WO2021261261A1 - Coating agent for paper substrates or plastic substrates, and paper substrates, plastic substrates, containers, and packaging material that have coating layer of said coating agent - Google Patents

Abstract

Provided is a coating agent for paper substrates or plastic substrates that comprises a binder resin (A), a photocatalyst (B), and an organic solvent. The photocatalyst (B) contains a divalent copper compound and a titanium oxide containing crystalline rutile titanium oxide, the crystalline rutile titanium oxide exhibiting a full width at half maximum of 0.65° or less for the most intense diffraction peak attributed to rutile titanium oxide, in a Cu-Kα line X-ray diffraction pattern, which is obtained by plotting the intensity of the diffraction line with respect to the diffraction angle 2θ, the crystalline rutile titanium oxide content in the titanium oxide being at least 50 mol%, and the anatase titanium oxide content in the titanium oxide being less than 50 mol%. The coating agent contains 0.5-80 mass% of the photocatalyst (B) with respect to the total solid content of the coating agent.

Description

A coating agent for a paper base material or a plastic base material, and a paper base material, a plastic base material, a container and a 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 and antiviral functions are also desired, and antiviral (especially) antiviral as a countermeasure against viral infections such as new influenza, SARS (severe acute respiratory syndrome), and norovirus. Measures against virus inactivation) are urgently needed.
As a coating agent having antiviral performance, for example, an antiviral coating agent containing one or more oxides selected from silver, zinc and copper and a double salt of molybdenum oxide is known (for example, Patent Document 1). reference).

As a material having antiviral properties, for example, a photocatalyst is known, and for example, a cloth to which a material having antiviral properties such as a photocatalyst is adhered is known (see, for example, Patent Document 1). However, coating agents using photocatalysts are not yet known.

Japanese Unexamined Patent Publication No. 2018-172306 Japanese Unexamined Patent Publication No. 2017-155368

The present invention is to provide a coating agent for a paper base material or a plastic base material that can easily impart antiviral properties to a base material such as a plastic material, a molded product, a film base material, and a packaging material.

That is, the present invention contains a binder resin (A), a photocatalyst (B), and an organic solvent, and the photocatalyst (B) contains titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound. In the X-ray diffraction pattern in which the crystalline rutile-type titanium oxide plots the diffraction line intensity with respect to the diffraction angle 2θ by Cu—Kα rays, the half-value total width of the strongest diffraction peak corresponding to the rutile-type titanium oxide is 0.65 degrees or less. Titanium oxide is a photocatalyst in which the content of the crystalline rutyl-type titanium oxide in the titanium oxide is 50 mol% or more and the content of anatase-type titanium oxide is less than 50 mol%, and the total amount of the coating agent solid content is However, a coating agent for a paper base material or a plastic base material containing 0.5 to 80% by mass of the photocatalyst (B) is provided.

The present invention also provides a paper base material or a plastic base material obtained by coating the above-mentioned coating agent on a paper base material and a film.

The present invention also provides a container and a packaging material using the above-mentioned paper base material or plastic base material.

According to the present invention, antiviral properties can be easily imparted to base materials such as plastic materials, molded products, film base materials, paper base materials, and packaging materials by coating.

(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 nitrate ester obtained by reacting natural cellulose with nitric acid and substituting three hydroxyl groups in the 6-membered ring of anhydrous glucopyranose group in natural cellulose with nitric acid group. 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 dimerized fatty acid (dimeric 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 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-Butandiol, 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 pimelic 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 (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 include the 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 amount of the urethane 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.

(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.
Examples of 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)
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 (by 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.
A combination selected from urethane-based resin / vinyl chloride-based resin, urethane-based resin / fibrous-based resin, polyamide-based resin / fibrous-based resin, acrylic resin / fibrous-based resin, and binder resin (A) is preferable. The total content of the two resins in 100% by mass is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.

Furthermore, urethane-based resin / vinyl chloride-based resin, urethane-based resin / fiber-based resin, polyamide-based resin / fiber-based resin, and acrylic-based resin / fiber-based resin are 95/5 to 20/80 by mass ratio, respectively. Is preferable. 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 the 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, and 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 base materials or plastic base materials of the present invention. Is the most preferable.

