JP7671412B2 - Water-based phosphorescent pigment composition - Google Patents

Description

The present invention relates to an aqueous phosphorescent pigment composition.

In emergencies such as major earthquakes or accidents, it may be necessary to evacuate from a room when lighting is lost. In such situations, it is important to have materials that can emit light even in the dark and show evacuation routes or destinations.

In particular, to safely evacuate large numbers of people from places such as hotels, event venues, airplanes and trains, it will be necessary to treat carpets and other flooring materials with phosphorescent materials to prevent confusion during evacuation.

In light of this situation, the use of phosphorescent materials using phosphorescent pigments such as phosphorescent fibers, phosphorescent tapes, and phosphorescent paints is being considered. Unlike regular fluorescent substances, which emit light for a short period of time, phosphorescent pigments emit a long-lasting glow, making them suitable for use in emergencies such as those mentioned above.

An example of a paint that uses phosphorescent pigments is the water-based emulsion paint disclosed in Patent Document 1.

Patent No. 6712710

However, when paint containing conventional phosphorescent pigments is applied to flooring materials such as carpet to, for example, draw a path to an emergency exit, the texture of the painted area changes significantly, making those areas feel hard. Since the painted areas are often indistinguishable under normal circumstances, sudden changes in hardness in different parts of the floor create an uncomfortable feeling when walking on them under normal circumstances.

Therefore, the object of the present invention is to provide a composition containing a phosphorescent pigment, which is capable of maintaining the flexibility of a fabric, such as a carpet, even when attached to the fabric.

The present invention provides the following:
[1] An aqueous phosphorescent pigment composition comprising an aqueous medium, and a polymer and a phosphorescent pigment dispersed in the aqueous medium,
The composition comprises one or more of the above polymers, and a 0.01 mm-thick film formed from the above polymer at 20° C. has a haze value of 35% or less as measured in accordance with JIS K7136:2000.

[2] The aqueous phosphorescent pigment composition described in [1], wherein the polymer is at least one selected from the group consisting of conjugated diene polymers, acrylic polymers, and urethane polymers.

[3] The aqueous phosphorescent pigment composition described in [1] or [2], wherein the conjugated diene polymer is at least one selected from the group consisting of styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-vinylpyridine rubber, butadiene rubber and natural rubber.

[4] An aqueous phosphorescent pigment composition described in any one of [1] to [3], wherein the polymer has a glass transition temperature of -40 to 10°C as measured at a heating rate of 10°C/min using a differential scanning calorimeter.

[5] The above phosphorescent pigment is a phosphorescent pigment obtained by doping a strontium aluminate compound with a lanthanoid rare earth element, in an aqueous phosphorescent pigment composition described in any of [1] to [4].

[6] An aqueous phosphorescent pigment composition described in any of [1] to [5], wherein the 90% volume cumulative diameter D90 of the phosphorescent pigment is 50 μm or less.

[7] An aqueous phosphorescent pigment composition described in any one of [1] to [6], further containing at least one selected from the group consisting of thickeners, drying inhibitors, pH adjusters, and preservatives.

[8] The aqueous phosphorescent pigment composition according to any one of [1] to [7], wherein when the aqueous phosphorescent pigment composition is applied to a fabric in an amount of 40 g/ ^m2 as a dry weight, the bending resistance of the fabric at 23°C measured by a handle-o-meter method after application is less than 300 mN.

[9] An aqueous phosphorescent pigment composition described in any one of [1] to [8], which is used by adhering to a fabric.

[10] An aqueous phosphorescent pigment composition described in any one of [1] to [9], for use in inkjet printing.

According to the present invention, there is provided a composition containing a phosphorescent pigment, which is capable of maintaining the flexibility of a fabric, such as a carpet, even when attached to the fabric.

The aqueous phosphorescent pigment composition according to the embodiment is an aqueous phosphorescent pigment composition containing an aqueous medium and a polymer and a phosphorescent pigment dispersed in the aqueous medium, the polymer being composed of one or more types, and the haze value of a 0.01 mm thick film formed from the polymer at 20°C is 35% or less according to JIS K7136:2000.

The aqueous medium is a medium that holds the polymer and the phosphorescent pigment in the water-based phosphorescent pigment composition and provides fluidity to the water-based phosphorescent pigment composition.

The aqueous medium basically contains water such as distilled water, ion-exchanged water, tap water, industrial water, etc., and may further contain water-soluble components (various additives, organic solvents, etc.).

The polymer is dispersed in the aqueous medium, but the polymer may be partially swollen in the aqueous medium or partially dissolved in the aqueous medium. The polymer typically forms particles (polymer particles) in the aqueous medium.

The polymer may be provided in the form of a dispersion (emulsion, latex, suspension, etc.) in an aqueous medium. The polymer may be one type or two or more types, but two or more types of polymers means that there are two or more types of polymers. When the polymer is provided as a dispersion, in order to provide two or more types of polymers, it is sufficient to simply mix a dispersion of polymer A (polymer A emulsion), a dispersion of polymer B (polymer B emulsion), and a dispersion of other polymers used as necessary.

The monomer units or structural units constituting each polymer may be of one type or of two or more types. Here, the monomer unit means a unit derived from a vinyl compound when a polymer is obtained by vinyl polymerization (for example, a unit represented by _-CH2 - ^CHR0- , where ^R0 is a group that forms a side chain of the vinyl compound). The structural unit means, in the case where a polymer is obtained by polyaddition, a unit represented by -NHCOO-R ¹ -OCONH-R ² - (R ¹ means a polyol residue, R ² means a polyisocyanate residue, and is a structural unit constituting polyurethane), in the case where a polymer is obtained by polycondensation, a unit represented by -RO-R ¹⁰ -COO-R ¹¹ -O- (R ¹⁰ means a polycarboxylic acid residue, R ¹¹ means a polyol residue, and is a structural unit constituting polyester), or a unit represented by -RO-R ²⁰ -CONH-R ²¹ -NH- (R ²⁰ means a polycarboxylic acid residue, R ²¹ means a polyamine residue, and is a structural unit constituting polyamide), etc.

The polymer preferably has a glass transition temperature (hereinafter sometimes abbreviated as "Tg") of -40 to 10°C, measured with a differential scanning calorimeter at a heating rate of 10°C/min. A Tg of -40°C or higher can prevent a sticky feel (tackiness) when applied to a fabric, for example. On the other hand, a Tg of 10°C or lower can prevent the entire fabric from becoming too hard when applied to a fabric, for example. The Tg may be -40 to 8°C, -35 to 6°C, or -30 to 6°C.

