JP2018127514A - Particle for hue adjustment and method for producing the same, resin composition for hue adjustment and sheet for hue adjustment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a particle for hue adjustment having excellent heat resistance, chemical resistance and light resistance.SOLUTION: A particle for hue adjustment has a light emitting material and a polymer with a glass transition temperature of 0°C or less.SELECTED DRAWING: None

Description

  The present invention relates to a hue adjusting particle, a production method thereof, a hue adjusting resin composition, and a hue adjusting sheet.

In recent years, improvements in design such as various signs attached to buildings, vehicles, electronic devices, and the like have been demanded. Among them, light emitting materials are used mainly for optical devices such as LED lighting. The purpose of using the luminescent material is not limited to ensuring brightness, imparting color, etc., but also for various purposes such as application to ultraviolet blocking and anti-counterfeiting.
In addition, since the luminescent material is used in various environments, it is desirable that the luminescent material is excellent in stability such as heat resistance, chemical resistance, and light resistance.

When using a light emitting material, there are cases where it is used by being dissolved or dispersed in a resin as a binder. For example, Patent Document 1 discloses a protective film having an adhesive layer in which a fluorescent dye is added to a transparent adhesive.
Patent Document 2 discloses luminescent particles coated with a propoxylated bisphenol A fumarate resin for the purpose of protecting the luminescent material used in the ink.

JP 2013-242166 A JP 2010-90379 A

  However, the protective film disclosed in Patent Document 1 may not be dissolved or dispersed in the adhesive resin depending on the type of the luminescent substance. Furthermore, the luminescent material may be quenched by the influence of the resin component.

  In addition, when the luminescent particles disclosed in Patent Document 2 are applied to a clear coat agent, a pressure-sensitive adhesive, etc., it is considered that transparency, pressure-sensitive adhesiveness, and the like are lowered.

  One aspect of the present invention is made in view of the above-described conventional circumstances, and is a hue adjusting particle having excellent heat resistance, chemical resistance, and light resistance, a method for producing the same, and a hue adjusting including the hue adjusting particle. An object of the present invention is to provide a resin composition. Furthermore, another aspect of the present invention is to provide a hue adjusting sheet that is excellent in transparency and adhesiveness and can be bonded to a transparent substrate such as glass and plastic while maintaining light emission. And

  As a result of intensive studies by the present inventors, it is possible to maintain stability such as heat resistance of the luminescent substance by using the color adjusting particles containing the luminescent substance and a polymer having a glass transition temperature of 0 ° C. or less. I found. Furthermore, the present inventors use a hue adjusting resin composition obtained by mixing hue adjusting particles and a transparent resin, so that the glass is excellent in transparency and adhesiveness, and has a light-emitting property. It was found that a hue adjusting sheet that can be bonded to a transparent substrate such as plastic can be obtained.

That is, one aspect of the present invention is as follows, for example.
<1> Hue adjusting particles containing a luminescent material and a polymer having a glass transition temperature of 0 ° C. or lower.
<2> The hue adjusting particles according to <1>, wherein the average particle diameter is 1 μm or less.
<3> The hue adjusting particles according to <1> or <2>, wherein the polymer includes a (meth) acrylic resin.
<4> The hue adjusting particle according to any one of <1> to <3>, wherein the light-emitting substance includes at least one selected from an organic phosphor and a rare earth metal complex.
<5> Hue adjustment according to any one of <1> to <4>, including a step of emulsion polymerization or suspension polymerization of a monomer composition containing a light-emitting substance and a polymerizable monomer having an unsaturated ethylene group. Method for producing particles.
<6> A hue-adjusting resin composition comprising the hue-adjusting particles according to any one of <1> to <4> and a transparent resin.
<7> The hue adjusting resin composition according to <6>, wherein the difference between the refractive index of the cured product of the transparent resin and the refractive index of the hue adjusting particles is within 0.01.
<8> The hue adjusting resin composition according to <6> or <7>, wherein the glass transition temperature of the transparent resin is 0 ° C. or lower.
<9> The hue adjusting resin composition according to any one of <6> to <8>, wherein the transparent resin includes a (meth) acrylic resin.
<10> The hue adjusting resin composition according to any one of <6> to <9>, further including an ultraviolet absorber.
<11> A hue adjusting sheet obtained by curing the hue adjusting resin composition according to any one of <6> to <10>.
<12> a base material;
A hue adjusting layer provided on at least one surface of the substrate, and obtained by curing the hue adjusting resin composition according to any one of <6> to <10>;
A hue adjusting sheet having

