JP2023012571A - Antibacterial coating agent and printed matter using the same - Google Patents

Abstract

To provide a coating agent which has good antibacterial property and printability, adhesion to a base material, friction resistance, heat resistance and blocking resistance to a base material, and has antibacterial property even after friction is added to a coating layer after coating agent printing.SOLUTION: An antibacterial coating agent contains a binder resin, an organic solvent and silver-zirconium phosphate particles, wherein the binder resin contains a set of resins composed of a combination of a polyurethane resin and a vinyl chloride-based resin or a combination of a polyamide resin and a nitrocellulose resin, and 0.05-0.9 mass% of the silver-zirconium phosphate particles is contained in the total mass of the antibacterial coating agent.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an antibacterial coating agent and its printed matter.

More specifically, it has good antibacterial properties and printability, good adhesion to substrates, abrasion resistance, heat resistance, and blocking resistance, and furthermore, after applying friction to the coating layer after printing the coating agent The present invention relates to a coating agent having antibacterial properties even if there is.

BACKGROUND ART In recent years, product packages and other packages are generally printed for decoration and surface protection. In addition, depending on the quality of printing, such as design, beauty, and luxury of printed matter, consumers will be motivated to purchase, and it is of great industrial value.

On the other hand, with the diversification of packages and the sophistication of packaging technology, printing inks are required to have high quality and performance. Examples of printing ink include flexographic ink, offset ink, gravure printing ink, etc. Among them, gravure printing ink is often used from the viewpoint of productivity because of its favorable printing speed.

The performance of gravure printing ink includes not only the quality of printing performance, but also the adhesion to the substrate, the blocking resistance to prevent the ink from set-off or adhesion to the back of the substrate when it is rolled up after printing, and the printing performance. Various resistances are required, such as anti-blocking properties so that layers do not adhere to each other, abrasion resistance so that printed surfaces are not damaged, heat resistance during bag making, oil resistance against oils and fats, and the like.

In addition, due to the recent rise in sanitation, bacteria, fungi, etc. have been found in food and pharmaceutical factories, buildings such as hospitals and nursing homes, food kitchen utensils, medical utensils, medical equipment, etc., and even general household items. Antibacterial agents, antiviral agents, antifungal agents, disinfectants, etc. are used for the purpose of preventing the spread and infection of the disease. Recently, however, various infectious diseases have emerged, and there is a growing desire to prevent infection from bacteria and viruses. Therefore, not only in public facilities but also in general households, a technique for imparting antibacterial and antiviral properties to various members is desired.

In the prior art, organic or inorganic antibacterial agents have been proposed as solutions to these problems. For example, organic iodine antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, thiazole antibacterial agents, benzimidazole antibacterial agents, isophthalonitrile antibacterial agents, phenol antibacterial agents, triazine antibacterial agents, bromine antibacterial agents antibacterial agents, quaternary ammonium salt antibacterial agents, organometallic antibacterial agents, and antibacterial materials in which metal ions are supported on substances such as zeolite and silica gel, and antibacterial coating agents using these have been developed. (Patent Documents 1 to 3). However, the variety of compounds that exhibit antibacterial properties is limited, and new materials that exhibit antibacterial properties are in demand.
In addition, in coated objects, the durability of the antibacterial effect is poor after being touched and rubbed many times in daily life, and the printability is poor in printing on substrates with a printing machine. I had a case.

Japanese Patent No. 6801137 JP 2017-39905 A JP 2017-137481 A

The present invention has good antibacterial properties and printability, good adhesion to substrates, abrasion resistance, heat resistance, and blocking resistance to substrates, and furthermore, the coating layer after printing of the coating agent is rubbed. To provide a coating agent having antibacterial properties even after being added.

As a result of extensive studies, the present inventors have found that the above problems can be solved by using the "antibacterial and antiviral coating agent" described below, and have completed the present invention.

That is, the present invention provides an antibacterial coating agent containing a binder resin, an organic solvent and silver-zirconium phosphate particles,
The binder resin comprises at least one combination of a polyurethane resin and a vinyl chloride resin, or a combination of a polyamide resin and a nitrocellulose resin,
It relates to an antibacterial coating agent containing 0.05 to 0.9% by mass of the silver-zirconium phosphate particles in the total mass of the antibacterial coating agent.

The present invention also relates to the above antibacterial coating agent, which further contains a chlorinated polyolefin resin.

The present invention also relates to the above antibacterial coating agent, which further contains fatty acid amide and/or hydrocarbon wax particles.

The present invention also relates to the above antibacterial coating agent, which further contains an extender pigment and/or fine resin particles.

The present invention also relates to a printed material having a printed layer containing the above antibacterial coating agent on a substrate.

According to the present invention, antibacterial properties and printability are good, adhesion to substrates, abrasion resistance, heat resistance, and blocking resistance to substrates are good, and furthermore, the coating layer after printing the coating agent is rubbed. It has become possible to provide a coating agent having antibacterial properties even after addition.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of embodiments of the present invention, and the present invention does not exceed the gist thereof. Content is not limited.

In the following description, "antibacterial coating agent" may be expressed as "antibacterial coating agent composition,""coating agent composition," or "coating agent." Moreover, the layer obtained by printing the antibacterial coating agent may be referred to as "antibacterial coat layer" or "coat layer". In addition, "printed matter" may be referred to as "coating agent printed matter", but they have the same meaning.
In addition, when it is used as a laminate or a packaging bag, the outermost surface becomes an antibacterial coating layer. May serve as a surface protective layer. "Parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

<Polyurethane resin>
The polyurethane resin used in the present invention can be synthesized, for example, by the methods described in JP-A-2013-256551 and JP-A-2016-043600. It is a polyurethane resin having urethane bonds obtained by reaction with isocyanate. Also, if necessary, the chain may be extended through a urea bond formed by the remaining isocyanate and polyamine.

