. Further, as a water-mixable organic solvent, alcohol-based substances such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketone-based substances such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) Examples thereof include various glycol ether-based organic solvents such as di) methyl ether, propylene glycol (mono, di) methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono, di) methyl ether. These can be used alone or in combination of two or more.

The organic solvent type liquid printing ink should also contain wax, chelate cross-linking agent, extender pigment, leveling agent, defoaming agent, plasticizer, infrared absorber, ultraviolet absorber, fragrance, flame retardant, etc., if necessary. You can also.

(Colorant)
The organic solvent type liquid printing ink uses the modified pigment as a colorant, but in addition, an organic pigment and / or an inorganic pigment used in general inks, paints, recording agents and the like may be used in combination. ..
Organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthanthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, and quinacridone. Pigments such as thioindigo-based, dioxazine-based, isoindoleinone-based, quinophthalone-based, azomethine-azo-based, flavanthron-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, and carbon black-based pigments can be mentioned. Also, for example, Carmin 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolon Orange, Carmin FB, Chromophthal Yellow, Chromophthal Red, Phtalocyanin Blue, Phtalussinin Green, Dioxazine Violet, Quinacridone Magenta, Kinacridone Red, Indance. Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments. Further, either an acid-treated pigment or an acid-treated pigment can be used.

Examples of the inorganic pigment include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum. Among the inorganic pigments, the use of titanium oxide is particularly preferable. Titanium oxide has a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.
Examples of non-white inorganic pigments include aluminum particles, mica (mica), bronze powder, chrome vermillion, yellow lead, cadmium yellow, cadmium red, ultramarine, dark blue, red iron oxide, yellow iron oxide, iron black, and zircon. Although aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and concentration.
The average particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably about 50 to 150 nm.
The pigment is in an amount sufficient to secure the concentration and coloring power of the water-based liquid printing ink, that is, 1 to 60% by mass with respect to the total mass of the ink, and 10 to 90% by mass with respect to the solid content mass ratio in the ink. It is preferably contained in proportion. In addition, these pigments can be used alone or in combination of two or more.

(Aqueous liquid printing ink)
In the water-based liquid printing ink, in addition to the modified pigment used in the present invention, a mixture to which a binder resin, an aqueous medium, a dispersant, a defoaming agent and the like described later are added is dispersed by a disperser to obtain a pigment dispersion. It is obtained by adding an additive such as a resin, an aqueous medium and, if necessary, a leveling agent to the obtained pigment dispersion and stirring and mixing. When a water-based liquid printing ink manufactured using a bead mill, Eiger mill, sand mill, gamma mill, attritor, etc., which is generally used for manufacturing gravure and flexo printing inks as a disperser, is used as flexographic ink. The viscosity may be as long as 7 to 25 seconds at 25 ° C. using Zahn Cup # 4 manufactured by Rigo Co., Ltd., and more preferably 10 to 20 seconds. The surface tension of the obtained flexographic ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. Tend to be easily connected, which tends to cause stains on the printed surface called a dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink on a substrate such as a film is lowered, which tends to cause repelling.

On the other hand, when the water-based liquid printing ink is used as a gravure ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigo Co., Ltd., more preferably 10 to 20 seconds. .. The surface tension of the obtained gravure ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m, as in the flexographic ink. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. Tend to be easily connected, which tends to cause stains on the printed surface called a dot bridge. On the other hand, when the surface tension exceeds 50 mN / m, the wettability of the ink on a substrate such as a film is lowered, which tends to cause repelling.

(Creation of printed matter)
Aqueous liquid printing ink has excellent adhesion to various base materials and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc., and is gravure by electronic engraving ingot. It is useful as an ink for gravure printing using a printing plate or for flexo printing using a flexo printing plate using a resin plate or the like.

The film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the water-based liquid ink of the present invention is, for example, 10 μm or less, preferably 5 μm or less.