  According to one embodiment of the present invention, it is possible to provide a hue adjusting particle excellent in heat resistance, chemical resistance and light resistance, a method for producing the same, and a hue adjusting resin composition including the hue adjusting particle. Furthermore, according to the other one aspect | mode of this invention, it is excellent in transparency and adhesiveness, and provides the hue adjustment sheet | seat which can be bonded to transparent base materials, such as glass and a plastic, holding luminescent property. Can do.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.
In the present disclosure, the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. .
In the present disclosure, the numerical ranges indicated using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of types of substances corresponding to each component, the content or content of each component means the total content or content of the plurality of types of substances unless otherwise specified.
In the present disclosure, a plurality of particles corresponding to each component may be included. When there are a plurality of types of particles corresponding to each component, the particle diameter of each component means a value for a mixture of the plurality of types of particles unless otherwise specified.
In the present disclosure, the term “layer” refers to a case where the layer is formed only in a part of the region in addition to the case where the layer is formed over the entire region. included.
In the present disclosure, “(meth) acryl” means at least one of acryl and methacryl, and “(meth) acrylate” means at least one of acrylate and methacrylate.

[Hue Adjusting Particles and Method for Producing the Same]
The hue adjusting particles of the present disclosure include a luminescent material and a polymer having a glass transition temperature of 0 ° C. or lower. The hue adjusting particles of the present disclosure are excellent in heat resistance, chemical resistance and light resistance.
Below, each component which comprises the particle | grains for hue adjustment of this indication is demonstrated.

<Luminescent material>
The light-emitting substance used in the present disclosure is not particularly limited and is appropriately selected depending on the purpose. However, a material that converts ultraviolet light into visible light is preferable from the viewpoint of design properties and conversion efficiency. The luminescent material preferably contains at least one selected from organic phosphors and rare earth metal complexes. As the luminescent substance, a compound having an upconversion function such as a carbon nanotube derivative or PdPh ₄ TBP (palladium (II) meso-tetraphenyl-tetrabenzoporphyrin) can also be used.

(Organic phosphor)
Examples of organic phosphors include organic dyes such as cyanine dyes, pyridine dyes, and rhodamine dyes. Specific examples of organic phosphors include Lumogen F Violet 570, Yello 083, Orange 240, and Red 300 manufactured by BASF Japan Ltd .; basic dye Rhodamine B manufactured by Taoka Chemical Industry Co., Ltd .; manufactured by Sumika Fine Chem Co., Ltd. Sumiplast Yellow FL7G, etc .; MACROLEX Fluorescent Red G, Bayer 10GN, etc. manufactured by Bayer; LS R-400, manufactured by Tail Navi Co., Ltd .;

(Rare earth metal complex)
The metal constituting the rare earth metal complex is preferably at least one of europium and samarium, more preferably europium, from the viewpoint of luminous efficiency. The ligand constituting the rare earth metal complex is not particularly limited as long as it can be coordinated to the rare earth metal, and can be appropriately selected according to the metal to be used. Among these, from the viewpoint of luminous efficiency, an organic ligand is preferable, and an organic ligand capable of forming a complex with at least one of europium and samarium is preferable.

In the present disclosure, the ligand constituting the rare earth metal complex is not limited, but the ligand includes a neutral ligand, a nitrogen-containing organic compound, a nitrogen-containing aromatic heterocyclic compound, and a phosphine oxide. In addition, it is preferably at least one selected from the group consisting of carboxylic acids and β-diketones that are anionic ligands.
Further, when β-diketone is used as a ligand of the rare earth metal complex, a general formula: R ₁ COCHR ₂ COR ₃ (wherein R ₁ is an aryl group, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aralkyl group) R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aralkyl group or an aryl group, and R ₃ represents an aryl group, an alkyl group, a cycloalkyl group or a cycloalkyl group. Β-diketones represented by an alkyl group, an aralkyl group or a substituted product thereof may be contained.