When the polymer is provided as a dispersion, the minimum film-forming temperature as specified in JIS K6828-2:2003, i.e., the minimum temperature at which a crack-free, uniform film is formed when the polymer dispersion is dried, can be 20°C or less, 15°C or less, 10°C or less, or 5°C or less.

The haze value of a 0.01 mm thick film formed from the polymer at 20°C must be 35% or less (i.e., 0 to 35%) in accordance with JIS K7136:2000.

There are no particular limitations on the polymer gel, but for example, it is preferable that the toluene-insoluble content is 40 to 95%. Having a content of 40% or more makes it easy to prevent the fabric from becoming sticky, and having a content of 95% or less makes it easy to prevent the coating film from becoming brittle and peeling off from the substrate.

In investigating various water-based phosphorescent pigment compositions, the inventors have discovered the new finding that when the composition is applied to a fabric such as a carpet, whether or not the flexibility of the fabric can be maintained is related to the haze value, which is an index of transparency. In other words, they have discovered the unexpected relationship that the maintenance of the flexibility of the fabric is closely related to the haze value, rather than being dependent on the type of polymer or the mechanical properties of the polymer.

Fabric means a material formed into a thin sheet using multiple fibers, and is classified into woven fabric, knitted fabric, lace, felt, nonwoven fabric, and paper according to the manufacturing method.

Woven fabric refers to fabric obtained by crossing warp and weft threads, and knitted fabric refers to knitted fabric obtained by making a loop with one or several threads and then passing the next thread through the loop to make a new loop. Lace refers to a cloth made of one or several threads with a cross-hatch pattern, and felt refers to a sheet of animal hair fibers compressed into a thin plate shape. Nonwoven fabric is a sheet in which fibers are intertwined without being woven (excluding paper, felt, and knitted fabric). Nonwoven fabrics include nonwoven fabrics made of short fibers (i.e. staples) (short fiber nonwoven fabrics) and nonwoven fabrics made of long fibers (i.e. filaments) (long fiber nonwoven fabrics). Short fiber nonwoven fabrics generally include carded nonwoven fabrics, airlaid nonwoven fabrics, and wet nonwoven fabrics. Long fiber nonwoven fabrics generally include spunbond nonwoven fabrics and spunlace nonwoven fabrics. Interfiber bonds in short fiber nonwoven fabrics and long fiber nonwoven fabrics include heat, adhesive resins, and interfiber hydrogen bonds, which are the same as interfiber bonds in paper, etc. Although not limited to this, the staple generally has a fiber length of several hundred mm or less.

The three most common weaves for textiles are plain weave, twill weave, and satin weave. Among woven fabrics, those generally called carpets (or rugs) include plain weave, tufted weave, Wilton weave, Gobelin weave, Axminster weave, moquette weave, jacquard weave, and hand weave.

The haze value in accordance with JIS K7136:2000 of a 0.01 mm thick film formed at 20°C may be 25% or less, 20% or less, 15% or less, 13% or less, 10% or less, 9% or less, 8% or less, or 6% or less.

The polymer may be a polymer that gives a value of less than 300 mN when the bending resistance of the solid content of the aqueous phosphorescent pigment composition is measured. This bending resistance is measured by the following method with reference to JIS L1096:2010 (E method, handle-o-meter method). That is, a roll-shaped cloth (cotton twill, longitudinal density: 114 threads/inch, transverse density: 54 threads/inch, basis weight: 305.1 g/m ² ) is coated with a dry weight of 40 g/m ² of the aqueous phosphorescent pigment composition (single-sided coating), dried at 130° C. for 10 minutes, and a test piece is cut out in a rectangular shape (24 cm x 1 cm) so that the width direction (TD direction) of the roll-shaped cloth is the long side. The bending resistance value measured by the handle-o-meter method with a clearance of 1 cm and a 981 mN measuring weight with the coated surface facing up is less than 300 mN for the entire solid content of the aqueous phosphorescent pigment composition.

The bending resistance value measured by the handle-ometer method described above may be 220 mN or more and less than 300 mN, 170 mN or more and less than 220 mN, or less than 170 mN.

The polymer may be at least one selected from the group consisting of a conjugated diene polymer, an acrylic polymer, and a urethane polymer. When the polymer is provided as a dispersion, it is provided as at least one selected from the group consisting of a conjugated diene polymer emulsion, an acrylic polymer emulsion, and a urethane polymer emulsion.

Examples of conjugated diene polymers include at least one selected from the group consisting of styrene-butadiene rubber (hereinafter sometimes abbreviated as "SBR"; modified products such as carboxyl-modified are also included in SBR), methyl methacrylate-butadiene rubber (hereinafter sometimes abbreviated as "MBR"; modified products such as carboxyl-modified are also included in MBR), acrylonitrile-butadiene rubber (hereinafter sometimes abbreviated as "NBR"; modified products such as carboxyl-modified, styrene-modified, and (meth)acrylate ester-modified are also included in NBR), styrene-butadiene-vinylpyridine rubber (hereinafter sometimes abbreviated as "VP"; modified products such as carboxyl-modified are also included in VP), butadiene rubber (hereinafter sometimes abbreviated as "BR"; modified products such as carboxyl-modified are also included in BR), and natural rubber (hereinafter sometimes abbreviated as "NR"; polyisoprene is also included in NR).

When the above-mentioned conjugated diene polymer is provided as a dispersion, it is provided as at least one type selected from the group consisting of styrene-butadiene rubber emulsion (styrene-butadiene rubber latex), methyl methacrylate-butadiene rubber emulsion (methyl methacrylate-butadiene rubber emulsion latex), acrylonitrile-butadiene rubber emulsion (acrylonitrile-butadiene rubber latex), styrene-butadiene-vinylpyridine rubber emulsion (styrene-butadiene-vinylpyridine rubber latex), butadiene rubber emulsion (butadiene rubber latex) and natural rubber emulsion (natural rubber latex).

Conjugated diene polymers include copolymers of aliphatic conjugated diene monomers (e.g., 10 to 80% by mass based on total monomers), ethylenically unsaturated carboxylic acid monomers (e.g., 0.5 to 15% by mass based on total monomers), and other copolymerizable monomers (e.g., 5 to 89.5% by mass based on total monomers).