(polyol)
The polyol preferably has an average of about 1.7 to 2.3 hydroxyl groups in one molecule, and more preferably has an average of 2 hydroxyl groups. Polyols include polyether polyols such as polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, etc.
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentadiol, methylpentadiol, hexadiol, octanediol, nonanediol , methyl nonanediol, diethylene glycol, triethylene glycol, dipropylene glycol, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimeline Acid, azelaic acid, sebacic acid, dibasic acid such as dimer acid, or polyester polyols which are dehydration condensation products with these anhydrides,
polycarbonate polyols, polybutadiene glycols, polyols obtained by adding ethylene oxide or propylene oxide to bisphenol A,
Various known polyols such as dimer diols, castor oil polyols, and hydrogenated castor oil polyols can be used.

Polyols may be used alone or in combination of two or more. The number average molecular weight of the polyol is 300 or more, preferably 500 to 6,000, more preferably 1,000 to 3,000, so that the solubility of the polyurethane resin and the blocking resistance to the substrate can be maintained. Among them, it is preferable to use at least one polyol selected from polyester polyols, polyether polyols and polycarbonate polyols. Moreover, the polyol may have a biomass-derived compound or raw material (biomass raw material) as a constituent element.

In the present invention, among polyols, polyester polyols are preferred from the viewpoint of adhesion to substrates. Moreover, when two or more polyols are used in combination, it is more preferable that the polyester polyol is contained in an amount of 40% by mass or more based on the total mass of the polyols, from the viewpoint of adhesion to the substrate and blocking resistance.

(aliphatic diol)
The polyol that constitutes the polyurethane resin preferably contains an aliphatic diol. An embodiment using the aliphatic diol is, for example, a structural unit derived from an aliphatic diol having a molecular weight of 180 or less, and two hydroxyl groups represented by the following general formula (1) form a urethane bond with an isocyanate compound. In this case, it does not mean an aliphatic diol constituting a polyol such as a polyester polyol. In addition, the polyester polyol may separately contain a structural unit composed of the aliphatic diol, and the use of such a polyester polyol is not excluded from the present invention.

General formula (1)

-NHCOO-R ¹ -OCONH-

(In the formula, R ¹ represents a substituted or unsubstituted alkylene group.)
More preferably, the aliphatic diol has a molecular weight of 130 or less. More specifically, the molecular weight of the alkylene group is preferably 140 or less, more preferably 100 or less. The alkylene group may have an alkyl group as a substituent.

Aliphatic diols include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. , 1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, branched diols such as methylnonanediol, Alicyclic diols such as cyclohexanedimethanol, cyclohexanediol, and the like can be mentioned, and a plurality of diols may be used in combination. Among them, an aliphatic diol having an alkyl group having 1 to 6 carbon atoms as a substituent is preferable because it has excellent adhesiveness to a substrate and improves the solubility of urethane, thereby improving the printability. More specifically, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, and neopentyl glycol are preferred. used.

Structural units derived from aliphatic diols having a molecular weight of 180 or less increase the urethane bond density and impart crystallinity and cohesion, while structural units derived from polyols contribute to flexibility and adhesiveness. Therefore, both blocking resistance and adhesion to a substrate can be achieved, and oil resistance is improved. The content of the aliphatic diol-derived structural units (excluding structural units contained in the polyol) in the total amount of the polyol-derived structural units is 10 to 60% by mass, preferably 20 to 40% by mass. When the amount is 10% by mass or more, the cohesive force of the urethane bond obtained by reacting with the isocyanate is improved, and the anti-blocking property to the anti-fogging film is excellent. When it is 60% by mass or less, the solubility of the polyurethane resin in solvents can be maintained satisfactorily.

Other polyol components include aromatic diols and aliphatic diols having a molecular weight exceeding 180, and these may be used in combination.

Diisocyanates are preferably used as polyisocyanates. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- aromatic diisocyanates such as phenylene diisocyanate, 1,4-phenylene diisocyanate and tolylene diisocyanate; aliphatic diisocyanates, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, Examples include alicyclic diisocyanates such as m-tetramethylxylylene diisocyanate, and dimer diisocyanates obtained by converting the carboxyl groups of dimer acids into isocyanate groups. Among them, isophorone diisocyanate and hexamethylene diisocyanate are preferred.

In order to obtain the polyurethane resin used in the present invention, the reaction molar ratio of NCO derived from polyisocyanate and OH containing polyol and aliphatic diol (NCO molar equivalent/OH molar equivalent) is 0.5 or more and 2 or less, preferably The reaction can be carried out so that the ratio is 1.05 or more and 3 or less, and then, if necessary, chain extension can be performed with the polyamine described above, and a reaction terminator can also be used to prevent excessive reaction.

The urethanization reaction may be carried out in an organic solvent or without a solvent. When an organic solvent is used, it may be appropriately selected from the viewpoint of temperature and viscosity during the reaction and control of side reactions. Further, when the urethanization reaction is carried out without a solvent, it is desirable to raise the temperature so as to obtain a sufficiently agitable viscosity in order to obtain a uniform polyurethane resin. The urethanization reaction is desirably carried out for 10 minutes to 5 hours, and the end point of the reaction is determined by viscosity measurement, NCO-derived peak by IR measurement, NCO % measurement by titration, and the like.

Polyamines used for chain extension are preferably aliphatic diamines such as ethylenediamine, 1,4-butanediamine, isophoronediamine and aminoethylethanolamine. Glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and triethylene glycol can also be used as chain extenders.
The reaction terminator includes monoalcohols such as methanol and ethanol, alkylamines such as n-propylamine, n-butylamine and di-n-butylamine, and alkanolamines such as monoethanolamine and diethanolamine.

The polyurethane resin may or may not have a urea bond. The production method in the case of having a urea bond is not particularly limited, but the number of isocyanate groups of the prepolymer having an isocyanate group at the end obtained by reacting an aliphatic diol and a polyol and a polyisocyanate is set to 1. The total number of amino groups in the chain extender and reaction terminator is preferably within the range of 0.5 to 1.3.