  Specific examples of β-diketones include acetylacetone, perfluoroacetylacetone, benzoyl-2-furanoylmethane, 1,3-di (3-pyridyl) -1,3-propanedione, benzoyltrifluoroacetone, and benzoyl. Acetone, 5-chlorosulfonyl-2-thenoyltrifluoroacetone, bis (4-bromobenzoyl) methane, dibenzoylmethane, d, d-dicamphorylmethane, 1,3-dicyano-1,3-propanedione, p -Bis (4,4,5,5,6,6,6-heptafluoro-1,3-hexanedinoyl) benzene, 4,4'-dimethoxydibenzoylmethane, 2,6-dimethyl-3,5- Heptanedione, dinaphthoylmethane, dipivaloylmethane, bis (perfluoro-2-propoxypropionyl) Methane, 1,3-di (2-thienyl) -1,3-propanedione, 3- (trifluoroacetyl) -d-camphor, 6,6,6-trifluoro-2,2-dimethyl-3,5 -Hexanedione, 1,1,1,2,2,6,6,7,7,7-decafluoro-3,5-heptanedione, 6,6,7,7,8,8,8-heptafluoro -2,2-dimethyl-3,5-octanedione, 2-furyltrifluoroacetone, hexafluoroacetylacetone, 3- (heptafluorobutyryl) -d-camphor, 4,4,5,5,6,6 6-heptafluoro-1- (2-thienyl) -1,3-hexanedione, 4-methoxydibenzoylmethane, 4-methoxybenzoyl-2-furanoylmethane, 6-methyl-2,4-heptanedione, 2 -Naftoy Rutrifluoroacetone, 3- (5-phenyl-1,3,4-oxadiazol-2-yl) -2,4-pentanedione, 3-phenyl-2,4-pentanedione, 3- [3 ′, 5′-bis (phenylmethoxy) phenyl] -1- (9-phenanthyl) -1-propane-1,3-dione, 5,5-dimethyl-1,1,1-trifluoro-2,4-hexanedione 1-phenyl-3- (2-thienyl) -1,3-propanedione, 3- (t-butylhydroxymethylene) -d-camphor, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,2,2,3,3,7,7,8,8,9,9,9-tetradecafluoro-4,6-nonanedione, 2,2,6,6-tetramethyl-3 , 5-Heptanedione, 4,4,4-trifluoro 1- (2-naphthyl) -1,3-butanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5 -Heptanedione, 2,2,6,6-tetramethyl-3,5-octanedione, 2,2,6-trimethyl-3,5-heptanedione, 2,2,7-trimethyl-3,5-octane Dione, 4,4,4-trifluoro-1- (2-thienyl) -1,3-butanedione (TTA), 1- (pt-butylphenyl) -3- (N-methyl-3-pyrrole) -1,3-propanedione (BMPP), 1- (pt-butylphenyl) -3- (p-methoxyphenyl) -1,3-propanedione (BMDBM), 1,3-diphenyl-1,3 -Propanedione, dibenzoylacetone, Isobutyroylmethane, dipivaloylmethane, 3-methylpentane-2,4-dione, 2,2-dimethylpentane-3,5-dione, 2-methyl-1,3-butanedione, 1,3-butanedione 3-phenyl-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 2, 2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, 2-acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl -1,3-propanedione, 1,3-diphenyl-2-methyl-1,3-propanedione, 1-ethoxy-1,3-butanedione, and the like.

  Examples of nitrogen-containing organic compounds, nitrogen-containing aromatic heterocyclic compounds, and phosphine oxides that are neutral ligands of rare earth metal complexes include 1,10-phenanthroline, 2,2′-bipyridyl, 2,2 ′: 6, 2 ″ -terpyridine, 4,7-diphenyl-1,10-phenanthroline, 2- (2-pyridyl) benzimidazole, triphenylphosphine oxide, tri-n-butylphosphine oxide, tri-n-octylphosphine oxide, tri -N-butyl phosphate, 5,6-dihydroxy-1,10-phenanthroline, 1-phenyl-3-methyl-4-benzoyl-5-pyrazole, 1-phenyl-3-methyl-4- (4-butylbenzoyl) -5-pyrazole, 1-phenyl-3-methyl-4-isobutyryl-5-pyrazole, - phenyl-3-methyl-4-trifluoroacetyl-5-pyrazole, and the like.