Examples of aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadiene, substituted and side-chain conjugated hexadienes, etc., and one or more of these can be used. From the viewpoints of ease of industrial production, availability, and cost, it is particularly preferable to use 1,3-butadiene.

As the ethylenically unsaturated carboxylic acid monomer, one or more monobasic or dibasic acids (anhydrides) such as itaconic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid can be used.

Other monomers include alkenyl aromatic monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, unsaturated monomers containing hydroxyalkyl groups, unsaturated carboxylic acid amide monomers, etc.

Examples of alkenyl aromatic monomers include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, divinylbenzene, etc. These can be used alone or in combination of two or more. Styrene is particularly preferred from the viewpoints of ease of industrial production, availability, and cost.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, etc. These can be used alone or in combination of two or more. From the viewpoints of ease of industrial production, availability, and cost, it is particularly preferable to use acrylonitrile or methacrylonitrile.

Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more. Methyl methacrylate is particularly preferred from the standpoint of ease of industrial production, availability, and cost.

Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. These can be used alone or in combination of two or more.

Examples of unsaturated carboxylic acid amide monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethyl acrylamide, etc. These can be used alone or in combination of two or more.

In addition to the above monomers, any of the monomers typically used in emulsion polymerization, such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, and vinylidene chloride, can be used.

In addition to the above-mentioned conjugated diene polymers, acrylic polymers can be used as the polymer dispersed in the aqueous medium of the water-based phosphorescent pigment composition. Here, the acrylic polymer refers to a polymer containing a monomer having a (meth)acryloyl group (CH ₂ ═CR ³⁰ -CO-, where R ³⁰ is a hydrogen atom or a methyl group) or a monomer copolymerizable with said monomer as a monomer unit. Here, (meth)acryloyl refers to acryloyl or methacryloyl, and the same applies to similar compounds.

The acrylic polymer may be provided as an aqueous dispersion, in which case the aqueous dispersion may be obtained by emulsion polymerization of the raw material monomers. The aqueous dispersion of the acrylic polymer may be a forced emulsion type aqueous dispersion in which a solution of the acrylic polymer in an organic solvent is dispersed in water and at least a portion of the organic solvent is removed.

As the acrylic polymer, an acrylic rubber having elastomeric properties can be used. As such an acrylic rubber, one having a Tg of -40 to 10°C as defined above is preferable.

The acrylic polymer is a copolymer of a low Tg monomer (a monomer that, when homopolymerized, has a Tg of 20°C or less, preferably 0°C or less, as defined above) and a high Tg monomer (a monomer that, when homopolymerized, has a Tg of 50°C or more, as defined above), and an acrylic polymer having a Tg of -40 to 10°C as a copolymer, as defined above, is preferred. At least one of the low Tg monomer and the high Tg monomer has the above-mentioned (meth)acryloyl group.

Low Tg monomers include acrylic acid esters of linear or branched non-tertiary alcohols having 1 to 12 carbon atoms, and the number of carbon atoms of the non-tertiary alcohol may be 4 to 12 or 4 to 8. Such non-tertiary alcohols include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propylheptanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, and the like.

That is, examples of low Tg monomers include n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethyl-hexyl acrylate, isooctyl acrylate, caprolactone acrylate, isodecyl acrylate, tridecyl acrylate, lauryl methacrylate, methoxy-polyethylene glycol-monomethacrylate, lauryl acrylate, ethoxy-ethoxyethyl acrylate, and ethoxylated-nonyl acrylate.

Examples of high Tg monomers include methacrylic acid esters of linear or branched non-tertiary alcohols having 1 to 2 or 6 to 18 carbon atoms, or acrylic acid esters of cyclic non-tertiary alcohols having 6 to 18 carbon atoms.

That is, examples of high Tg monomers include methyl methacrylate, ethyl methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, and propyl methacrylate.

In addition to the above, examples of high Tg monomers include styrene, alkylstyrenes (methylstyrene, etc.), (meth)acrylic acid, (meth)acrylamide, N-alkylacrylamides (N-octylacrylamide, etc.), N,N-dialkylacrylamides (N,N-dimethylacrylamide, etc.), (meth)acrylonitrile, etc.

In addition to the conjugated diene polymers and acrylic polymers mentioned above, urethane polymers can also be used as polymers dispersed in the aqueous medium of the water-based phosphorescent pigment composition.

A urethane polymer is a polymer having a urethane bond based on the reaction of an isocyanate group with a hydroxyl group, and may have, in addition to the urethane bond, a urea bond based on the reaction of an isocyanate group with an amino group or water, or an amide bond based on the reaction of an isocyanate group with a carboxy group. Furthermore, it may have an allophanate group based on the reaction of an isocyanate group with a urethane bond, or a biuret group based on the reaction of an isocyanate group with a urea bond.

The urethane polymer is obtained by the reaction of polyisocyanate and polyol, and in addition to the polyol, a compound containing active hydrogen other than the polyol (such as a polyamine) may be added. In addition, in order to improve water dispersibility, it is possible to use a polyol having a hydrophilic group. Examples of the hydrophilic group include a carboxy group or a salt thereof, a sulfonic acid group or a salt thereof, and a group having a polyoxyethylene skeleton.

The urethane polymer may be provided as an aqueous dispersion, in which case it may be a self-emulsifying or forced-emulsifying aqueous dispersion.

A self-emulsifying water dispersion can be obtained by dispersing the polyurethane having the hydrophilic groups introduced thereinto (the polyurethane can be polymerized with an organic solvent such as acetone and then the organic solvent can be removed after dispersion in water), or by dispersing the isocyanate prepolymer having the hydrophilic groups introduced thereinto into water and extending the chains with a chain extender.

Forced emulsification type aqueous dispersions can be obtained by dispersing a polyurethane solution (a solution of solution-polymerized polyurethane or an organic solvent solution of solvent-free synthesized polyurethane) in water and then removing the organic solvent.

Polyisocyanates that are used as raw materials for urethane polymers include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, etc.

Aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, and 4,4'-diphenyl ether. Diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

Examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, etc.

Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, etc.

Alicyclic polyisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate, etc.

Polyols used as raw materials for urethane polymers include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, etc.

The polyester polyols include one or more dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, and fumaric acid, or their anhydrides; and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and the like. and one or more of the following polyols: 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol.