The polyurethane resin preferably has a weight average molecular weight of 8,000 to 80,000, more preferably 10,000 to 60,000. It is preferable that the glass transition temperature is 0° C. or lower. -40°C to -5°C is more preferred, and -35 to -10°C is even more preferred. This is because the affinity with the vinyl chloride resin is improved.
Further, it preferably has an amine value and/or a hydroxyl value of a polyurethane resin, and the amine value is preferably 0.5 to 20 mgKOH/g, more preferably 1 to 15 mgKOH/g. Also, the hydroxyl value is preferably 0.5 to 30 mgKOH/g, more preferably 1 to 20 mgKOH/g. Within the above range, the adhesiveness to the substrate is improved, and the action with the silver-zirconium phosphate particles facilitates the expression of antibacterial properties.

<Vinyl chloride resin>
The vinyl chloride resin used in the present invention is not particularly limited as long as it contains structural units derived from vinyl chloride and structural units derived from other monomers. Among them, vinyl chloride-vinyl acetate copolymer resin is preferable.

(vinyl chloride-vinyl acetate copolymer resin)
A vinyl chloride-vinyl acetate copolymer resin is obtained by copolymerizing a vinyl chloride monomer and a vinyl acetate monomer. As for the molecular weight, a weight average molecular weight of 5,000 to 100,000 is preferable, and 20,000 to 70,000 is more preferable. The structure derived from the vinyl acetate monomer in 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer resin is preferably 1 to 30% by mass, and the structure derived from the vinyl chloride monomer is preferably 70 to 95% by mass. . In this case, the solubility in organic solvents is improved, and the adhesiveness to the substrate and the physical properties of the coat layer are improved. Moreover, it preferably has a hydroxyl group, and can be obtained by further using vinyl alcohol in the copolymerization or by partially saponifying vinyl acetate. The monomer ratio of vinyl chloride, vinyl acetate and vinyl alcohol affects the properties of the resin film and resin dissolution behavior. and vinyl alcohol imparts good solubility in polar solvents. The vinyl chloride-vinyl acetate copolymer resin preferably has a hydroxyl value of 50 to 180 mgKOH/g, more preferably 70 to 160 mgKOH/g. Also, the glass transition temperature is preferably 50°C to 90°C.

The combination of the polyurethane resin and the vinyl chloride resin functions as a binder resin. It is preferable that the total amount of the urethane resin and the vinyl chloride resin is 60% by mass in the total amount of the binder resin. It is still more preferable to contain 80% by mass. This is because the adhesiveness to the substrate is improved.
Furthermore, it is preferable that the solid content mass ratio of the polyurethane resin and the vinyl chloride resin (polyurethane resin/vinyl chloride resin) is 95/5 to 50/50. This is because the adhesiveness to the substrate, anti-blocking property, antibacterial property, and printability are improved at this compounding ratio and combination.

<Polyamide resin>
The polyamide resin used in the present invention is not limited to the following, but is preferably an organic solvent-soluble thermoplastic polyamide obtained by polycondensation of a polybasic acid and a polyvalent amine. In particular, it is preferably a polyamide resin containing a reaction product of an acid component containing a polymerized fatty acid and/or a dimer acid and an aliphatic and/or aromatic polyamine, and further containing a portion of primary and secondary monoamines. is preferred.

Polybasic acids used as raw materials for polyamide resins include, but are not limited to, adipic acid, sebacic acid, azelaic acid, phthalic anhydride, isophthalic acid, suberic acid, glutaric acid, fumaric acid, and pimeline. acid, oxalic acid, malonic acid, succinic acid, maleic acid, terephthalic acid, 1,4-cyclohexyldicarboxylic acid, trimellitic acid, dimer acid, hydrogenated dimer acid, polymerized fatty acids, etc. Among them, dimer acid or polymerized A polyamide resin containing a structure derived from a fatty acid as a main component (50% by mass or more in the polyamide resin) is preferred. Here, the polymerized fatty acid is obtained by a cyclization reaction of an unsaturated fatty acid or the like, and includes a monobasic fatty acid, a dimerized polymerized fatty acid (dimer acid), a trimerized polymerized fatty acid, and the like. Fatty acids constituting the dimer acid or polymerized fatty acid are preferably derived from natural oils such as soybean oil, palm oil and rice bran oil, and are preferably obtained from oleic acid and linoleic acid.
A monocarboxylic acid can also be used together with a polybasic acid. Monocarboxylic acids used in combination include acetic acid, propionic acid, lauric acid, palmitic acid, benzoic acid, and cyclohexanecarboxylic acid.

Polyamines include polyamines, primary or secondary monoamines, and the like. Examples of polyamines used in polyamide resins include aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine and methylaminopropylamine, and aliphatic polyamines such as diethylenetriamine and triethylenetetramine. , cyclohexylene diamine, isophorone diamine, and the like. Examples of araliphatic polyamines include xylylenediamine, and examples of aromatic polyamines include phenylenediamine and diaminodiphenylmethane. Further, primary and secondary monoamines include n-butylamine, octylamine, diethylamine, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, and the like.

The weight average molecular weight of the polyamide resin is preferably in the range of 2,000 to 50,000 from the viewpoint of solubility, and is 2,000 to 30,000 or 3,000 to 20,000. is still more preferable, and 4,000 to 15,000 is even more preferable. When it is 2,000 or more, the coat layer strength of the coating agent is good, and the abrasion resistance, heat resistance and printability are improved. When the molecular weight is 50,000 or less, the viscosity of the coating agent can be lowered and the storage stability is improved.
The polyamide resin preferably has a softening point of 80 to 140°C, more preferably 90 to 130°C. When the softening point is 80° C. or higher, the surface tack of the coat layer of the printed matter is good, and blocking is prevented. When the softening point is 140° C. or lower, the coating layer becomes flexible and the adhesiveness to the substrate is improved. In addition, a softening point represents the value measured by JISK2207 (ring and ball method).
Further, it preferably has the amine value and/or acid value of a polyamide resin, and the amine value is preferably 0.5 to 20 mgKOH/g, more preferably 1 to 15 mgKOH/g. Also, the acid value is preferably 0.5 to 17 mgKOH/g, more preferably 1 to 15 mgKOH/g.
Furthermore, in the case of a polyamide resin having the structure, weight average molecular weight, softening point, amine value, and acid value within the ranges described above, it acts with the silver-zirconium phosphate particles to easily exhibit antibacterial properties.
Preferred polyamide resins include the Rheomide series manufactured by Kao Corporation.