As a rare earth metal complex having the above ligand, for example, from the viewpoint of wavelength conversion efficiency, for example, Eu (TTA) ₃ phen ((1,10-phenanthroline) tris [4,4,4-trifluoro-1 -(2-thienyl) -1,3-butanedionato] europium (III)), Eu (BMPP) ₃ phen ((1,10-phenanthroline) tris [1- (pt-butylphenyl) -3- (N -Methyl-3-pyrrole) -1,3-propanedionate] europium (III)) and Eu (BMDBM) ₃ phen ((1,10-phenanthroline) tris [1- (pt-butylphenyl) -3 -(P-Methoxyphenyl) -1,3-propanedionate] europium (III)) can be preferably used.

  In the hue adjusting particles of the present disclosure, the luminescent material is in a state of being coated with a polymer. The reason for coating the luminescent material with a polymer is to maintain the stability of the luminescent material, such as heat resistance, chemical resistance, and weather resistance. In addition, organic phosphors, metal rare earth complexes, and the like, which are light-emitting substances, can suppress concentration quenching by coating with a polymer.

(polymer)
The polymer used in the present disclosure is not particularly limited as long as the glass transition temperature is 0 ° C. or lower. When the glass transition temperature of the polymer is 0 ° C. or lower, it tends to be able to suppress a decrease in the adhesive strength of the transparent resin when mixed with a transparent resin described later used as an adhesive.
The glass transition temperature of a polymer refers to a value measured by differential scanning calorimetry.
The glass transition temperature of the polymer is preferably −10 ° C. or lower, and more preferably −20 ° C. or lower.

The type of polymer used in the present disclosure is not particularly limited as long as the glass transition temperature is 0 ° C. or lower, and a resin such as (meth) acrylic resin, urethane resin, epoxy resin, polyester resin, polyethylene resin, polyvinyl chloride resin, etc. There can be mentioned. Since the average particle diameter of the hue adjusting particles is preferably 1 μm or less, it is preferable that a (meth) acrylic resin is included from the viewpoint of the production method. The proportion of the (meth) acrylic resin in the polymer is not particularly limited, and is preferably 50% by mass to 100% by mass, and more preferably 80% by mass to 100% by mass.
The (meth) acrylic resin preferably has a hydroxy group in order to improve the adhesiveness of the hue adjusting sheet described later. The (meth) acrylic resin having a hydroxy group can be prepared by using at least one of an acrylic acid alkyl ester having a hydroxy group and a methacrylic acid alkyl ester having a hydroxy group as at least a part of the polymerizable monomer.

  The method for producing the hue adjusting particles is not particularly limited, and a luminescent substance is dissolved or dispersed in a polymerizable monomer having an unsaturated ethylene group to form a monomer composition, and this monomer composition is polymerized (bulk polymerization, Suspension polymerization, emulsion polymerization, solution polymerization, etc.), casting method, melting method and the like. From the viewpoint of ease of post-treatment, a method including a step of emulsion polymerization or suspension polymerization of a monomer composition containing a light-emitting substance and a polymerizable monomer having an unsaturated ethylene group is preferred. From the viewpoint, a method including a step of emulsion polymerization is more preferable. The polymer according to the present disclosure is formed by polymerizing a polymerizable monomer having an unsaturated ethylene group.

  The content of the luminescent material in the hue adjusting particles is not particularly limited and can be appropriately selected according to the purpose, the type of the luminescent material, etc., but is preferably 0.001% by mass to 1% by mass. More preferably, it is 1 mass%-0.5 mass%.

  There is no limitation in particular in the polymerizable monomer which has an unsaturated ethylene group contained in a monomer composition, For example, acrylic acid, methacrylic acid, and these alkylesters are mentioned.