Examples of polyether polyols include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., using as an initiator a compound having two active hydrogen groups, such as a low molecular weight polyol or a low molecular weight polyamine such as ethylene diamine, propylene diamine, toluene diamine, metaphenylenediamine, diphenylmethane diamine, xylylene diamine, etc. Polyether polyols also include polyether polyols obtained by ring-opening polymerization of alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and cyclic ether monomers such as tetrahydrofuran.

Examples of polycarbonate polyols include those obtained by a dealcoholization or dephenolization reaction between one or more low molecular weight polyols and one or more carbonates, such as dialkyl carbonates (e.g., dimethyl carbonate, diethyl carbonate), alkylene carbonates (e.g., ethylene carbonate, propylene carbonate), diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, and diindanyl carbonate.

Examples of polyolefin polyols include hydroxyl-terminated polybutadiene and its hydrogenated products, and hydroxyl-containing chlorinated polyolefins.

In an aqueous phosphorescent pigment composition, a phosphorescent pigment is dispersed in addition to a polymer in an aqueous medium.

Luminescent pigments, also known as phosphorescent fluorescent materials or phosphorescent materials, are materials that emit light for long periods of time, from several tens of minutes to several hours, even after the external stimulus has ceased, unlike fluorescent materials, which have an extremely short afterglow time and lose their luminescence when the external stimulus has ceased.

Examples of phosphorescent pigments include ZnS:Cu (emitting color: green), ZnS:Cu,Mn,Co (emitting color: orange), ZnCdS:Cu (emitting color: yellow to orange), CaS:Eu,Tm (emitting color: red), CaS:Bi (emitting color: purple-blue), CaSrS:Bi (emitting color: blue), SrAl ₂ O ₄ :Eu,Dy (emitting color: green), Sr ₄ Al ₁₄ O ₂₅ :Eu,Dy (emitting color: blue-green), CaAl ₂ O ₄ :Eu,Nd (emitting color: purple), Sr ₂ MgSi ₂ O ₇ :Eu,Dy (emitting color: blue), Y ₂ O ₂ S:Eu,Mg,Ti (emitting color: red), and the like.

The phosphorescent pigment is preferably one having a host crystal of a compound represented by MAl ₂ O ₄ (wherein M is at least one of calcium, strontium, and barium), to which europium is added as an activator and at least one of cerium, praseodymium, neodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium is added as a co-activator.

Among these, a phosphorescent pigment having a compound represented by SrAl ₂ O ₄ as a host crystal, europium added as an activator, and dysprosium added as a co-activator is useful.

As the phosphorescent pigment, an acid/phosphate-treated phosphorescent pigment is preferred because of its high water resistance. Such a phosphorescent pigment is produced, for example, by preparing a phosphorescent pigment raw material powder made by doping a lanthanoid rare earth element into a strontium aluminate compound, adding this phosphorescent pigment raw material powder to an aqueous solution containing at least one inorganic acid selected from hydrochloric acid, nitric acid, and sulfuric acid, and at least one phosphate selected from sodium dihydrogen phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate (at this time, the weight ratio of phosphorescent pigment raw material powder to phosphate is 100:4-14, and the amount of inorganic acid in the aqueous solution is such that the pH of the aqueous solution is 5.0 or less), stirring at a temperature of 20-30°C, performing an acid/phosphate treatment, and then washing the obtained phosphorescent pigment with water or neutralizing it with an alkaline aqueous solution and drying (for example, see the description in Patent No. 5967787).

The phosphorescent pigment may have a 90% volume cumulative diameter D90 of 50 μm or less. The 90% volume cumulative diameter D90 may be 40 μm or less. The 50% volume cumulative diameter D50 of the phosphorescent pigment may be 20 μm or less, or may be 15 μm or less.

If the water-based phosphorescent pigment composition can be inkjet printed, it is useful, for example, when it is attached to a long piece of fabric. In such a case, it is preferable that the particle size of the phosphorescent pigment is equal to or smaller than the inner diameter of the nozzle of the inkjet printer. Inkjet printers have various nozzle inner diameters depending on the application, ranging from large ones of 50 μm or more to small ones of 20 μm or less. From the viewpoint of the resolution of the printed matter, it is preferable to make the nozzle inner diameter small, and in such cases, nozzles with inner diameters of 20 μm or less are often used. Therefore, it is preferable that the particle size of the phosphorescent pigment is also 1 μm or less (for example, a phosphorescent pigment with a 50% volume cumulative diameter D50 of 1.0 μm or less). It is preferable that the particle size of the phosphorescent pigment (for example, a 50% volume cumulative diameter D50) is 1/10 or less of the inner diameter of the nozzle.

A useful method for producing a phosphorescent pigment having a 50% volume cumulative diameter D50 of 1.0 μm or less is to use a phosphorescent pigment as a starting material, which contains a mother crystal and an activator and has a 50% volume cumulative diameter D50 of less than 1.0 μm, and to mix the phosphorescent pigment starting material with a predetermined amount of a compound containing an activator for the phosphorescent pigment, and to bake the resulting mixture at a predetermined temperature and in a predetermined atmosphere.

Specifically, the starting phosphorescent pigment has a composition represented by SrAl ₂ O ₄ :Eu, Dy, or a composition represented by Sr ₄ Al ₁₄ O ₂₅ :Eu, Dy, and in the mixing step, a compound containing Eu and a compound containing Dy are mixed with the starting phosphorescent pigment so that Eu is 0.5 mol % to 4 mol % and Dy is 1 mol % to 8 mol %, and in the firing step, firing is performed in a reducing atmosphere at a temperature of 1000°C to 1400°C (for example, see the description in JP 2019-210337 A).

The water-based phosphorescent pigment composition contains the above-mentioned aqueous medium, polymer, and phosphorescent pigment as essential components, but may also contain at least one selected from the group consisting of a thickener (a water-soluble polymer such as sodium polyacrylate, an aqueous dispersion of cellulose nanofiber, etc.), an anti-drying agent (glycerin, diethylene glycol, etc.), a pH adjuster, and a preservative, and in addition to these, additive components that are soluble or dispersible in the aqueous medium can be added as necessary.