(Photocatalyst (B))
The photocatalyst (B) is a photocatalyst containing titanium oxide containing crystalline rutyl-type titanium oxide and a divalent copper compound, and the crystalline rutile-type titanium oxide is a diffraction line with respect to a diffraction angle 2θ by Cu—Kα rays. In the X-ray diffraction pattern in which the intensity is plotted, the half-value total width of the strongest diffraction peak corresponding to rutile-type titanium oxide is titanium oxide of 0.65 degrees or less, and the content of the crystalline rutile-type titanium oxide in the titanium oxide. It is a photocatalyst having an amount of 50 mol% or more and an anatase-type titanium oxide content of less than 50 mol%.

By using a combination of rutile-type and highly crystalline crystalline rutile-type titanium oxide and a divalent copper compound, a photocatalyst with excellent antiviral properties in bright and dark places and organic compound decomposition in bright places (visible). A visible light responsive photocatalyst) having photocatalytic activity such as antiviral property can be obtained in the light region. Further, since the divalent copper compound is less likely to be discolored due to oxidation like the monovalent copper compound, discoloration over time can be suppressed.

In the present invention, the "bright place" means a place where visible light exists, and the "dark place" means a place where light does not exist.

Here, the photocatalytic activity means at least one selected from photo-induced degradability and photo-induced hydrophilization. Photo-induced degradability is the action of oxidatively decomposing organic substances adsorbed on the surface treated with titanium oxide, and photo-induced hydrophilicity is the hydrophilicity of the surface treated with titanium oxide that is easily compatible with water. It is an action to become. It is considered that this photoinduced hydrophilicity is caused by the increase of hydroxyl groups on the surface of titanium oxide due to the holes generated and diffused by photoexcitation.

The virus means a DNA virus and an RNA virus, but also includes a bacteriophage (hereinafter, may be abbreviated as "phage") which is a virus that infects bacteria.

Next, each component of the photocatalyst (B) will be described.
(Titanium oxide)
The titanium oxide used in the photocatalyst (B) contains crystalline rutile-type titanium oxide.

In the present invention, the crystalline rutile-type titanium oxide is an X-ray diffraction pattern in which the diffraction line intensity with respect to the diffraction angle 2θ by Cu—Kα rays is plotted, and the half-value full width of the strongest diffraction peak corresponding to the rutile-type titanium oxide is 0. It means titanium oxide of .65 degrees or less.

If the full width at half maximum is larger than 0.65 degrees, the crystallinity deteriorates and the antiviral property in the dark is not sufficiently expressed. From this point of view, the full width at half maximum is preferably 0.6 degrees or less, more preferably 0.5 degrees or less, still more preferably 0.4 degrees or less, still more preferably 0.35 degrees. ..

The content of crystalline rutile-type titanium oxide in titanium oxide (hereinafter, may be referred to as "rutileization rate") is 50 mol% or more. When the content is 50 mol% or more, the antiviral property of the obtained photocatalyst in a bright place and a dark place becomes sufficient, and the organic compound decomposing property in the bright place and particularly the visible light responsiveness are also sufficient. It becomes a thing. From this viewpoint, the rutileization rate is preferably 90 mol% or more, more preferably 94 mol% or more. This rutile formation rate is a value measured by XRD as described later.

From the above viewpoint, the content of anatase-type titanium oxide in titanium oxide (hereinafter, may be referred to as “anatase formation rate”) is preferably low, and the anatase formation rate is less than 50 mol%, preferably 10 mol. %, More preferably less than 7 mol%, still more preferably 0 mol% (ie, free of anatase-type titanium oxide). This anatase formation rate is also a value measured by XRD in the same manner as the rutile formation rate.

The specific surface area of titanium oxide is preferably 1 to 200 m ² / g. When it is 1 m ² / g or more, the specific surface area is large, so that the frequency of contact with viruses, fungi and organic compounds increases, and the obtained photocatalyst has antiviral properties in bright and dark places, organic compound degradability and antibacterial properties. Excellent in sex. On the other hand, when it is 200 m ² / g or less, the handleability is excellent. From these viewpoints, the specific surface area of titanium oxide is more preferably 3 to 100 m ² / g, further preferably 4 to 70 m ² / g, and particularly preferably 8 to 50 m ² / g. Here, the specific surface area is a value measured by the BET method by nitrogen adsorption.