Specific examples of alkyl acrylates and alkyl methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. Acrylic acid unsubstituted alkyl ester and methacrylic acid unsubstituted alkyl ester; dicyclopentenyl (meth) acrylate; dicyclopentanyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; benzyl (meth) acrylate; , 2,6,6-pentamethylpiperidyl methacrylate; 2,2,6,6-tetramethylpiperidyl methacrylate; a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid (for example, Polyethylene glycol di (meth) acrylate (having 2 to 14 “—CH ₂ CH ₂ O—”), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) acrylate (“—CH ₂ CH (CH ₃ ) O— ”having 2 to 14), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A polyoxyethylene di (meth) acrylate, Phenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, etc.); α, β-unsaturated carboxylic acid added to glycidyl group-containing compound (Trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc.); a polyvalent carboxylic acid (phthalic anhydride, etc.), a substance having a hydroxy group and an ethylenically unsaturated group (for example, β-hydroxyethyl (meth) acrylate); urethane (meth) acrylate (for example, reaction product of tolylene diisocyanate and 2-hydroxyethyl (meth) acrylate, trimethylhexamethylene diisocyanate) Anate, a reaction product of cyclohexanedimethanol and 2-hydroxyethyl (meth) acrylic acid ester); an acrylic acid-substituted alkyl ester or a methacrylic acid-substituted alkyl ester in which a hydroxy group, an epoxy group, a halogen group or the like is substituted on these alkyl groups And so on.

  Examples of the compound that can be copolymerized with acrylic acid, methacrylic acid, alkyl acrylate ester or alkyl methacrylate ester include acrylamide, acrylonitrile, diacetone acrylamide, styrene, vinyltoluene, and the like. These vinyl monomers can be used alone or in combination of two or more.

<Radical polymerization initiator>
In the present disclosure, it is preferable to use a radical polymerization initiator in order to polymerize a monomer composition containing a polymerizable monomer having an unsaturated ethylene group. As the radical polymerization initiator, a commonly used radical polymerization initiator can be used without particular limitation. For example, a peroxide is preferable. Specifically, inorganic peroxides, organic peroxides and azo radical initiators that generate free radicals by heat are preferred.

  Examples of inorganic peroxides include potassium persulfate (dipotassium peroxosulfate), sodium persulfate, and ammonium persulfate.

  Organic peroxides include isobutyl peroxide, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, bis-s-butyl. Peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecano Acid, bis-2-ethoxyethyl peroxydicarbonate, bis (ethylhexyl) peroxydicarbonate, t-hexyl peroxyneodecanoate, bismethoxybutyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl ) Peroxydicarbonate, t -Butylperoxyneodecanoate, t-hexylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3- Tetramethylbutylperoxy-2-ethylhexanoate, succinic peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 4-methylbenzoyl peroxide, t-butylperoxy-2-ethylhexanoate, m-toluoylbenzoyl peroxide, benzoyl Peroxide, t-butyl per Xyisobutyrate, 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis ( t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexanone, 2,2-bis ( 4,4-dibutylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3 , 5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5- (M-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (Benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) ) Valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexane, t-butylcumyl peroxide, p-menthane hydroperoxy Id, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Examples include cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and bis (1-phenyl-1-methylethyl) peroxide.

  As the azo radical initiator, azobisisobutyronitrile (AIBN, trade name V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylisobutyronitrile) (trade name) V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2,4-dimethylvaleronitrile) (trade name V-65, manufactured by Wako Pure Chemical Industries, Ltd.), dimethyl-2,2 ′ -Azobis (isobutyrate) (trade name V-601, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name V-70, Wako Pure Chemical) Kogyo Co., Ltd.).

  The usage-amount of a radical polymerization initiator can be suitably selected according to the kind of polymerizable monomer which has an unsaturated ethylene group, the refractive index of the resin particle formed, etc., and is used by the usage-amount normally used. Specifically, for example, the polymerizable monomer having an unsaturated ethylene group can be used in a range of 0.01% by mass to 2% by mass, and used in a range of 0.05% by mass to 1% by mass. It is preferable to do.