(Binder resin)
The binder resin for water-based liquid printing ink is not particularly limited, and urethane resin, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, acrylic acid used in general water-based liquid printing inks. Acrylic copolymers such as potassium-acrylonitrile copolymer, acrylic acid ester polymer emulsion, polyester urethane dispersion, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid alkyl ester copolymer; styrene- Acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid- Acrylic acid alkyl ester styrene-acrylic acid resin such as copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene-acrylic acid copolymer; vinylnaphthalene-maleic acid copolymer; vinyl acetate-ethylene homoweight Combines, vinyl acetate-fatty acid vinyl ethylene copolymers, vinyl acetate-maleic acid ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers and other vinyl acetate-based copolymers and theirs. Acrylic acid can be used. These binder resins can be used alone or in admixture of two or more.

Among them, it is preferable to use an acrylic resin or a urethane resin as the binder resin because it is easily available, and an acrylic acid ester-based polymer emulsion and a polyester-based urethane dispersion are particularly preferable.

The binder resin is preferably 5 to 50% by mass in terms of solid content of the aqueous liquid printing ink of the present invention. When it is 5% by mass or more, the strength of the ink coating film does not decrease, and the adhesion to the substrate, the water friction resistance, and the like are kept good. On the contrary, when it is 50% by mass or less, the decrease in coloring power can be suppressed, the high viscosity can be avoided, and the workability does not decrease. Of these, 5 to 40% by mass is still more preferable, and 5 to 20% by mass is most preferable.

(Aqueous medium)
Examples of the aqueous medium for the aqueous liquid printing ink include water, an organic solvent miscible with water, and a mixture thereof. Examples of the organic solvent to be mixed with water include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; polyalkylene glycols. Alkyl ethers; examples include lactam solvents such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. Further, as the aqueous medium, only water or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable, from the viewpoint of safety and environmental load.

The water-based liquid printing ink can also contain the above-mentioned colorants, extender pigments, pigment dispersants, leveling agents, defoamers, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like. Among them, fatty acid amides such as oleic acid amide, stearate amide, and erucic acid amide for imparting abrasion resistance and slipperiness, and silicon-based, non-silicon-based defoaming agents and pigments for suppressing foaming during printing. Various dispersants and the like that improve the wetting of the hydrate are useful.

The present invention will be described in more detail by way of examples. Hereinafter, both "part" and "%" are based on the mass standard.

(Adjustment of varnish A)
As a vinyl chloride-vinyl acetate copolymer resin, varnish A was obtained by dissolving Solvine A manufactured by Nisshin Chemical Industry Co., Ltd. in the following ratio.
Solvine A 25 parts Methyl ethyl ketone 75 parts

(Adjustment of varnish B)
As the fibrin-based resin, varnish B was prepared by dissolving CAB-381-01 manufactured by Eastman Chemical Company in the following ratio.
CAB-381-01 20 parts Ethyl acetate 80 parts

(Adjustment of varnish C)
(Adjustment of polyurethane resin solution U)
100 parts of polyester polyol (hydroxyl value: 108 mgKOH / g) made from neopentyl glycol and sebacic acid and isophorone diisocyanate 32.3 in a four-necked flask equipped with a stirrer, thermometer, recirculation cooler and nitrogen gas introduction tube. Parts are charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to produce a urethane prepolymer having an isocyanate group content of 3.08% by mass, and then 71.2 parts of ethyl acetate is added thereto to make the urethane prepolymer uniform. It was made into a solution. Next, the urethane prepolymer solution was added to a mixture consisting of 8.47 parts of isophorondiamine, 0.46 parts of di-n-butylamine, 143 parts of ethyl acetate and 115 parts of isopropyl alcohol, and the mixture was stirred and reacted at 45 ° C. for 5 hours. A polyurethane resin solution U was obtained. The obtained polyurethane resin solution U had a resin solid content concentration of 29.9% by mass and a weight average molecular weight of the resin solid content of 54,000.