Titanium oxide includes those produced by the vapor phase method and those produced by the liquid phase method, and either of them can be used, but titanium oxide produced by the vapor phase method is more preferable.

The gas phase method is a method of obtaining titanium oxide by a gas phase reaction with oxygen using titanium tetrachloride as a raw material. Titanium oxide obtained by the vapor phase method has a uniform particle size and at the same time has high crystallinity because it goes through a high temperature process during production. As a result, the obtained photocatalyst has good antiviral properties, organic compound decomposability and antibacterial properties in bright and dark places.

On the other hand, the liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing a liquid in which a titanium oxide raw material such as titanium chloride or titanyl sulfate is dissolved. Titanium oxide produced by the liquid phase method tends to have a low crystallinity of rutile and a large specific surface area. In this case, it may be calcined to obtain titanium oxide having optimum crystallinity and specific surface area. The vapor phase method is more preferable because it takes time and effort.

As titanium oxide, it is more advantageous to use commercially available titanium oxide as it is, considering the process of catalyst preparation.

(Divalent copper compound)
The photocatalyst (B) contains a divalent copper compound. This divalent copper compound alone does not have antiviral properties in bright and dark places, organic compound degradability in bright places, and visible light responsiveness, but by combining with the above-mentioned crystalline rutile-type titanium oxide, it is possible to make bright spots. And antiviral property in the dark, organic compound decomposition property in the light place, and visible light responsiveness are sufficiently expressed. Further, since the divalent copper compound has less discoloration due to oxidation or the like than the monovalent copper compound, the photocatalyst using this divalent copper compound suppresses the discoloration.

The divalent copper compound is not particularly limited, and examples thereof include one or two types of a divalent copper inorganic compound and a divalent copper organic compound.

Divalent copper Inorganic compounds include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate and copper ammonium chloride, copper pyrophosphate, and copper carbonate. 1 selected from the group consisting of an inorganic acid salt of divalent copper, a halide of divalent copper composed of copper chloride, copper fluoride and copper bromide, and a group consisting of copper oxide, copper sulfide, azurite, malakite and copper azide. Species or two or more species are mentioned.

Examples of the divalent copper organic compound include a divalent copper carboxylate. Examples of the carboxylate of divalent copper include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid. Copper, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, melitonic acid Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, acetylacetone copper, ethylacetate acetate, isokichi One selected from the group consisting of copper herbate, β-resorcylate copper, diacetate acetate copper, formyl succinate copper, salicylamine acid copper, bis (2-ethylhexanoic acid) copper, sebacate copper and naphthenate copper or Two or more types can be mentioned. Other divalent copper organic compounds are selected from the group consisting of oxine copper, acetylacetone copper, ethylacetoacetate copper, trifluoromethanesulfonate copper, phthalocyanine copper, copper ethoxydo, copper isopropoxide, copper methoxyde, and copper dimethyldithiocarbamate. One kind or two or more kinds are mentioned.

Among the above divalent copper compounds, preferably one or more of copper oxide, a halide of divalent copper, an inorganic acid salt of divalent copper and a carboxylate of divalent copper, for example, divalent copper. A halide, one or more of an inorganic acid salt of divalent copper and a carboxylate of divalent copper.

Further, examples of the divalent copper compound include a divalent copper compound represented by the following general formula (1).
Cu ₂ (OH) ₃ X (1)

In the general formula (1), X is an anion, preferably a halogen such as Cl, Br, I, a conjugate base of a carboxylic acid such as _{CH 3} COO, or an inorganic acid such as _{NO 3} , (SO ₄ ) _1/2. Conjugate base, or OH.

Of these divalent copper compounds, divalent copper inorganic compounds are more preferable, and copper oxide is further preferable, from the viewpoint of less impurities and economic viewpoint. Further, a divalent copper compound represented by the above general formula (1) is also preferable. The divalent copper compound may be anhydrous or hydrated.