(Refractive index)
The refractive index of the hue adjusting particles is desirably approximated to the refractive index of the cured product of the transparent resin to be used from the viewpoint of maintaining the transparency of the hue adjusting sheet described later. More specifically, the difference between the refractive index of the cured product of the transparent resin and the refractive index of the hue adjusting particles is more preferably within 0.01. Therefore, a polymerizable monomer having an unsaturated ethylene group constituting the polymer used for the hue adjusting particles may be selected in accordance with the refractive index of the cured product of the transparent resin to be used.
In the present disclosure, the refractive index of the hue adjusting particles refers to a value measured by an immersion method in an environment of 25 ° C. In the present disclosure, the refractive index of the hue adjusting sheet described later refers to a value measured in an environment of 25 ° C. by the Abbe method.

(Average particle size)
The average particle diameter of the hue adjusting particles is preferably 1 μm or less, and more preferably 0.05 μm to 0.15 μm. If the average particle diameter of the hue adjusting particles is within the above range, the hue adjusting particles can be suitably used as a component of the pressure-sensitive adhesive or nano-coating agent.
The average particle diameter of the hue adjusting particles refers to a volume-based average particle diameter (volume average particle diameter) measured by a laser diffraction / scattering method.

[Hue Adjustment Resin Composition]
The hue adjusting resin composition of the present disclosure includes the hue adjusting particles of the present disclosure and a transparent resin. The hue adjusting resin composition can be obtained by mixing the hue adjusting particles and the transparent resin. Examples of the mixing method include a method in which a liquid in which hue adjusting particles are dispersed in a solvent such as ethyl acetate is mixed with a transparent resin. The content of the hue adjusting particles in the hue preparing resin composition is not particularly limited. For example, the content of the hue adjusting particles in the solid content of 100 parts by mass of the hue preparing resin composition is 0.1 mass. Part to 50 parts by weight, preferably 1 part to 20 parts by weight.

(Transparent resin)
The transparent resin in the present disclosure is not particularly limited as long as it is transparent, and a resin according to the purpose may be used. In the present disclosure, the term “transparent” means that the transmittance of light having a wavelength of 1 nm to 400 nm to 800 nm is 90% or more. For example, when the resin composition for hue preparation is used as an adhesive, the glass transition temperature of the transparent resin is preferably 0 ° C. or lower. The method for measuring the glass transition temperature of the transparent resin is the same as the method for measuring the glass transition temperature of the polymer described above.
The glass transition temperature of the transparent resin is more preferably −10 ° C. or lower, and further preferably −20 ° C. or lower.
Examples of the transparent resin include urethane resin, epoxy resin, polyester resin, polyethylene resin, polyvinyl chloride resin, (meth) acrylic resin, etc., and hydroxyl group, carboxy group, amino group in the resin skeleton or side chain. It preferably contains a reactive functional group such as an isocyanate group. Although there is no restriction | limiting in particular as a monomer compound used as the raw material of transparent resin, It is preferable that the (meth) acrylic acid ester containing a hydroxyl group is included at least.

Examples of the (meth) acrylic resin used as the transparent resin include epoxy (meth) acrylate, urethane (meth) acrylate, and acrylic (meth) acrylate. The (meth) acrylic resin preferably contains a hydroxy group.
Examples of commercially available (meth) acrylic resins containing a hydroxy group include Hitachi Chemical 5505, Hitachi 5507, and Hitachi 1005B manufactured by Hitachi Chemical Co., Ltd.

The hue adjusting resin composition may contain an ultraviolet absorber. Although it does not specifically limit as a ultraviolet absorber, The compound which has an unsaturated double bond is preferable. Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, triazine compounds, cyanoacrylate compounds, formamidine compounds, oxanilide compounds, salicylate compounds, and the like. Commercially available products include “Tinuvin 327”, “Tinubin 328”, “Tinubin 400”, “Tinubin 460” “Tinubin 479”, “Tinubin 900”, “Tinubin 928”, “Ubinar 3035” (above, BASF Japan Ltd.) Product), “Seesorb 100”, “Seesorb 101”, “Seesorb 103”, “Seesorb 151”, “Seesorb UV-1” (manufactured by Sipro Kasei Co., Ltd.), and the like. These ultraviolet absorbers may be used alone or in combination of two or more. Moreover, you may use together with a light stabilizer.
When the hue adjusting sheet of the present disclosure obtained by using the hue adjusting resin composition is used in an application exposed to light such as sunlight, by including an ultraviolet absorber in the hue adjusting resin composition. Deterioration of the substrate and the like due to ultraviolet rays can be prevented.