(Preparation of nitrocellulose solution N)
Industrial vitrified cotton H1 / 2 (nitrocellulose, solid content 70%, viscosity 9.0-14.9% at a solution concentration of 25.0% by JIS K-6703, manufactured by Taihei Chemical Products Co., Ltd.) in 37.5 parts , 62.5 parts of a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methyl cyclohexane (ratio of 25/25/13/10 by weight) was added and sufficiently mixed to prepare a nitrocellulose solution N.

(Preparation of rosin resin solution R)
50 parts of rosin resin (trade name: NEOCITE F-896, manufactured by Gangnam Kasei Co., Ltd.) was dissolved in 50 parts of isopropyl alcohol to obtain a rosin resin solution R having a solid content of 50%.

40 parts of the obtained polyurethane resin solution U, 25 parts of the nitrocellulose solution N, and 5 parts of the rosin resin solution R were added to obtain varnish C.

(Examples 1 to 5 Comparative Examples 1 to 6 An example of a coating agent containing varnish A and varnish B as a binder resin and an antibacterial agent)
(Example 1 Method of adjusting coating agent)
40 parts of varnish A, 20 parts of varnish B, 16 parts of n-propyl acetate, 2.5 parts of monosizer ATBC (plastic agent for ink manufactured by DIC Co., Ltd.), LUWAX AF-31 (manufactured by BASF) 0.3 parts of polyethylene wax), 1 part of Zeomic AJ-10N (Cinenen Zeomic Co., Ltd.) as a silver-based antibacterial agent, and 1 part of Flownon SP-1000AF as a settling inhibitor (Note that Flownon SP- 1000AF (manufactured by Kyoeisha Chemical Co., Ltd.) is a mixture of higher fatty acid amide and butyl acetate / ethanol / methanol / water, and the solid content of fatty acid amide is 10% by mass, so the amount of solid content added is 0.1. A total of 100 parts was stirred and mixed with methyl ethyl ketone as the balance to prepare the coating agent (1).

(Coating method on film)
After adjusting the viscosity of the coating agent (1) with a diluting solvent of methyl ethyl ketone / ethyl acetate = 1/1 with Zahn Cup # 3 for 16 seconds, "Takenate D-160N" (Mitsui Chemicals, Inc.), which is an isocyanate as a curing agent, is used. A polyethylene terephthalate (PET) film (E5102 12 μm manufactured by Toyo Spinning Co., Ltd.) was coated with a 175-line / inch gravure plate, and the organic solvent was dried to prepare the film of Example 1.

(Examples 2 to 5)
The coating agents and films of Examples 2 to 5 were prepared in the same manner as in Example 1 except that the composition of the coating agent was as shown in Table 1. In Example 4, the curing agent "Takenate D-160N (manufactured by Mitsui Chemicals, Inc.)" is not blended.

(Comparative Example 1 Method of adjusting coating agent))
One part of Zeomic AJ-10N (Sinanen Zeomic Co., Ltd.) as a silver-supporting zeolite, which is a silver-based antibacterial agent, and Fronon SP-1000AF (Fronon SP-1000AF is a higher fatty acid amide and butyl acetate / ethanol / methanol) as an anti-precipitation agent. / A total of 98 parts are stirred and mixed in the same manner as in Example 1 except that 1 part is not mixed (manufactured by Kyoeisha Chemical Co., Ltd.), which is a mixture with water and has a solid content of 10% by mass of fatty acid amide, and Comparative Example 1 The gravure coating agent (H1) was adjusted.

(Coating method on film)
The film of Comparative Example 1 was prepared in the same manner as the method of coating the film of Example 1 with the coating agent (H1).

(Comparative Examples 2 to 6)
The coating agents and films of Comparative Examples 2 to 6 were prepared in the same manner as in Comparative Example 1 except that the composition of the coating agent was as shown in Table 2.