When the aqueous phosphorescent pigment composition contains a thickener, a drying inhibitor, and a preservative, the polymer content can be, for example, 1 to 20 mass%, 1 to 15 mass%, or 1 to 10 mass%, the phosphorescent pigment can be, for example, 5 to 25 mass%, 5 to 20 mass%, or 5 to 15 mass%, the thickener content can be, for example, 0.1 to 1 mass%, 0.1 to 0.8 mass%, or 0.1 to 0.5 mass%, and the preservative content can be, for example, 0.05 to 0.5 mass%, 0.05 to 0.3 mass%, or 0.05 to 0.2 mass%. When the aqueous phosphorescent pigment composition contains a pH adjuster, the pH adjuster content is preferably such that the pH of the aqueous phosphorescent pigment composition as a whole is weakly alkaline to neutral (for example, pH 7 to 11, pH 7 to 10, or pH 7 to 8). All of these contents are based on the total amount of the aqueous phosphorescent pigment composition.

The viscosity of the aqueous phosphorescent pigment composition at 23°C can be 1 to 200 mPa·s, 1 to 100 mPa·s, or 1 to 50 mPa·s when measured 30 seconds after the start of rotation at a rotation speed of 60 rpm using a B-type viscometer (for example, TVB-10 manufactured by Toki Sangyo Co., Ltd.) in accordance with the measurement method of JIS K7117-1.

The method for producing the water-based phosphorescent pigment composition is to mix the polymer dispersion (polymer emulsion) and the phosphorescent pigment, for example, at room temperature (23°C). When mixing, additives such as thickeners, drying inhibitors, and preservatives can be added as necessary.

The present invention will now be described with reference to examples, but the present invention is not limited to the following examples.

[Polymer preparation]
(Preparation Example 1: Emulsion A)
In a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 0.16 parts by mass of sodium hydrogen carbonate, 0.6 parts by mass of sodium dodecylbenzenesulfonate, 5.2 parts by mass of styrene, 2.7 parts by mass of 1,3-butadiene, 0.1 parts by mass of methyl methacrylate, 4 parts by mass of cyclohexene, 1.2 parts by mass of acrylic acid, 1 part by mass of hydroxyethyl acrylate, and 0.5 parts by mass of fumaric acid were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 68°C, and 66.3 parts by mass of styrene, 23 parts by mass of 1,3-butadiene, 1 part by mass of t-dodecyl mercaptan, and 0.5 parts by mass of sodium dodecylbenzenesulfonate were continuously added over 450 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was carried out to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion A.

(Preparation Example 2: Emulsion B)
In a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 8.0 parts by mass of styrene, 5.0 parts by mass of 1,3-butadiene, 0.5 parts by mass of methyl methacrylate, 1 part by mass of acrylonitrile, 0.5 parts by mass of acrylic acid, 1 part by mass of hydroxyethyl acrylate, 1.5 parts by mass of fumaric acid, 2 parts by mass of cyclohexene, 0.05 parts by mass of t-dodecyl mercaptan, 0.5 parts by mass of sodium hydrogen carbonate, and 0.5 parts by mass of sodium dodecylbenzenesulfonate were charged under a nitrogen atmosphere and stirring was started. 1 part by mass of potassium persulfate was added to raise the temperature inside the reactor to 66 ° C., and 52 parts by mass of styrene, 24 parts by mass of 1,3-butadiene, 4 parts by mass of acrylonitrile, 2.5 parts by mass of methyl methacrylate, and 0.45 parts by mass of t-dodecyl mercaptan were continuously added over 530 minutes.
Thereafter, the temperature inside the polymerization reactor was raised to 70° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion B.

(Preparation Example 3: Emulsion C)
In a pressure-resistant polymerization reactor, 120 parts by mass of polymerization water, 6.1 parts by mass of styrene, 4.0 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of itaconic acid, 0.03 parts by mass of ethylene glycol dimethacrylate, and 0.25 parts by mass of sodium dodecylbenzenesulfonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70° C., and 54.1 parts by mass of styrene, 34 parts by mass of 2-ethylhexyl acrylate, and 0.27 parts by mass of ethylene glycol dimethacrylate were continuously added over 300 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was carried out to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion C.

(Preparation Example 4: Emulsion D)
In a pressure-resistant polymerization reactor, 120 parts by mass of polymerization water, 5.5 parts by mass of styrene, 4.5 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of itaconic acid, 0.2 parts by mass of ethylene glycol dimethacrylate, and 0.25 parts by mass of sodium dodecylbenzenesulfonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70° C., and 49.1 parts by mass of styrene, 37.5 parts by mass of 2-ethylhexyl acrylate, and 1.7 parts by mass of ethylene glycol dimethacrylate were continuously added over 300 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion D.

(Preparation Example 5: Emulsion E)
In a pressure-resistant polymerization reactor, 120 parts by mass of polymerization water, 5.2 parts by mass of styrene, 4.7 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of itaconic acid, 0.03 parts by mass of ethylene glycol dimethacrylate, and 0.25 parts by mass of sodium dodecylbenzenesulfonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70° C., and 47 parts by mass of styrene, 41.3 parts by mass of 2-ethylhexyl acrylate, and 0.27 parts by mass of ethylene glycol dimethacrylate were continuously added over 300 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion E.

(Preparation Example 6: Emulsion F)
In a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 6.7 parts by mass of styrene, 6.6 parts by mass of 1,3-butadiene, 0.3 parts by mass of methyl methacrylate, 0.5 parts by mass of acrylonitrile, 1.0 parts by mass of hydroxyethyl acrylate, 0.5 parts by mass of acrylic acid, 1.5 parts by mass of fumaric acid, 2 parts by mass of cyclohexene, 0.3 parts by mass of sodium dodecylbenzenesulfonate, and 0.3 parts by mass of sodium bicarbonate were charged under a nitrogen atmosphere and stirring was started. 1 part by mass of potassium persulfate was added to raise the temperature inside the reactor to 66°C, and 40.3 parts by mass of styrene, 37.4 parts by mass of 1,3-butadiene, 2.2 parts by mass of methyl methacrylate, 3 parts by mass of acrylonitrile, and 0.5 parts by mass of t-dodecyl mercaptan were continuously added over 510 minutes.
Thereafter, the temperature inside the polymerization reactor was raised to 80° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion F.