<Nitrocellulose resin>
The nitrocellulose resin used in the present invention is obtained as a nitrate ester by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the 6-membered ring of the anhydride glucopyranose group in the natural cellulose with nitric acid groups. Those having an average polymerization degree of 20 to 200, more preferably 30 to 150 are preferred. When the average degree of polymerization is 20 or more, the strength of the coat layer is improved and the abrasion resistance is improved, which is preferable. Moreover, when the average degree of polymerization is 200 or less, the solubility in a solvent, the low-temperature stability of the coating agent, and the compatibility with the combined resin are improved, which is preferable. As for the molecular weight, a weight average molecular weight of 5,000 to 200,000 is preferable, and 10,000 to 50,000 is more preferable. Also, it preferably has a glass transition temperature of 120° C. to 180° C. and a nitrogen content of 10.5 to 12.5 mass %.
Preferred nitrocellulose resins include DLX series manufactured by Nobel Enterprises, TR series manufactured by TNC INDUSTRIAL, and the like.

The combination of the polyamide resin and the nitrocellulose resin functions as a binder resin. It is preferable to contain a total of 60% by mass of the polyamide resin and the nitrocellulose resin in the total amount of the binder resin. It is still more preferable to contain 80% by mass.
Furthermore, it is preferable that the solid mass ratio of the polyamide resin to the nitrocellulose resin (polyamide resin/nitrocellulose resin) is 95/5 to 50/50. This is because various resistances of the coating layer such as antibacterial properties, abrasion resistance, heat resistance, and blocking resistance, as well as printability, are improved at this compounding ratio and combination.

<Silver-zirconium phosphate particles>
The silver-zirconium phosphate particles used in the present invention are used to exhibit antibacterial properties. A hexagonal zirconium phosphate, which is an inorganic ion exchanger, has silver ions supported by ion exchange. Zirconium-centered oxygen octahedrons and phosphorus-centered oxygen tetrahedrons are three-dimensionally formed by oxygen sharing. and has silver ions in its skeleton. When the coating layer has a set of resins consisting of the silver-zirconium phosphate particles and a combination of a polyurethane resin and a vinyl chloride resin, or a combination of a polyamide resin and a nitrocellulose resin, antibacterial properties In addition, the adhesiveness to the base material, abrasion resistance, heat resistance, blocking resistance, etc. can be improved, so it is suitable.

The silver-zirconium phosphate particles are preferably contained in an amount of 0.05 to 0.9% by mass, more preferably 0.05 to 0.6% by mass, based on the total mass of the antibacterial coating agent. When the amount is 0.05% by mass or more, antibacterial properties are exhibited, and when the amount is 0.9% by mass or less, printability is improved. Also, the average particle size of the silver-zirconium phosphate particles is preferably 0.1 to 12 μm, more preferably 1 to 5 μm. Preferred silver-zirconium phosphate particles include Novaron AG series manufactured by Toagosei Co., Ltd., and the like.

In the present invention, the average particle size refers to a D50 value measured by a laser diffraction/scattering method. can be measured.

<Chlorinated polyolefin resin>
It is preferable to use a chlorinated olefin resin for the coating agent of the present invention. The chlorine content of the chlorinated olefin resin is preferably from 25 to 45% by mass, more preferably from 26 to 40% by mass, in order to improve adhesion to substrates treated for easy adhesion. Here, the chlorine content in the present invention refers to the percentage by mass of chlorine atoms contained in 100% by mass of the chlorinated olefin resin. Also, from the viewpoint of solubility in a mixed solvent such as an ester solvent/alcohol solvent, the weight average molecular weight of the chlorinated polyolefin resin in the present invention is preferably 5,000 to 30,000. From the viewpoint of balance with blocking resistance, the coating agent composition preferably contains 0.1 to 3% by mass of the chlorinated olefin resin. More preferably, it is 0.2 to 2% by mass.
In the present invention, the chlorinated polyolefin resin has a structure in which the hydrogen of the α-olefin polymer represented by the following general formula (2) is substituted with chlorine.
general formula (2)

_CH2 =CH-R3

(In the formula, R3 is an alkyl group having 1 or more carbon atoms.)
Since the chlorinated polyolefin resin has a flexible alkyl group as a branched structure, it is a viscous liquid even at low temperatures, and the above amount improves adhesion to substrates. The polyolefin structure in the chlorinated polyolefin resin is not particularly limited. For example, resins containing homopolymers or copolymers of α-olefin unsaturated hydrocarbons such as polypropylene, poly-1-butene and poly-4-methyl-1-pentene are preferred. Among them, those containing a polypropylene structure (that is, a chlorinated polypropylene structure) are particularly preferred. In this case, when used in combination with a polyurethane resin having a polyester structural unit composed of a diol having an alkyl substituent and a dibasic acid, excellent adhesion to a substrate can be obtained.

Further, the chlorinated polyolefin resin may be a copolymer resin with other monomers, and there is no particular limitation as long as the chlorine content is the above. Preferred copolymerizable monomers include acrylic monomers, acidic monomers, vinyl acetate monomers, and styrene monomers. Examples of acrylic monomers include the acrylic monomers described above, and acidic monomers include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic anhydride, Aconitic acid, hymic acid anhydride, (meth)acrylic acid and the like can be mentioned.