The copper equivalent content of the divalent copper compound is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide. When it is 0.01 part by mass or more, the antiviral property, the organic compound decomposing property and the antibacterial property in a bright place and a dark place become good. Further, when the amount is 20 parts by mass or less, the surface of titanium oxide is prevented from being covered, the function as a photocatalyst (organic compound decomposability, antibacterial property, etc.) is satisfactorily exhibited, and the antiviral performance is improved with a small amount. It can be improved and is economical. From this viewpoint, the copper equivalent content of the divalent copper compound is more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of titanium oxide. Even more preferably, it is 0.3 to 10 parts by mass.

Here, the copper equivalent content of the divalent copper compound with respect to 100 parts by mass of this titanium oxide can be calculated from the charged amount of the raw material of the divalent copper compound and the raw material of titanium oxide. The copper equivalent content can also be specified by measuring the photocatalyst by ICP (inductively coupled plasma) emission spectroscopy, which will be described later.

As described above, the photocatalyst (B) contains titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound as essential components, but other optional components as long as the object of the present invention is not impaired. May be contained. However, from the viewpoint of improving the function as a photocatalyst and the antiviral performance, the content of the essential component in the photocatalyst (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and further. It is preferably 99% by mass or more, and more preferably 100% by mass.

The photocatalyst (B) can be produced by carrying out a mixing step of mixing titanium oxide containing crystalline rutile-type titanium oxide and a raw material for a divalent copper compound. Further, a heat treatment step of heat-treating the mixture obtained by this mixing step may be further carried out to obtain a photocatalyst. A photocatalyst can also be obtained by suspending titanium oxide in an aqueous solution of a copper compound and adsorbing it. Specifically, the photocatalyst (B) can be produced by the method described in Japanese Patent No. 5343176.

When the primary particle size of the photocatalyst (B) is in the range of about 200 to 400 nm and the secondary particle size is about 3 to 10 μm, it is preferable because it can be dispersed in the coating agent and has excellent photocatalytic activity such as antiviral property.
The method for measuring the primary particle size is a value measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM).
The photocatalyst (B) is preferably contained in an amount of 0.5% by mass or more based on the total solid content of the coating agent for paper base material or plastic base material of the present invention in order to exhibit photocatalytic activity such as antiviral property. It is preferably contained in an amount of 1% by mass or more, preferably 5% by mass or more, and preferably 10% by mass or more. On the other hand, in order to prevent deterioration of adhesion and abrasion resistance, the photocatalyst (B) is preferably contained in an amount of 80% by mass or less based on the total solid content of the coating agent for paper base material or plastic base material of the present invention. It is preferably contained in an amount of 5% by mass or less, preferably 55% by mass or less, preferably 50% by mass or less, preferably 30% by mass or less, and most preferably 20% by mass or less.

(Organic solvent (C))
The organic solvent (C) used in the coating agent for a paper base material or a plastic base material of the present invention is not particularly limited, but is an aromatic hydrocarbon-based solvent such as toluene, xylene, Solbesso # 100, and Solbesso # 150. Organic solvents, hexane, methylcyclohexane, heptane, octane, decane and other aliphatic hydrocarbon organic solvents, methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate and the like. Examples thereof include various ester-based organic solvents. Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl can be used as water-mixable organic solvents. 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 work hygiene during printing and 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 mixed solution of isopropyl alcohol / ethyl acetate / methoxypropanol is more preferable from the viewpoint of solubility in polyurethane resin and nitrified cotton. 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 can be produced by dissolving and / or dispersing the binder resin (A), the photocatalyst (B), or the like in an organic solvent. As the disperser, commonly used examples such as a roller mill, a ball mill, a pebble mill, an attritor, and a sand mill 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, the coating layer formed by using the coating agent has a structure in which a part of the photocatalyst (B) is exposed. Cheap. Therefore, the coating layer in the present invention can maximize the antiviral function. 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 thereof 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 or the like obtained by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method or 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. 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 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 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) as the coating method, 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)
The organic solvent type 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. It is useful as an ink for gravure printing using a gravure printing plate according to the above, 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 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 the 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. Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketone-based solvents such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl can be used as water-mixable organic solvents. 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.