(Preparation Example 7: Emulsion G)
In a pressure-resistant polymerization reactor, 95 parts by mass of polymerization water, 7.2 parts by mass of styrene, 2.3 parts by mass of 1,3-butadiene, 1.2 parts by mass of acrylic acid, 0.5 parts by mass of fumaric acid, 2 parts by mass of hydroxyethyl acrylate, 6 parts by mass of cyclohexene, 0.03 parts by mass of t-dodecyl mercaptan, 0.9 parts by mass of sodium dodecylbenzenesulfonate, and 0.3 parts by mass of sodium hydrogen carbonate were charged under a nitrogen atmosphere and stirring was started. 1 part by mass of potassium persulfate was added to raise the temperature inside the reactor to 70°C, and 19.5 parts by mass of styrene, 5.3 parts by mass of 1,3-butadiene, and 0.06 parts by mass of t-dodecyl mercaptan were continuously added over 150 minutes. Immediately after the addition of each monomer and other compounds was completed, 28.0 parts by mass of styrene, 34 parts by mass of 1,3-butadiene, and 0.36 parts by mass of t-dodecyl mercaptan were continuously added over 360 minutes.
Thereafter, the temperature inside the polymerization reactor was raised to 85° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion G.

(Preparation Example 8: Emulsion H)
In a pressure-resistant polymerization reactor, 105 parts by mass of polymerization water, 5.2 parts by mass of styrene, 4.6 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of itaconic acid, 0.2 parts by mass of ethylene glycol dimethacrylate, 0.3 parts by mass of sodium dodecylbenzenesulfonate, and 0.3 parts by mass of sodium bicarbonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70°C, and 45.8 parts by mass of styrene, 40.6 parts by mass of 2-ethylhexyl acrylate, 2.1 parts by mass of ethylene glycol dimethacrylate, 0.7 parts by mass of sodium dodecylbenzenesulfonate, and 10 parts by mass of polymerization water were continuously added over 300 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion H.

(Preparation Example 9: Emulsion I)
A pressure-resistant polymerization reactor was charged with 0.8 parts by mass of itaconic acid, 0.04 parts by mass of sodium alkyldiphenyletherdisulfonate, 0.24 parts by mass of turpentine oil, 1.4 parts by mass of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate, and 100 parts by mass of polymerization water under a nitrogen atmosphere, and stirring was started, and the temperature inside the reactor was raised to 67° C. When the temperature reached 67° C., 0.33 parts by mass of potassium persulfate was added, and immediately after the completion of the addition of potassium persulfate, 9.6 parts by mass of 1,3-butadiene, 14.2 parts by mass of methyl methacrylate, 0.06 parts by mass of t-dodecyl mercaptan, 0.012 parts by mass of turpentine oil, and 0.06 parts by mass of a sodium salt of a β-naphthalenesulfonic acid-formalin condensate were continuously added over a period of 100 minutes. After the addition was completed, the reaction was continued for 80 minutes, and then 20.4 parts by mass of 1,3-butadiene, 31.0 parts by mass of methyl methacrylate, 0.14 parts by mass of t-dodecyl mercaptan, 0.027 parts by mass of turpentine oil, and 0.14 parts by mass of sodium salt of β-naphthalenesulfonic acid formalin condensate were continuously added over 270 minutes. After the addition was completed, stirring was continued for 90 minutes, and then 0.2 parts by mass of itaconic acid, 0.01 parts by mass of turpentine oil, and 0.05 parts by mass of sodium salt of β-naphthalenesulfonic acid formalin condensate were added. Furthermore, 6 parts by mass of 1,3-butadiene, 17.8 parts by mass of methyl methacrylate, 0.1 parts by mass of t-dodecyl mercaptan, 0.05 parts by mass of turpentine oil, and 0.35 parts by mass of sodium salt of β-naphthalenesulfonic acid formalin condensate were continuously added over 120 minutes.
Thereafter, the polymerization was terminated when the polymerization conversion rate reached 98% or more. The pH of the resulting emulsion was then adjusted to 7.0 with potassium hydroxide, and steam distillation was carried out to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion I.

(Preparation Example 10: Emulsion J)
In a pressure-resistant reaction vessel, 2 parts by mass of methyl methacrylate, 0.13 parts by mass of sodium dodecylbenzenesulfonate, 0.2 parts by mass of potassium persulfate, and 65 parts by mass of polymerization water were charged under a nitrogen atmosphere, and after thorough stirring, the temperature inside the reactor was raised to 60° C. The reaction was terminated when the polymerization conversion rate reached 99% or more, and the temperature was lowered to 35° C. After the temperature was lowered, 0.15 parts by mass of sodium dodecylbenzenesulfonate was added to obtain a seed latex.
In a pressure-resistant reaction vessel, the seed latex obtained under a nitrogen atmosphere was charged with 11 parts by mass of styrene, 14 parts by mass of 1,3-butadiene, 13 parts by mass of methyl methacrylate, 1 part by mass of acrylic acid, 0.5 parts by mass of t-dodecyl mercaptan, and 32 parts by mass of polymerization water, and stirring was started. 0.3 parts by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 60°C, and the reaction was carried out for 305 minutes. Thereafter, 0.5 parts by mass of sodium dodecylbenzenesulfonate was added, and 75 minutes after the completion of the addition, 36 parts by mass of styrene, 23 parts by mass of 1,3-butadiene, 0.4 parts by mass of t-dodecyl mercaptan, and 1 part by mass of acrylic acid were continuously added over 270 minutes. After the completion of the addition, 0.15 parts by mass of sodium dodecylbenzenesulfonate and 0.05 parts by mass of sodium persulfate were added to the reaction vessel, and the temperature inside the reactor was raised to 70°C.
The temperature inside the reactor was maintained at 70° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the resulting emulsion was adjusted to 7.0 with an aqueous potassium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion J.

(Preparation Example 11: Emulsion K)
In a pressure-resistant polymerization reactor, 130 parts by mass of polymerization water, 1.6 parts by mass of styrene, 4.7 parts by mass of 1,3-butadiene, 6.5 parts by mass of acrylonitrile, 2.5 parts by mass of itaconic acid, 2.0 parts by mass of fumaric acid, 11 parts by mass of cyclohexene, 0.03 parts by mass of t-dodecyl mercaptan, 1.1 parts by mass of sodium dodecylbenzenesulfonate, and 0.5 parts by mass of sodium hydrogen carbonate were charged under a nitrogen atmosphere, and after sufficient stirring, 1.2 parts by mass of potassium persulfate was added and the temperature inside the reactor was raised to 70° C. 25.5 parts by mass of styrene, 36.2 parts by mass of 1,3-butadiene, 19 parts by mass of acrylonitrile, 2.0 parts by mass of acrylic acid, and 0.12 parts by mass of t-dodecyl mercaptan were continuously added over 390 minutes.
Thereafter, the temperature inside the polymerization reactor was raised to 85° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was carried out to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion K.