(Examples of Examples 6 to 10 Comparative Examples 7 to 12 A coating agent containing varnish C as a binder resin and an antibacterial agent)
(Example 6)
70 parts of varnish C, 6 parts of methylcyclohexane, 1 part of lauric acid amide (weight average molecular weight 199.3 CAS number 1120-16-7), 0 part of monosizer ATBC (plastic agent for ink manufactured by DIC Co., Ltd.) .5 parts, 2 parts of titanium TAA chelating agent (manufactured by BORICA: titanium acetylacetonate CAS: 17927-27-9), Zeomic AJ-10N as a silver-supported zeolite which is a silver-based antibacterial agent (Cinenen Zeomic Co., Ltd.) 1 part, 1 part of Flownon SP-1000AF as a sedimentation inhibitor (Note that Flownon SP-1000AF (manufactured by Kyoeisha Chemical Co., Ltd.) is a mixture of higher fatty acid amide and butyl acetate / ethanol / methanol / water, and is a solid content. Since a certain fatty acid amide is 10% by mass, the amount of solid content added is 0.1), and the balance of methyl ethyl ketone is mixed in a total of 100 parts to prepare the coating agent (6).

(Coating method on film)
The viscosity of the coating agent (6) was adjusted to 16 seconds with Zahn Cup # 3 using a diluting solvent of methyl ethyl ketone / ethyl acetate / isopropyl alcohol = 2/2/1, and then biaxially stretched polypropylene was subjected to corona discharge treatment on one side. The treated surface of the film (FOR thickness 20 μm manufactured by Futamura Chemical Co., Ltd.) was coated and the organic solvent was dried to prepare the film of Example 6.

(Examples 7 to 10)
The coating agents and films of Examples 7 to 10 were prepared in the same manner as in Example 6 except that the composition of the coating agent was as shown in Table 3.

(Comparative Example 7 Method of adjusting coating agent))
A total of 98 parts were stirred and mixed in the same manner as in Example 6 except that Zeomic AJ-10N (Cinenen Zeomic Co., Ltd.) as a silver-supported zeolite which is a silver-based antibacterial agent and Fronon SP-1000AF as a settling inhibitor were not blended. The gravure coating agent (H7) of Comparative Example 7 was adjusted.

(Coating method on film)
The film of Comparative Example 7 was prepared in the same manner as the method of coating the film of Example 6 with the coating agent (H7).

(Comparative Examples 8 to 12)
The coating agents and films of Comparative Examples 8 to 12 were prepared in the same manner as in Comparative Example 7 except that the composition of the coating agent was as shown in Table 4.

(Evaluation method)
The films of Examples 1 to 10 and Comparative Examples 1 to 12 produced by the above method were evaluated as follows.

(Abrasion resistance)
The printed surface of each film was rubbed with high-quality paper using a Gakushin type friction resistance tester, and the degree of peeling of the printed layer was visually determined. (100 round trips with a load of 200 g)

(Evaluation criteria)
5: The printed film does not separate from the film at all.
4: As the area ratio of the printed film, less than 20% is detached from the film.
3: As the area ratio of the printed film, 20% or more and less than 40% are desorbed from the film, which is within the practical range.
2: As the area ratio of the printing film, 40% or more and less than 60% are detached from the film.
1: As the area ratio of the printed surface, 60% or more is detached from the film.

(Solvent resistance)
The printed surface was rubbed 20 times with a cotton swab soaked with ethanol, and the degree of peeling of the printed layer was visually determined.

(Coating surface evaluation)
The surface of the film coated with the coating agent was visually evaluated.
◯: Good with no unevenness on the surface
Δ: Some irregularities are seen on the surface ×: Many irregularities are seen on the surface, so it was regarded as defective.