Organic solvent-based liquid printing inks should also contain waxes, chelate crosslinkers, extender pigments, leveling agents, defoamers, plasticizers, infrared absorbers, UV absorbers, fragrances, flame retardants, etc., as needed. 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, anthraquinone, 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, Phthalussinin 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 exhibits 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, chrome yellow, cadmium yellow, cadmium red, ultramarine, navy 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 chrome yellow or non-leafing is used 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 flexographic printing using a flexographic 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 the 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- Styrene-acrylic acid resin such as acrylic acid alkyl ester copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene-acrylic acid copolymer; vinylnaphthalene-maleic acid copolymer; vinyl acetate-ethylene homoweight Compounds, 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. Salt 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 base material, 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, stearic acid 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 with reference to Examples. Hereinafter, both "part" and "%" are based on the mass standard.
The weight average molecular weight (in terms of polystyrene) was measured by GPC (gel permeation chromatography) in the present invention using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: Uses 4 TSKgelGMHR-N manufactured by Tosoh Corporation.
Column temperature: 40 ° C.
Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
Flow rate: 1.0 ml / min.
Sample concentration: 0.4% by mass.
Sample injection volume: 100 microliters.
Detector: Differential refractometer.
The viscosity was measured at 25 ° C. with a Tokimec B-type viscometer.

The acid value of the wax indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the wax solid content, and each dried resin wax is subjected to potassium hydroxide according to JIS K2501. -Calculated from potentiometric titration with an ethanol solution.

(Adjustment of nitrocellulose resin solution N)
Industrial vitrified cotton L1 / 8 (nitrocellulose, solid content 30%, viscosity 1.6-2.9% at a solution concentration of 25.0% by JIS K-6703, manufactured by Taihei Chemicals Limited) 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 resin solution N.

(Preparation of Cellulose Ester Resin Solution C1)
20 parts of cellulose acetate propionate CAP482-0.5 (manufactured by Eastman Chemical Co., Ltd.) is mixed with a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methylcyclohexane (25/25/13/10 by weight). 80 parts were added and mixed well to prepare a cellulose ester resin solution C1.

(Preparation of Cellulose Ester Resin Solution C2)
20 parts of cellulose acetate butyronate CAB381-0.5 (manufactured by Eastman Chemical Co., Ltd.) is mixed with a mixed solution of isopropyl alcohol / ethyl acetate / normal propyl acetate / methylcyclohexane (25/25/13/10 by weight). 80 parts were added and mixed well to prepare a cellulose ester resin solution C2.

(Preparation of dimer acid-modified polyamide resin solution Pa)
100 parts of dimer acid (Haridimer 270S; manufactured by Harima Kasei Co., Ltd.), tall oil fatty acid (Hartol FA-1; Harima Kasei (Harima Kasei)) in a four-necked flask equipped with a stirrer, thermometer, recirculation cooler and nitrogen gas introduction tube. (Manufactured by Co., Ltd.) 1 part, 5 parts of sebacic acid, 10 parts of ethylenediamine, 5 parts of hexamethylenediamine, and 0.24 parts of triphenylphosphine were added to create a nitrogen atmosphere in the system, and further, stirring for homogenization under a nitrogen stream was performed. While slowly raising the temperature to 200 ° C. Subsequently, dehydration condensation was carried out at 200 ° C. for 5 hours with stirring, and a dimer acid-modified polyamide resin derived from a toll fatty acid having a solid content of 20%, a softening point of 123 ° C., an amine value of 2, an acid value of 8, and a number average molecular weight of 10,000. Solution Pa was obtained.

(Preparation of polyurethane resin solution Pu)
162.58 parts of Mn2,000 polyester polyol (DIC: Polylite OD-X-2044) obtained from adipic acid and neopentyl glycol in four flasks equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube. And polypropylene glycol (manufactured by Mitsui Chemicals, Actol D-1000) 40.65 parts, isophorone diisocyanate 66.23 parts, ethyl acetate 50 parts, DICNAME 425 (manufactured by DIC) 0.03 parts, and 75 ° C. under a nitrogen stream. Was reacted for 3 hours. Then, 2.17 parts of 2-butyl-2-ethylpropanediol having a number average molecular weight (Mn) of 160.3 was added, and the mixture was further reacted at 75 ° C. for 3 hours. After completion of the reaction, 200 parts of normal propyl acetate was added to dilute the reaction solution. After cooling the reaction solution to 45 ° C. or lower, 200 parts of isopropyl alcohol was added. The reaction mixture was kept at about 35 to 40 ° C., 23.53 parts of isophorone diamine was dissolved in 100 parts of ethyl acetate and added dropwise, and the mixture was reacted at 50 ° C. for 3 hours under a stirring frame. Then, 4.84 parts of cyclohexylamine was added and reacted at 50 ° C. for 30 minutes under a stirring frame. Finally, 150 parts of ethyl acetate was added to obtain a polyurethane resin solution (Pu) having a non-volatile content of 30.0%, a Gardner viscosity V (25 ° C.) and Mw 40,000.