(Preparation Example 12: Emulsion L)
Nalstar SR-110 (carboxy-modified SBR) manufactured by Nippon A&L Co., Ltd. was used as emulsion L.

(Preparation Example 13: Emulsion M)
Cyatex NA-106 (carboxy-modified NBR) manufactured by Nippon A&L Co., Ltd. was used as emulsion M.

(Preparation Example 14: Emulsion N)
In a pressure-resistant polymerization reactor, 57 parts by mass of 1,3-butadiene, 37 parts by mass of acrylonitrile, 6 parts by mass of methacrylic acid, 0.5 parts by mass of t-dodecyl mercaptan, 0.1 parts by mass of sodium dodecylbenzenesulfonate, 0.1 parts by mass of potassium chloride, 0.03 parts by mass of ethylenediaminetetraacetic acid, 0.0004 parts by mass of ferrous sulfate, and 125 parts by mass of polymerization water were charged under a nitrogen atmosphere, and after sufficient stirring, 0.06 parts by mass of potassium persulfate and 0.04 parts by mass of sodium formaldehyde sulfoxylate were added, and the temperature inside the reactor was raised to 30 ° C. Next, when the polymerization conversion rate reached 25%, 0.5 parts by mass of sodium dodecylbenzenesulfonate and 1 part by mass of polymerization water were added. 240 minutes after the addition, the temperature was raised to 45 ° C., and the temperature inside the reaction vessel was maintained at 45 ° C. thereafter.
Next, when the polymerization conversion rate reached 60%, 0.8 parts by mass of sodium dodecylbenzenesulfonate and 1.5 parts by mass of polymerization water were continuously added. Next, 0.04 parts by mass of potassium persulfate, 0.02 parts by mass of sodium formaldehyde sulfoxylate, and 0.5 parts by mass of polymerization water were added over 90 minutes. The polymerization conversion rate was confirmed every 90 minutes, and potassium persulfate, sodium formaldehyde sulfoxylate, and polymerization water were added in the above amounts and times until the polymerization conversion rate reached 95%. After the polymerization conversion rate reached 95%, the temperature inside the reaction vessel was raised to 50°C, and the reaction was stopped when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with potassium hydroxide, and steam distillation was performed to remove unreacted monomers and other low-boiling point compounds, to obtain Emulsion N.

(Preparation Example 15: Emulsion O)
Nikasol FX-2033 (acrylic emulsion) manufactured by Nippon Carbide Industries Co., Ltd. was used as emulsion O.

(Preparation Example 16: Emulsion P)
In a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 6.0 parts by mass of styrene, 4.0 parts by mass of 1,3-butadiene, 1.0 parts by mass of methyl methacrylate, 1.0 parts by mass of hydroxyethyl acrylate, 2.0 parts by mass of fumaric acid, 2 parts by mass of cyclohexene, 0.15 parts by mass of sodium dodecylbenzenesulfonate, and 0.3 parts by mass of sodium bicarbonate were charged under a nitrogen atmosphere and stirring was started. 1 part by mass of potassium persulfate was added and the temperature inside the reactor was raised to 70°C, and 54.0 parts by mass of styrene, 29.0 parts by mass of 1,3-butadiene, 3.0 parts by mass of methyl methacrylate, 0.47 parts by mass of t-dodecyl mercaptan, and 0.1 parts by mass of sodium dodecylbenzenesulfonate were continuously added over 420 minutes. After the addition of each monomer and other compounds was completed, 0.1 parts by mass of t-dodecyl mercaptan was immediately added and reacted for 150 minutes while maintaining the temperature at 70°C.
Thereafter, the temperature inside the polymerization reactor was raised to 85° C., and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH of the obtained emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was carried out to remove unreacted monomers and other low boiling point compounds, thereby obtaining Emulsion P.

(Preparation Example 17: Emulsion Q)
Emulsion Q was obtained by mixing emulsion O and emulsion P in a dry weight ratio of 1:1.

(Preparation Example 18: Emulsion R)
UW-1013D-C1 (urethane dispersion) manufactured by UBE Corporation was used as emulsion R.

(Preparation Example 19: Emulsion S)
Emulsion P and emulsion R were mixed in a dry weight ratio of 1:1 to obtain emulsion S.

(Preparation Example 20: Emulsion T)
Emulsion T was obtained by mixing emulsion O and emulsion R in a dry weight ratio of 1:1.

For the emulsions obtained in the above preparation examples, Tg, gel (%) and haze value were measured using the following methods.

[Tg]
The emulsion was cast on a glass plate and dried at 70°C for 4 hours to prepare a film, which was then packed in an aluminum pan and set in a differential scanning calorimeter (DSC7020: manufactured by Hitachi High-Tech Science Corp.). After cooling to -100°C, the apparatus was heated at a heating rate of 10°C/min to plot a DSC curve and a DSC differential curve.
Tg refers to the intersection of the tangents of the start and maximum inflection points of the endothermic heat of the phase change in the DSC curve, which are read, and the tangents of the respective points are drawn. When there are a plurality of endothermic heat start points, the start and maximum inflection points of the endothermic heat of the phase change in the DSC curve are read for each peak having a peak height ratio of 70% or more relative to the maximum peak height of the DSC differential curve, and the intersection of the tangents of the respective points is calculated, and the average of these is taken as the Tg value. The peak height refers to the length of the perpendicular line drawn from the peak top of the DSC differential curve to the straight line connecting the start and end points of the endothermic heat of the DSC differential curve.

[Haze value]
The emulsion was applied onto a PET film having a thickness of 0.1 mm using a rod bar (#8) and air-dried at 20°C for 10 minutes to obtain a film. The film thickness was 0.01 mm. After leaving the film standing overnight in an environment of 23°C and 50% RH, the haze value (JIS K7136:2000) was measured using a haze meter (HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd.). This value is designated as H1. As a blank, the haze value (JIS K7136:2000) of a PET film not coated with the emulsion was also measured in the same manner. This value is designated as H2. The haze value was calculated by subtracting H1 from H2 (blank correction).

[Preparation of Water-Based Phosphorescent Pigment Composition]
The components were mixed at room temperature (23°C) so that the mass percentages relative to the total mass of the composition were as shown in Table 1 below, to obtain a composition. The preservative used was Levanax BX-150, an isothiazolinone preservative manufactured by Shoei Chemical Co., Ltd. The thickener used was sodium polyacrylate (solid content 15±0.5%, pH 9.0±0.5%, B-type viscosity 4000-6000 mPa·s). The phosphorescent pigment used was SrAl ₂ O ₄ :Eu,Dy (emission color: green) manufactured by LTI Corporation, which had a 90% volume cumulative diameter D90 of 40 μm or less and a 50% volume cumulative diameter D50 of 10±4 μm.