  The content of the ultraviolet absorber is preferably 0.1 parts by mass to 10 parts by mass, and 0.5 parts by mass to 1 part by mass when the solid content of the hue adjusting resin composition is 100 parts by mass. More preferably. In the case where a light emitting material that is excited by ultraviolet rays is used, the light emitting property is not greatly affected as long as it is within the above range.

The hue adjusting resin composition may contain curing components such as a polymerization initiator and a curing agent in order to cure the transparent resin.
Examples of the method for curing the hue adjusting resin composition include UV curing and thermosetting. Depending on the curing mode, the hue adjusting resin composition may contain a photopolymerization initiator, a thermal polymerization initiator, or the like. Moreover, you may mix and harden the hardening | curing agent which reacts with the reactive substituent which transparent resin has. For example, when the transparent resin has a hydroxy group, an isocyanate curing agent can be used. Examples of the isocyanate-based curing agent include Sumijour N3300 manufactured by BAYER, Duranate AE710-100 manufactured by Asahi Kasei Corporation, and the like.
The content of the curing component can be appropriately adjusted in view of the type of the curing component, the curing method, the type of the transparent resin, and the like.

[Hue adjustment sheet]
The first hue adjusting sheet of the present disclosure is obtained by curing the hue adjusting resin composition of the present disclosure. The method for curing the hue adjusting resin composition is not particularly limited, and examples thereof include UV curing and thermosetting.
Although the average thickness in the 1st hue adjustment sheet | seat is not specifically limited, For example, it is preferable that they are 5 micrometers-500 micrometers, and it is more preferable that they are 10 micrometers-100 micrometers.
The 1st hue adjustment sheet | seat may contain the ultraviolet absorber. By curing the hue adjusting resin composition of the present disclosure including the ultraviolet absorber, the ultraviolet absorber can be included in the first hue adjusting sheet.

The 2nd hue adjustment sheet | seat of this indication has a base material and the hue adjustment layer which is provided in the at least one surface of the said base material, and hardens the hue adjustment resin composition of this indication.
The method for curing the hue adjusting resin composition to form the hue adjusting layer is not particularly limited, and examples thereof include UV curing and thermosetting.
Although the average thickness of a hue adjustment layer is not specifically limited, For example, it is preferable that they are 5 micrometers-500 micrometers, and it is more preferable that they are 10 micrometers-100 micrometers.
The hue adjustment layer may contain an ultraviolet absorber. By curing the hue adjusting resin composition of the present disclosure including the ultraviolet absorber, the ultraviolet absorber can be included in the hue adjusting layer in the second hue adjusting sheet.

  If the base material used by this indication is transparent, it will not specifically limit, The base material normally used in the said technical field can be used. Examples of the substrate include glass, polycarbonate, polymethyl (meth) acrylate, polyethylene terephthalate (PET), polyolefin and the like. The thickness of a base material is not specifically limited, You may use what was match | combined with the objective.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” and “part” are based on mass.