(Adjustment of acrylic resin solution Ac)
A solid acrylic resin (Dianal BR-90 manufactured by Mitsubishi Chemical Corporation) was stirred and dissolved with ethyl acetate to prepare a 30% solution, which was used as an acrylic resin solution Ac.

(Adjustment of vinyl chloride vinyl acetate copolymer resin solution Ev)
A 25% solution of vinyl chloride vinyl acetate copolymer resin having a hydroxyl group (resin monomer composition is by mass%, vinyl chloride / vinyl acetate / vinyl alcohol = 92/3/5, hydroxyl value (mgKOH) = 64) is prepared with ethyl acetate. This was designated as a vinyl chloride vinyl acetate copolymer resin solution Ev.

<Preparation of photocatalyst>
First, the properties of the titanium oxide raw material (manufactured by Showa Denko Ceramics Co., Ltd.) used were measured as follows.

(BET specific surface area)
The BET specific surface area of the titanium oxide raw material was measured using a fully automatic BET specific surface area measuring device "Macsorb, HM model-1208" manufactured by Mountech Co., Ltd.
(Rutile content (rutileization rate) and crystallinity (full width at half maximum) in titanium oxide raw material)
The content (rutile formation rate) and crystallinity (half-value full width) of rutile-type titanium oxide in the titanium oxide raw material were measured by powder X-ray diffraction method.

That is, for the dried titanium oxide raw material, using PANalytical's "X'pertPRO" as a measuring device, using a copper target, and using a Cu-Kα1 wire, a tube voltage of 45 kV, a tube current of 40 mA, and a measurement range of 2θ = 20. X-ray diffraction measurement was performed under the conditions of ~ 100 deg, sampling width 0.0167 deg, and scanning speed 3.3 deg / min.

The peak height (Hr) corresponding to the rutile type crystal, the peak height (Hb) corresponding to the brookite type crystal, and the peak height (Ha) corresponding to the anatase type crystal were obtained, and titanium oxide was calculated by the following formula. The content of rutile-type titanium oxide (rutileization rate) in the rutile type was determined.

Rutileization rate (mol%) = {Hr / (Ha + Hb + Hr)} × 100
In addition, the content of anatase-type titanium oxide (anatase conversion rate) and the content of brookite-type titanium oxide (brookite conversion rate) in titanium oxide were calculated by the following formulas, respectively.

Anatase formation rate (mol%) = {Ha / (Ha + Hb + Hr)} × 100
Brookite conversion rate (mol%) = {Hb / (Ha + Hb + Hr)} x 100
In the X-ray diffraction pattern obtained by the above X-ray diffraction measurement, the strongest diffraction peak corresponding to rutile-type titanium oxide was selected, and the full width at half maximum was measured.

(Primary particle size)
For the average primary particle size (DBET) (nm), the specific surface area S (m ² / g) of titanium oxide was measured by the BET one-point method, and the following formula DBET = 6000 / (S × ρ).
Calculated from. Here, ρ indicates the density of titanium oxide (g / cm ³ ).

Table 1 shows the measurement results of the titanium oxide raw material used.

(Manufacturing Example 1)
Distilled water 100mL to suspend the 6 g (manufactured by Showa Denko Ceramics Co.) titanium oxide material (100 parts by _{weight), CuCl 2 · 2H 2 O} ( Kanto Chemical of 0.0805G (0.5 part by weight of copper equivalent) (Manufactured by Co., Ltd.) was added and stirred for 10 minutes. A 1 mol / L sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) aqueous solution was added so that the pH became 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry. The slurry was filtered, the obtained powder was washed with pure water, dried at 80 ° C., and crushed with a mixer to obtain a sample (photocatalyst).