<Fatty acid amide>
It is preferable to use a fatty acid amide for the coating agent of the present invention. Examples of fatty acid amides include saturated fatty acid amides, unsaturated fatty acid amides, and modified fatty acid amides. 5% by mass. Blocking resistance is further improved by using it together with the binder resin of the present invention.

<Hydrocarbon wax particles>
It is preferable to use hydrocarbon wax particles for the coating agent of the present invention. Hydrocarbon waxes include polyolefin waxes, paraffin waxes and the like, and are preferably contained in the coating agent composition in an amount of 0.1 to 3% by mass, more preferably 0.3 to 2.5% by mass. Friction resistance is further improved by using it together with the binder resin of the present invention.

<Extender pigment>
An extender pigment is preferably used in the coating agent of the present invention in order to improve blocking resistance and matting effect. It is preferably contained in the coating agent composition in an amount of 1 to 20% by mass, more preferably 5 to 15% by mass. Extender pigments include silica, barium sulfate, kaolin, clay, calcium carbonate, magnesium carbonate and the like.

<Resin fine particles>
In the coating agent of the present invention, the resin fine particles can control the light diffusivity by means of their inherent refractive index, and can impart desired design properties such as glossiness, mattness and transparency. The refractive index of the resin fine particles used is preferably 1.40 or more, more preferably 1.45 or more. Moreover, it is preferably 1.75 or less, more preferably 1.70 or less, and further preferably 1.60 or less. Examples of the resin fine particles include polyacrylic fine particles, polyamino fine particles, polyolefin fine particles, and polystyrene fine particles, and it is preferable to contain at least one selected from the above fine particles. The average particle size of the fine resin particles is preferably 0.5 to 10 μm, more preferably 1 to 8 μm. This is because the abrasion resistance and the matting effect are improved.
In addition, the content of resin fine particles is 1 to 10% by mass in the coating agent composition, depending on the degree of abrasion resistance (slipperiness) and matting effect desired, and the particle size and type of resin fine particles to be added. is preferred, and more preferably 1 to 5% by mass. The fine resin particles do not contain hydrocarbon wax particles.

As the resin fine particles, the polyacrylic fine particles are Artpearl GS series and Artpearl J series manufactured by Neagari Kogyo Co., Ltd., the polyamino fine particles are Optobeads series manufactured by Nissan Chemical Industries, and the polyolefin fine particles are Flowbeads LE series manufactured by Sumitomo Seika Co., Ltd. The fine particles of polystyrene resin include the Fine Pearl series manufactured by Matsuura Co., Ltd., the Fine Powder MP series manufactured by Soken Chemical Co., Ltd., the Techpolymer SBX series manufactured by Sekisui Kasei Co., Ltd., and the Techpolymer SSX series.

<Other binder resin>
As the binder resin, resins other than polyurethane resins, vinyl chloride resins, polyamide resins, and nitrocellulose resins may be used in combination as long as they have binder performance. Examples include polyolefin resins, ethylene-vinyl acetate copolymer resins, Polyester resin, acrylic resin, urethane-acrylic resin, styrene resin, styrene-acrylic acid resin, styrene-maleic acid resin, maleic anhydride resin, maleic acid resin, vinyl acetate resin, rosin resin, rosin-modified maleic acid resin, cycloolefin Examples include resins, alkyd resins, terpene resins, phenol-modified terpene resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyral, petroleum resins, silicone resins and modified resins thereof. These resins can be used alone or in combination of two or more. The content thereof is preferably 0 to 30% by mass, preferably 0 to 15% by mass, based on 100% by mass of the solid content of the binder resin. % is more preferred. The binder resin does not contain chlorinated polyolefin resin.

Additives such as pigment dispersants, leveling agents, cross-linking agents, surfactants, plasticizers, and adhesion aids may optionally be added.
<Organic solvent>
Organic solvents used in the ink composition of the present invention mainly include alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol, ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and acetic acid. Ester-based organic solvents such as methyl, ethyl acetate, propyl acetate, and butyl acetate; aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, and n-octane; and cyclohexane, methylcyclohexane, ethylcyclohexane, and cycloheptane. , cyclooctane and other alicyclic hydrocarbon-based organic solvents. Considering the solubility and drying properties of the binder resin, it is preferable to use them by mixing. The amount of these organic solvents used is preferably 30% by mass or more in the total amount of the ink. It should be noted that the main component of the organic solvent is preferably a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent in order to avoid odors during printing and to deal with the environment. is preferably 50:50 to 90:10.

<Manufacture of coating agent>
The coating agent of the present invention includes, for example, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, an organic solvent, and antibacterial agent particles, and if necessary, an extender pigment and/or resin fine particles dissolved in an organic solvent and/or It can be manufactured by dispersing. Specifically, for example, silver-zirconium phosphate particles, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, extender pigment and/or fine resin particles are mixed and dispersed in an organic solvent to prepare a dispersion. A coating agent can be produced by further blending a polyurethane resin, a chlorinated polyolefin resin, fatty acid amide and/or hydrocarbon wax particles, or, if necessary, other resins and additives into the resulting dispersion. The particle size distribution of the dispersion can be adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the dispersion, the viscosity of the dispersion, and the like. As the dispersing machine, commonly used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be suitably used.

<Base material>
The coating agent of the present invention is printed on a substrate to form a printed matter. Although the substrate is not particularly limited, it is preferably a film substrate. Examples include polyolefin substrates such as polyethylene and polypropylene, polyester substrates such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene, AS resin, ABS resin, and the like. film bases such as polystyrene bases, nylon bases, polyamide bases, polyvinyl chloride bases, polyvinylidene chloride bases, cellophane bases, and film bases composed of composite materials thereof. The plastic substrate may be vapor-deposited with a metal such as silica, alumina, or aluminum or a metal oxide, and the vapor-deposited surface may be coated with a paint such as polyvinyl alcohol. In general, the surface of the substrate to be printed is often subjected to surface treatment such as corona treatment. Furthermore, as the base material, a film obtained by processing a plastic film such as coating and kneading of an antifogging agent, surface coating and kneading of a matting agent in advance can also be used.
Further, the base material may be a single layer, or may be a laminate (base material layer) in which two or more base materials are laminated. The substrates constituting the substrate layer may be the same or different.
Among them, a polyolefin base material is preferable. The polyolefin substrate may or may not be subjected to corona discharge treatment or other surface treatment.