(Antibacterial test)
JIS Z2801-2010 Apply the compositions of Examples and Comparative Examples in accordance with the description of "Antibacterial processed products-Antibacterial test method / Antibacterial effect" (mainly "5 Test methods") for plastic products, etc. The test was carried out using the obtained film as a sample. The strains in the test bacterial solution were Escherichia coli (NBRC3972) and Staphylococcus aureus (NBRC12732). Was brought into close contact with each other and cultured at 35 ± 1 ° C. and a relative humidity of 90% or more for 24 hours. Then, the bacterial solution was washed out, and the viable cell count per 1 cm2 of the sample was measured.
When the obtained antibacterial activity value is 2.0 or more, it is defined as having an antibacterial effect, and this is used as a criterion.
The antibacterial activity value is calculated by the following formula.
Antibacterial activity value (R) = Ut-At
Ut: Log of viable cell count after culturing of uncoated sample with antibacterial coating agent
At: Log of viable cell count after culture of antibacterial agent-added sample

The evaluation was performed by the following A to C.
A: Antibacterial activity value (R) is 3.0 or more (with antibacterial property)
B: Antibacterial activity value (R) is 2.0 or more and less than 3.0 (highly likely to have antibacterial activity).
C: Antibacterial activity value (R) is less than 2.0 (no antibacterial property)

The composition of the coating agent is shown in Tables 1 to 4, and the physical characteristics of the film having the coating layer are shown in Tables 5 to 8.

(Examples of Examples 11 to 15 Comparative Examples 13 to 18 A coating agent containing varnish A and varnish B as a binder resin and an antifungal agent)
(Example 11 Method of adjusting coating agent)
40 parts of varnish A, 20 parts of varnish B, 16 parts of n-propyl acetate, 2.5 parts of monosizer ATBC (plastic agent for ink manufactured by DIC Co., Ltd.), LUWAX AF-31 (polyethylene manufactured by BASF). 0.3 parts of wax), 1 part of Essenguard 10 (Sina-Nenzeomic Co., Ltd.) as an organic-inorganic composite type antifungal agent, 1 part of Flownon SP-1000AF as a settling inhibitor (Note that Flownon SP-1000AF (Kyoeisha) (Manufactured by Chemical Co., Ltd.) is a mixture of higher fatty acid amide and butyl acetate / ethanol / methanol / water, and the solid content of fatty acid amide is 10% by mass, so the amount of solid content added is 0.1). A total of 100 parts of the rest of the methyl ethyl ketone was stirred and mixed to prepare the coating agent (11).

(Coating method on film)
After adjusting the viscosity of the coating agent (11) with a diluting solvent of methyl ethyl ketone / ethyl acetate = 1/1 with Zahn Cup # 3 for 16 seconds, "Takenate D-160N" (Mitsui Chemicals, Inc.), which is an isocyanate as a curing agent, is used. A polyethylene terephthalate (PET) film (E5102 12 μm manufactured by Toyo Spinning Co., Ltd.) was coated with a 175-line / inch gravure plate, and the organic solvent was dried to prepare the film of Example 11.

(Examples 12 to 15)
The coating agents and films of Examples 12 to 15 were prepared in the same manner as in Example 11 except that the composition of the coating agent was as shown in Table 9. In Example 14, the curing agent "Takenate D-160N (manufactured by Mitsui Chemicals, Inc.)" is not blended.

(Comparative Example 13 Method of adjusting coating agent))
The gravure coating agent (H13) of Comparative Example 13 in the same manner as in Example 1 except that the organic-inorganic composite antifungal agent Essenguard 10 (Sina Nenzeomic Co., Ltd. system) and the sedimentation inhibitor Fronon SP-1000AF were not blended. Was adjusted.

(Coating method on film)
The film of Comparative Example 13 was prepared in the same manner as the method of coating the film of Example 11 with the coating agent (H13).

(Comparative Examples 14 to 18)
The coating agents and films of Comparative Examples 14 to 18 were prepared in the same manner as in Comparative Example 13 except that the composition of the coating agent was as shown in Table 10.

(Evaluation method)
The friction resistance, solvent resistance, and coating surface evaluation of the films of Examples 11 to 15 and Comparative Examples 13 to 18 produced by the above method are the same evaluation methods as those of Examples 1 to 10 and Comparative Examples 1 to 12. I went there.