The composition obtained above was stirred with water to obtain a water-based phosphorescent pigment composition. The amount of water was adjusted so that the total solids content of the water-based phosphorescent pigment composition was 70%. The compositions using emulsions A and B are the water-based phosphorescent pigment compositions of Comparative Examples 1 and 2, and the compositions using emulsions C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, and T are the water-based phosphorescent pigment compositions of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and 18, respectively.

[Preparation of fabric coated with water-based phosphorescent pigment composition]
The aqueous phosphorescent pigment compositions of Comparative Examples 1 and 2 and Examples 1 to 18 were diluted to a total solid content concentration of 50% by mass immediately before spray coating, stirred, filtered through a 200 mesh filter, and spray-coated onto fabric using a spray gun set SSG-15S-LC manufactured by KINKI.
A roll of fabric (manufactured by Shikisen Co., Ltd., cotton twill, with sill) was unwound and cut into a piece of fabric measuring 25 cm in the MD direction (length direction) and 30 cm in the TD direction (width direction) (30 cm x 25 cm). The water-based phosphorescent pigment composition diluted as described above was applied to the back surface of the cut fabric (the outer surface opposite to the inner surface of the winding) to a dry weight of 40 g/ ^m2 (single-sided coating), and dried in a hot air oven at 130°C for 10 minutes.
Immediately after being taken out of the hot air oven, while still hot, the fabric coated with the water-based phosphorescent pigment composition was sandwiched between 2 cm thick polycarbonate plates, and the fabric was stretched.

[Bending resistance by handle-o-meter method]
A strip-shaped test piece measuring 24 cm x 1 cm was cut out from the fabric coated with the aqueous phosphorescent pigment composition. The bending resistance was measured by the handle-o-meter method using a No. 226 handle-o-meter manufactured by Yasuda Seiki Seisakusho Co., Ltd., with a clearance of 1 cm, a measuring weight of 981 mN, and the coated surface facing up.
At this time, six test pieces were taken out from each piece of fabric, and after obtaining an evaluation value of n6, the highest and lowest values were excluded and the average value was calculated for the remaining four points. Two fabric test pieces were prepared for each emulsion, and the respective average values were further averaged to obtain the Handle-O-Meter measurement value.
Specifically, the process is as follows. Taking emulsion A as an example, emulsion A was applied to a fabric to obtain two sheets of coated fabric, A1 and A2, and six fabric test pieces of the above size were obtained from each of A1 and A2. This resulted in a total of 12 fabric test pieces, A1-1, A1-2, A1-3, A1-4, A1-5, A1-6; A2-1, A2-2, A2-3, A2-4, A2-5, A2-6.
For A1-1, A1-2, A1-3, A1-4, A1-5 and A1-6, the bending resistance was measured by the handle-ometer method under the above conditions, and the average value (A1-ave) was calculated from the four measured values excluding the maximum and minimum bending resistance values.
Similarly, for A2-1, A2-2, A2-3, A2-4, A2-5, and A2-6, the bending resistance was measured by the handle-ometer method under the above conditions, and the average value (A2-ave) was calculated from the four measured values excluding the maximum and minimum bending resistance values.
The average value of A1-ave and A2-ave was determined as the bending resistance (mN) of emulsion A measured by the handle-ometer method.

[Sensory evaluation]
A 25 cm x 2 cm test piece for sensory evaluation was obtained from the same fabric test piece used for the bending resistance by the handle-o-meter method. 20 subjects were divided into 4 groups of 5 people each, and each group was given a test piece for sensory evaluation, and asked to give a rating of 4 ranks from the hardest (D) to the softest (A). From hard to soft, the ratings were D<C<B<A, and after counting, the rating given by the largest number of people for each emulsion was used as the rating for the sensory evaluation of that emulsion. The evaluation of the sensory test was performed according to Table 2 below. C to A were determined to be practically acceptable hardness.

The Tg and haze value of the emulsion, as well as the bending resistance and sensory test evaluation results of the water-based phosphorescent pigment composition using the handle-o-meter method, are shown in Table 3. The sensory test data shows the percentage of the number of subjects who gave ratings A to D.

Claims (8)

A water-based phosphorescent pigment composition comprising an aqueous medium, one or more polymers dispersed in the aqueous medium , and a phosphorescent pigment having a 90% cumulative volume diameter D90 of 50 μm or less ,
the polymer is at least one selected from the group consisting of a conjugated diene polymer, an acrylic polymer, and a urethane polymer;
The emulsion of the polymer is applied onto a PET film having a thickness of 0.1 mm, air-dried at 20° C. for 10 minutes to give a thickness of 0.01 mm, and allowed to stand overnight in an environment of 23° C. and 50% RH. When the haze value of the film measured in accordance with JIS K7136:2000 is H1, and the haze value of the PET film not coated with the emulsion is measured in accordance with JIS K7136:2000 is H2, the blank-corrected haze value calculated by H1-H2 is 35% or less . The aqueous phosphorescent pigment composition according to claim 1, wherein the conjugated diene polymer is at least one selected from the group consisting of styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-vinylpyridine rubber, butadiene rubber, and natural rubber. The aqueous phosphorescent pigment composition according to claim 1, wherein the polymer has a glass transition temperature of -40 to 10°C as measured by a differential scanning calorimeter at a heating rate of 10°C/min. The aqueous phosphorescent pigment composition according to claim 1, wherein the phosphorescent pigment is a strontium aluminate compound doped with a lanthanoid rare earth element. The aqueous phosphorescent pigment composition according to claim 1, further comprising at least one selected from the group consisting of a thickener, a drying inhibitor, a pH adjuster, and a preservative. 2. The water-based phosphorescent pigment composition according to claim 1, wherein the aqueous solution of the composition has a stiffness of less than 300 mN at 23° ^C measured by a handle-o-meter method when the aqueous solution of the composition is applied to a fabric in an amount of 40 g/m2 as a dry weight. The aqueous phosphorescent pigment composition according to claim 1, which is used by adhering it to a fabric. The water-based phosphorescent pigment composition according to any one of claims 1 to 7 , which is for ink-jet printing.