The obtained sample (photocatalyst) was heated in a hydrofluoric acid solution to completely dissolve it, and the extract was quantified by ICP emission spectroscopic analysis. As a result, copper ions were 0.5 parts by mass with respect to 100 parts by mass of titanium oxide. That is, the total amount of the copper ions of the feed (CuCl ₂ · 2H ₂ O derived) were supported on the surface of titanium oxide.

The sample (photocatalyst) obtained in Production Example 1 was analyzed by the following method.

(Rutilated titanium oxide content (rutileization rate) and crystallinity (full width at half maximum))
With respect to the sample (photocatalyst) obtained in Production Example 1, the content (rutileization rate) and crystallinity (half-value full width) of rutile-type titanium oxide in titanium oxide were measured by powder X-ray diffraction method.

That is, the powder obtained by grinding the dried photocatalyst in a mortar was used as a sample. For this sample, using PANalytical's "X'pertPRO" as a measuring device, using a copper target, and using a Cu-Kα1 wire, a tube voltage of 45 kV, a tube current of 40 mA, a measurement range of 2θ = 20 to 100 deg, and a sampling width of 0. X-ray diffraction measurement was performed under the conditions of 1.0167 deg and a scanning speed of 3.3 deg / min.

The peak height (Hr) corresponding to the rutile type crystal, the peak height (Hb) corresponding to the brookite type crystal, and the peak height (Ha) corresponding to the anatase type crystal were obtained, and titanium oxide was calculated by the following formula. The content of rutile-type titanium oxide (rutileization rate) in the rutile type was determined.

Rutileization rate (mol%) = {Hr / (Ha + Hb + Hr)} × 100
In the X-ray diffraction pattern obtained by the above X-ray diffraction measurement, the strongest diffraction peak corresponding to rutile-type titanium oxide was selected, and the full width at half maximum was measured.

(Identification of divalent copper compound)
The divalent copper compound present in the sample (photocatalyst) obtained in Production Example 1 was identified by X-ray diffraction measurement using the above measuring device and measuring conditions. The results are shown in Table 2.

[Examples and Comparative Examples]
According to the formulation shown in Table 3, the binder resin, the photocatalyst, and the organic solvent were uniformly mixed with a bead mill to obtain a coating agent composition.

<Manufacturing of a laminated body having a coating layer>
[Creating a gravure coating]
The viscosity of the obtained coating agents of Examples and Comparative Examples was adjusted to 16 seconds (25 ° C.) with Zahn Cup # 3 (manufactured by Rigosha) using any of the mixed solvents A to D shown in the table, and the plate depth was adjusted. Examples 1 to 4 are biaxially stretched polypropylene films (OPP films), Examples 5 to 9 are polyethylene terephthalate films (PET films), and Examples 10 to are coated balls by a gravure calibrator equipped with a 35 μm gravure plate. The laminate printed on paper was left for one day to prepare a laminate for evaluation.

[Flexographic coating creation]
The viscosity of the obtained coating agents of Examples and Comparative Examples was adjusted to 20 seconds (25 ° C.) with Zahn Cup # 3 (manufactured by Rigosha) using any of the mixed solvents A to D shown in Table 3, and 120 wires were used. The laminate printed on coated cardboard and PET film was left for one day by a flexographic calibrator equipped with a / cm anilox roll to prepare a laminate for evaluation.

In Table 3, the numbers are parts.

Using the obtained laminate (base material having a coating layer), adhesion, abrasion resistance, and antiviral property were evaluated.

[Evaluation item 1: Adhesion]
A cellophane tape (Nichiban 12 mm width) was attached to the printed surface, and the appearance of the printed film when the tape was rapidly peeled off was visually determined in the following five stages.
When printing on coated cardboard 5: Paper peeling, no peeling between coating agent layers 4: Paper peeling, peeling between coating agent layers less than 25 3: Paper peeling, peeling between coating agent layers 25-75%
2: Paper peels off, peeling between coating agent layers is 75% or more 1: Paper does not peel off When printing on film 5: Coating agent does not peel off from film 4: Coating agent peeling is less than 25% 3: Coating agent peeling 25-50%
2: 50-75% of coating agent peeling
1: Coating agent peeling is 75-100%

[Evaluation item 2: Friction resistance]
The friction resistance of the produced printed matter was evaluated using a robust Gakushin tester. As the friction element, copy paper was used, and the state of the surface of the printed matter after a load of 500 g and 100 reciprocations was visually determined in the following five stages.