(Mold resistance test)
A PET film coated with the compositions of Examples and Comparative Examples in accordance with "Method B Glucose-added Inorganic Salt Agar Medium" of "Annex A Plastic Product Test" of JIS Z2911-2018 "Mold Resistance Test Method". Was used as a sample for testing. The following five types of mixed spore suspensions were used as the test solution.
Aspergillus niger NBRC105649
Penicillium pinophilum NBRC100533
Paecilomyces variotii NBRC107725
Trichoderma virens NBRC6355
Chaetomium globosum NBRC6347
Mold growth after placing the sample on a glucose-added inorganic salt agar medium, dropping 0.1 ml of the mixed spore suspension onto the coated surface of the coating agent, and culturing at 29 ± 1 ° C. and a relative humidity of 90% or more for 4 weeks. Was observed with the naked eye and with a 50x actual state microscope, and evaluated according to the following criteria.
0: No mold growth is observed with the naked eye or under a microscope.
1: Mold growth is not observed with the naked eye, but it can be clearly confirmed under a microscope.
2: Mold growth is observed with the naked eye, and the area of the growth part is less than 25% of the total area of the sample.
3: Mold growth is observed with the naked eye, and the area of the growth part is 25% or more and less than 50% of the total area of the sample.
4; Mycelium grows well, and the area of the growing part is 50% or more of the total area of the sample.
5; The growth of hyphae is intense and covers the entire surface of the material.

The composition of the coating agent is shown in Tables 9 to 10, and the physical characteristics of the film having the coating layer are shown in Tables 11 to 12.

As a result, the coating agent of the example was excellent in printability, had no unevenness on the surface, and was good, and exhibited excellent antibacterial properties.
Comparative Examples 1, 4 and 5 did not contain silver-supported zeolite, but did not show antibacterial properties. Further, Comparative Examples 2, 3 and 6 contained silver-supported zeolite, but the amount of fatty acid amide, which is an inhibitor of sedimentation, was less than a predetermined amount or was not blended, and the evaluation of the coated surface was low.
The same tendency was observed in Examples 6 to 10 and Comparative Examples 7 to 12 in which the resin system was changed. Further, also in Examples 11 to 15 and Comparative Examples 13 to 18 of the fixed-term inorganic composite type fungicide, if the amount of the fatty acid amide added as the antisettling agent is appropriate, the fungicide resistance is determined. It has become possible to achieve both coating surface evaluation.

Claims

It contains a binder resin (A), an antibacterial agent and / or an antifungal agent (B), an antisettling agent (C), and an organic solvent, and the antisettling agent (C) is used as the antibacterial agent and / or the antifungal agent. A coating agent for a paper base material or a plastic base material, which comprises 0.1 to 50.0% by mass with respect to (B).
The coating agent for a paper base material or a plastic base material according to claim 1, wherein the binder resin (A) contains a fibrous resin, a polyamide resin, a urethane resin, an acrylic resin, or a vinyl chloride resin.
The binder resin is a urethane resin / vinyl chloride resin, a urethane resin / fiber element resin, a polyamide resin / fiber element resin, an acrylic resin / fiber element resin, or a vinyl chloride resin / fiber element resin. The coating agent for a paper base material or a plastic base material according to claim 1 or 2, which is a combination selected from the resin.
The coating agent for a paper base material or a plastic base material according to any one of claims 1 to 3, wherein the antibacterial agent and / or the antifungal agent (B) is a silver-supported zeolite.
The coating agent for a paper base material or a plastic base material according to any one of claims 1 to 4, wherein the anti-precipitation agent (C) is fatty acid amide.
The coating agent for a paper base material or a plastic base material according to any one of claims 1 to 5, which contains an isocyanate compound (E).
A paper base material or a plastic base material obtained by coating a paper base material and a film with the coating agent according to any one of claims 1 to 6. It was
The paper base material or plastic base material according to claim 7, wherein the paper base material or plastic base material further has a printing ink layer.
Containers and packaging materials using the paper base material or plastic base material according to claim 7 or 8.