Antifog agents are preferably surfactants, for example, ionic surfactants such as sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, and ethylene oxide adducts. One or more agents can be used.

<Printed Matter>
The printed matter of the present invention is formed by printing the coating agent on a substrate. After printing on a base material using the coating agent of the present invention, a coating layer is formed by removing volatile components such as organic solvents to obtain an antibacterial printed matter. The printing method is a gravure printing method. For example, the inks are diluted with a diluting solvent to a viscosity and concentration suitable for gravure printing, and supplied singly or mixed to each printing unit for printing. Then, it can be obtained by fixing the coat layer by drying in an oven.
Also, there may be layers other than the layers described above. Examples of the other layers include a primer layer, a pattern layer and a thermoplastic resin layer, an anchor coat layer, and the like. As will be described later, it is also preferable that the printed matter of the coating agent has a pattern layer formed from printing ink between the substrate and the coating layer.

<Coating layer>
When the coating agent is used in combination with the binder resin, the flexibility of the coating film is increased by softening the coating layer. Inevitably, silver-zirconium phosphate particles are buried in the coating film, which inhibits the expression of antibacterial properties, and it is possible to prevent separation from the coating layer after rubbing the coating layer, and the antibacterial performance is maintained. easier to do. The coat layer is preferably positioned as a surface protective layer.

<Pattern layer>
The printed matter may have a pattern layer between the substrate and the coat layer. The pattern layer can be obtained by forming a pattern layer on the substrate using a rotary printing method such as a gravure printing method or a flexographic printing method. For example, printing ink is diluted with an organic solvent to a viscosity and concentration suitable for gravure printing, and is supplied to each printing unit for printing. Although the printing method is not particularly limited, preferred examples include screen printing, gravure printing, flexographic printing, offset printing, and inkjet printing, with gravure printing being particularly preferred. Examples of such inks include printing inks described in Japanese Patent No. 6376269, Japanese Patent Application Laid-Open No. 2020-59806, and the like.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Parts and % in the present invention represent parts by mass and % by mass unless otherwise specified.

(amine value)
The amine value was measured by the following method according to JISK0070 (1992).
-Method for measuring amine value Accurately weigh 0.5 to 2 g of a sample (sample amount: Sg). 30 mL of neutral ethanol (BDG neutral) is added to the precisely weighed sample to dissolve it. The resulting solution is titrated with a 0.2 mol/L ethanolic hydrochloric acid solution (potency: f). The end point is the point at which the color of the solution changes from green to yellow. Using the titration amount (AmL) at this time, the amine value is determined by the following (Equation 5).
(Formula 5) Amine value = (A x f x 0.2 x 56.108) / S

(Weight average molecular weight)
The weight average molecular weight was obtained by GPC (gel permeation chromatography) method. The molecular weight distribution was measured using "Shodex GPCS System-21" manufactured by Showa Denko Co., Ltd. to obtain the polystyrene equivalent molecular weight. Measurement conditions are shown below.
Column: Use the following multiple columns connected in series.
TSKgel SuperAW2500 manufactured by Tosoh Corporation,
manufactured by Tosoh Corporation, TSKgel SuperAW3000,
TSKgel SuperAW4000 manufactured by Tosoh Corporation,
TSKgel guard column SuperAWH manufactured by Tosoh Corporation
Detector: RI (differential refractometer),
Measurement conditions: column temperature 40°C,
Eluent: dimethylformamide Flow rate: 0.5 mL/min

<Synthesis Example 1> (Synthesis of polyurethane resin PU1)
A condensate of 3-methyl-1,5-pentanediol having a number average molecular weight (hereinafter referred to as Mn) of 2,000 and adipic acid was placed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube. Polyester polyol (abbreviated as "MPD / AdA") 100.0 parts, polypropylene glycol 100.0 parts, cyclohexanedimethanol 1.6 parts, N-methyldiethanolamine 1.3 parts, isophorone diisocyanate 61.5 parts, 0.06 parts of stannous 2-ethylhexylate, 2.6 parts of 2-diethylaminoethanol and 40.0 parts of ethyl acetate were charged, reacted at 90° C. for 2 hours under a nitrogen stream, and 50.0 parts of ethyl acetate was added. After cooling, 357.1 parts of a solvent solution of a terminal isocyanate prepolymer was obtained. The resulting isocyanate terminated prepolymer 357 was then added to a mixture of 23.6 parts isophoronediamine, 1.5 parts ethanolamine, 0.08 parts di-n-butylamine, 278.9 parts ethyl acetate and 246.0 parts isopropyl alcohol. .1 part was slowly added at room temperature, then allowed to react at 50°C for 1 hour. Then, after adding 3.2 parts of isophorone diisocyanate to adjust the viscosity, the solid content was adjusted to 30% with a solvent obtained by mixing ethyl acetate/isopropyl alcohol at a mass ratio of 2/1, and the amine value was 14.0 mgKOH/ A polyurethane resin (PU1) having a weight average molecular weight of 40,000 was obtained.