5: The printed surface has not changed 4: There are few scratches on the printed matter surface 3: There are many scratches on the printed matter surface 2: Part of the coating agent has peeled off and the base material is visible 1: The coating agent has peeled off and the base material Is only

(Evaluation item 3 Evaluation of antiviral property)
An anti-phage virus test (see JIS R1756) was performed on the evaluation printed matter obtained above.
1) As for the light irradiation conditions, the light of the white fluorescent lamp was cut off from ultraviolet rays by the N113 filter, and the illuminance was set to 1000 lux.
2) A 100 μL Qβ phage solution having a known concentration was dropped on a 5 cm × 5 cm evaluation printed matter, and then sandwiched between 5 cm × 5 cm glass plates.
3) Samples irradiated with light for 2 hours were collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, applied to an agar medium, and evaluated by counting the number of colonies after culturing. The antiviral property was evaluated by the degree of inactivation of Qβ phage, and the inactivation degree -2 to -5 was evaluated as having antiviral property.
The degree of inactivation is -1 for 90%, the degree of inactivation is -2 for 99%, and the degree of inactivation is -3 for 99.9%, indicating that the antiviral property is high. The detection limit is inactivation degree -5.

Tables 4 to 6 show the evaluation results of the laminate using the compositions of Examples and Comparative Examples.
The blanks indicate unblended.

The raw material names in the table are as follows.
Chlorinated polyolefin solution Ep: Supercron 360T (manufactured by Nippon Paper Industries, Ltd.)
Hydrophobic silica: Syricia 350D (manufactured by Fuji Silysia Chemical Ltd.)
Wax 1: Mitsui High Wax 220MP (manufactured by Mitsui Chemicals, Inc.)
Wax 2: Amide AP-1 (manufactured by Mitsubishi Chemical Corporation)
Plasticizer 1: Eposizer W-100EL (manufactured by DIC Corporation)
Plasticizer 2: ATBC
Chelating agent: Olga Chix TC-100 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
Polyester: Barnock D-50-75 (manufactured by DIC Corporation)

From the above results, the coating agent of the present invention can impart good antiviral properties to these substrates by a simple method, that is, simply by applying it to a paper substrate or a plastic substrate, and it is possible to impart good antiviral properties to these substrates. It has become clear that it is possible to provide sex base materials, packaging materials, containers, etc. In addition, the coating agent of the present invention can exhibit sufficient antiviral properties while maintaining adhesion and abrasion resistance.

Claims (6)

1. Containing a binder resin (A), a photocatalyst (B), and an organic solvent,
   The photocatalyst (B) contains titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound.
   In the X-ray diffraction pattern in which the crystallized rutile-type titanium oxide plots the diffraction line intensity with respect to the diffraction angle 2θ by Cu—Kα rays, the half-value total width of the strongest diffraction peak corresponding to the rutile-type titanium oxide is 0.65 degrees or less. Is titanium oxide
   A photocatalyst in which the content of the crystalline rutile-type titanium oxide in the titanium oxide is 50 mol% or more and the content of the anatase-type titanium oxide is less than 50 mol%.
   Coating agent A coating agent for a paper base material or a plastic base material, which comprises 0.5 to 80% by mass of the photocatalyst (B) with respect to the total amount of solid content.
2. 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.
3. Claim 1 or claim 1, wherein the binder resin is a combination selected from a urethane-based resin / vinyl chloride-based resin, a urethane-based resin / fiber-based resin, a polyamide-based resin / fiber-based resin, and an acrylic resin / fiber-based resin. 2. The coating agent for a paper base material or a plastic base material according to 2.
4. 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 3.
5. The paper base material or plastic base material according to claim 4, wherein the paper base material or plastic base material further has a printing ink layer.
6. A container or packaging material using the paper base material or plastic base material according to claim 4 or 5.