<Synthesis Example 2> (Synthesis of polyurethane resin PU2)
A condensate of 3-methyl-1,5-pentanediol having a number average molecular weight (hereinafter referred to as Mn) of 2,000 and sebacic acid was placed in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube. 103.2 parts of polyester polyol (abbreviated as "MPD/SeA"), 35.2 parts of neopentyl glycol, 121.4 parts of isophorone diisocyanate, 0.03 parts of stannous 2-ethylhexylate and 65.5 parts of ethyl acetate. 1 part was charged and reacted at 90° C. for 2 hours under nitrogen stream, 165.3 parts of ethyl acetate was added and cooled to obtain 490.2 parts of a solvent solution of terminal isocyanate prepolymer. Then, 490.2 parts of the resulting terminal isocyanate prepolymer was slowly added to a mixture of 33.6 parts of isophoronediamine, 1.2 parts of di-n-butylamine, 237.5 parts of ethyl acetate and 200.6 parts of isopropyl alcohol at room temperature. and then reacted at 50° C. for 1 hour. Then, after adding 5.3 parts of isophorone diisocyanate to adjust the viscosity, the solid content was adjusted to 30% with a solvent obtained by mixing ethyl acetate/isopropyl alcohol at a mass ratio of 3/2, and the amine value was 8.2 mg KOH/ A polyurethane resin (PU2) having a weight average molecular weight of 40,000 was obtained.
In addition, the abbreviations in Table 1 indicate the following.
MPD: 3-methyl-1,5-pentanediol AdA: adipic acid SeA: sebacic acid PPG: polypropylene glycol CHDM: cyclohexanedimethanol MDA: N-methyldiethanolamine NPG: neopentyl glycol IPA: isopropyl alcohol

<Preparation of vinyl chloride-vinyl acetate copolymer resin solution>
30 parts of vinyl chloride-vinyl acetate copolymer resin (manufactured by Nisshin Chemical Co., Ltd., product name Solbin TA5R) is mixed and dissolved in 70 parts of ethyl acetate to obtain a vinyl chloride-vinyl acetate copolymer resin solution with a solid content of 30% (salt vinegar may be abbreviated as Biwanis). The hydroxyl value of Solbin TA5R is 140 mgKOH/g.

<Adjustment of polyamide resin solution>
Polyamide resin (manufactured by Kao Corporation Rheomide S-8200 (weight average molecular weight 10,000, softening point 115 ° C., amine value 3.5 mgKOH / g, acid value 5.0 mgKOH / g, having a structural unit derived from dimer acid), A polyamide resin solution was obtained by adjusting the solid content to 30% with a solvent obtained by mixing isopropyl alcohol/methylcyclohexane at a mass ratio of 5/5.

<Adjustment of nitrocellulose resin solution>
A nitrocellulose resin (DLX5-8 manufactured by Nobel) was mixed with ethyl acetate/ethyl alcohol at a mass ratio of 5/5 to adjust the solid content to 30%, and a nitrocellulose resin solution (abbreviated as nitrocellulose varnish) was prepared. may be used).

<Antibacterial agent>
Silver-zirconium phosphate (Novaron AG300 manufactured by Toagosei Co., Ltd.)
<Chlorinated polyolefin resin>
Chlorinated polyolefin varnish (Superchron 370M manufactured by Nippon Paper Industries Co., Ltd.)
<Fatty acid amide>
Palmitic acid amide Ethylene bis fatty acid amide <hydrocarbon wax>
Polyethylene wax (manufactured by Mitsui Chemicals, product name Hi-Wax 320MP)
Paraffin wax (manufactured by Micro Powders, product name MP-22XF)
<Extender pigment>
Calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: calcium carbonate PC)
<Resin fine particles>
Polystyrene fine particles (average particle size 6.1 μm, styrene-divinylbenzene copolymer)

<Example 1>
33 parts of polyurethane resin solution (PU1), 16 parts of vinyl chloride resin solution, 0.2 parts of silver-zirconium phosphate, 0.5 parts of chlorinated polyolefin varnish, 0.4 parts of palmitic acid amide, 1.2 parts of polyethylene wax 10 parts of calcium carbonate, 3.5 parts of polystyrene fine particles, 35.2 parts of a mixed solvent consisting of n-propyl acetate: isopropyl alcohol: propylene glycol monomethyl ether (abbreviated as PGM) = 70:20:10 (weight ratio) were kneaded in a sand mill (Eiger Mill) to prepare an antibacterial coating agent (coating agent S1).

<Examples 2 to 14>
Antibacterial coating agent compositions (coating agents S2 to S14) were obtained in the same manner as in Example 1 except that the raw materials and compounding ratios shown in Table 2 were used.

<Example 15>
Polyamide resin solution 34.0 parts, nitrocellulose resin solution 22.0 parts, silver-zirconium phosphate 0.2 parts, chlorinated polyolefin varnish 1.0 parts, palmitic acid amide 0.8 parts, ethylene bis fatty acid amide 0.2 parts. 8 parts, polyethylene wax 0.8 parts, paraffin wax 0.8 parts, polystyrene fine particles 2.0 parts, n-propyl acetate: ethyl acetate: isopropyl alcohol: methylcyclohexane (abbreviated as MCH) = 20:20:20: 40 (weight ratio) was mixed with a stirrer to prepare an antibacterial coating agent (coating agent S15).

<Examples 16 to 26>
Antibacterial coating agent compositions (coating agents S16 to S26) were obtained in the same manner as in Example 15 except that the raw materials and compounding ratios shown in Table 3 were used.

<Comparative Examples 1 to 4>
Antibacterial coating agent compositions (coating agents T1 to T4) were obtained in the same manner as in Example 1, except that the raw materials and compounding ratios shown in Table 4 were used.

<Comparative Examples 5 to 8>
Antibacterial coating agent compositions (coating agents T5 to T8) were obtained in the same manner as in Example 15 except that the raw materials and compounding ratios shown in Table 5 were used.

<Printing antibacterial coated printed matter>
The antibacterial coating agent obtained in Example 1 was diluted with a diluting solvent (n-propyl acetate:ethyl acetate:isopropyl alcohol:methylcyclohexane=35:30:20:15 (weight ratio)) and applied to a Zahn cup No. 3 for 15 seconds, and used as a diluted antibacterial coating agent for printing.
Next, a corona discharge-treated polypropylene film (D-SHNY01, 28 μm, manufactured by DIC Corporation) is printed with an etching plate having a plate depth of 30 microns using a gravure proof printing machine (drying temperature: 50° C., printing speed: 50 m/s). minutes) to obtain a print.

Polypropylene film prints were obtained in the same manner as described above, except that the antibacterial coating agents obtained in Examples 2-26 were used.

Polypropylene film prints were obtained in the same manner as above, except that the antibacterial coating agents obtained in Comparative Examples 1 to 8 were used.

Using the antibacterial coating agents obtained in Examples 1 to 26 and Comparative Examples 1 to 8 and their printed matter, the following evaluations were carried out. The results are shown in Tables 2-5.

<Adhesion>
Adhesive tape (product name: cellophane tape) was attached to the coat layer surface of the printed matter printed on the polypropylene film of Examples 1 to 26 and Comparative Examples 1 to 8, and the degree of peeling of the coat layer from the film when the tape was quickly peeled off. The adhesiveness was evaluated from In addition, evaluation was performed after leaving still at 25 degreeC for 24 hours after printing.
A. B. Less than 5% of the coating layer peeled from the film. C. The area where the coat layer is separated from the film is 5% or more and less than 15%. D. The area where the coat layer is separated from the film is 15% or more and less than 25%. The area where the coating layer is peeled off from the film is 25% or more.

<Abrasion resistance>
High-quality paper was applied to the coated layer surface of the printed matter printed on the polypropylene films of Examples 1 to 26 and Comparative Examples 1 to 8, and evaluated using a Gakushin type rubbing fastness tester. The evaluation conditions were a load of 500 g and 100 reciprocations of friction, and the abrasion resistance was evaluated from the degree of peeling of the coating layer from the film after the friction.
A. B. Less than 5% of the coating layer peeled from the film. C. The area where the coat layer is separated from the film is 5% or more and less than 15%. D. The area where the coat layer is separated from the film is 15% or more and less than 25%. The area where the coating layer is peeled off from the film is 25% or more.

<Blocking resistance>
The coating agent prints printed on the polypropylene films of Examples 1 to 26 and Comparative Examples 1 to 8 were cut into 4 cm squares, each printed surface and non-printed surface were combined, and a load of 20 kg/cm ² was applied, and an atmosphere of 60 ° C. After leaving for 24 hours at , the printed surface was peeled off, and the blocking resistance was evaluated from the degree of peeling of the coat layer.
A. B. Less than 5% of the coating layer peeled off from the film. C. The area where the coat layer is separated from the film is 5% or more and less than 15%. D. The area where the coat layer is separated from the film is 15% or more and less than 25%. The area where the coating layer is peeled off from the film is 25% or more.

<Printability>
The coating agents obtained in Examples 1 to 26 and Comparative Examples 1 to 8 were diluted with a solvent (n-propyl acetate:ethyl acetate:isopropyl alcohol:methylcyclohexane=35:30:20:15 (weight ratio) to was adjusted to 15 seconds (25° C.) with a Zahn cup No. 3, and after 90 minutes of idling of the plate in the printing press, the area of the plate fogging portion was visually determined and evaluated.
A. B. The plate fogging area cannot be visually confirmed. C. The plate fogging area is more than 0% and less than 5%. D. Those having a plate fogging area of 5% or more and less than 10%. The plate fogging area is 10% or more. A, B, and C are in the range of practically no problem.

<Antibacterial properties>
For the coating agent prints printed on the polypropylene films of Examples 1 to 26 and Comparative Examples 1 to 8, Japanese Industrial Standards JIS Z 2801: 2000 "Antibacterial processed products-antibacterial test method/antibacterial effect" 5.2 Plastic products, etc. An antibacterial activity test against Escherichia coli or Staphylococcus aureus was conducted according to the test method. An antibacterial activity value of 2 or more was judged to be effective.
In addition, the antibacterial properties of the obtained coating agent printed matter were also confirmed after the above abrasion resistance test was carried out.

In particular, the antibacterial coating agent of the present invention exhibited a unique effect of exhibiting good antibacterial properties even under the severe conditions of rubbing the printed material of the coating agent with a load of 500 g and 100 times.

According to the present invention, antibacterial properties and printability are good, adhesion to substrates, abrasion resistance, heat resistance, and blocking resistance to substrates are good, and furthermore, the coating layer after printing the coating agent is rubbed. It was possible to provide a coating agent having antibacterial properties even after addition.
In particular, in the antibacterial test of the present application (the antibacterial property of the printed matter of the coating agent and the antibacterial property of the printed matter after the abrasion resistance test), Comparative Examples 1 and 5 containing no silver-zirconium phosphate particles and Comparative Example 3 containing no polyurethane resin , Comparative Example 4 containing no vinyl chloride resin, Comparative Example 7 containing no polyamide resin, and Comparative Example 8 containing no nitrocellulose did not meet the criteria. In addition, Comparative Examples 2 and 6, in which the content of silver-zirconium phosphate particles exceeded 0.9% by mass, resulted in poor printability.

Claims (5)

An antibacterial coating agent containing a binder resin, an organic solvent and silver-zirconium phosphate particles,
The binder resin comprises at least one combination of a polyurethane resin and a vinyl chloride resin, or a combination of a polyamide resin and a nitrocellulose resin,
An antibacterial coating agent containing 0.05 to 0.9% by mass of the silver-zirconium phosphate particles in the total mass of the antibacterial coating agent. The antibacterial coating agent according to claim 1, further comprising a chlorinated polyolefin resin. 3. The antimicrobial coating agent according to claim 1, wherein the antimicrobial coating agent further contains fatty acid amide and/or hydrocarbon wax particles. The antibacterial coating agent according to any one of claims 1 to 3, further comprising an extender pigment and/or fine resin particles. A printed matter having a printed layer comprising the antibacterial coating agent according to any one of claims 1 to 4 on a substrate.