[Example 1]
(Preparation of particles for hue adjustment)
In a 500 mL four-necked round bottom separable flask, 8.4 g of surfactant Neoperex G-15 (manufactured by Kao Corporation) and 318 g of pure water are added, three faddler stirrers, temperature sensor and nitrogen inlet tube Attached. The separable flask was capped, a reflux tube was attached, cooling water was passed through, a water bath was attached and water was added, and stirring was started at 140 rpm using a three-one motor. Put 8.3 g of methyl acrylate, 54.2 g of butyl acrylate, 3.3 g of ethylene glycol dimethacrylate, 0.7 g of 1,2,2,6,6-pentamethylpiperidyl methacrylate into the sample tube. 0.3 g of fluorescent substance LS R-400 (manufactured by Tail Navi) was added and dissolved in the monomer. This liquid was added into the flask, a nitrogen supply tube was attached to the nitrogen introduction tube, and nitrogen was introduced into the slurry at 50 ml / min. After 1 hour, the nitrogen supply was switched from the slurry to the gas phase, and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., a solution prepared by dissolving 0.06 g of dipotassium peroxosulfate as a radical initiator in 11.3 g of pure water was added to initiate polymerization. Sampling was conducted after 6 hours, and it was confirmed that the polymerization rate was 95% or more and then cooled. The slurry liquid after synthesis was subjected to a laser diffraction scattering particle size distribution measuring device (manufactured by Beckman Coulter, trade name: LS13320), using a pump speed of 50%, a refractive index of phosphor-containing particles of 1.48, and a refractive index of water of 1.33. As a result, when the average particle diameter was measured, the volume average particle diameter was 98 nm. 40 g of anhydrous sodium sulfate was placed in a 1 L flask, 400 g of pure water was added and dissolved, the slurry was slowly added thereto, and the mixture was stirred for 1 hour to salt out the particles and filtered. Furthermore, washing with pure water and filtration were repeated to remove the surfactant, and drying at 60 ° C. yielded hue adjusting particles.

(Preparation of solvent dispersion of hue adjusting particles)
Put 2 g of hue adjusting particles prepared in the previous section and 18 g of ethyl acetate into a 50 cc sample tube, perform ultrasonic irradiation for 10 minutes, and further stir at 300 rpm for 30 minutes using a magnetic stirrer. % Solvent dispersion was obtained.

(Preparation of hue adjusting resin composition)
To a 20 cc sample tube, add 10 g of a transparent resin, HITAROID 5507 (solid content 40%, glass transition temperature -33 ° C., manufactured by Hitachi Chemical Co., Ltd.), 8 g of the dispersion liquid for adjusting the hue prepared in the previous section. After mixing well, the mixture was mixed with a mix rotor for 1 hour to obtain a particle resin mixture.
In a 20 cc sample tube, 18 g of the particle resin mixture prepared in the previous section, 0.002 g of Duranate AE710-100 (manufactured by Asahi Kasei Co., Ltd.) which is an isocyanate curing agent, and Tinuvin 460 (manufactured by BASF Japan) which is an ultraviolet absorber. 04 g was added and mixed with a mix rotor for 1 hour to obtain a hue adjusting sheet coating solution (hue adjusting resin composition).

(Preparation of hue adjustment sheet)
On a PET film (Cosmo Shine (registered trademark) A-4300, manufactured by Toyobo Co., Ltd.), the color adjusting sheet coating solution prepared in the previous section is applied with a thickness of 100 μm using an applicator, and cured and dried at 100 ° C. for 30 minutes. A hue adjusting layer was formed on the surface of the PET film. After drying, a release film (separator) was laminated on the hue adjustment layer surface using a hand roller to obtain a hue adjustment sheet.

[Example 2]
Monomers used for the preparation of hue adjusting particles are 6.9 g of methyl acrylate, 54.2 g of butyl acrylate, 1.4 g of 2-hydroxyethyl acrylate, 3.3 g of ethylene glycol dimethacrylate, 1, 2, 2, 6 A hue adjusting sheet was produced in the same manner as described in Example 1 except that 0.7 g of 1,6-pentamethylpiperidyl methacrylate was used. The volume average particle diameter of the slurry liquid after synthesis was 104 nm.

[Comparative Example 1]
A hue adjusting sheet was produced in the same manner as described in Example 1 except that the hue adjusting particles were not added.

[Comparative Example 2]
A hue adjusting sheet in the same manner as described in Example 1 except that 0.0004 g of a rare earth metal complex (luminescent material) R-400 (manufactured by Tail Navi) is used instead of the hue adjusting particles. Was made.

[Comparative Example 3]
The monomer used for the preparation of the hue adjusting particles is 62.5 g of methyl methacrylate, 3.3 g of ethylene glycol dimethacrylate, 0.7 g of 1,2,2,6,6-pentamethylpiperidyl methacrylate, A hue adjusting sheet was prepared in the same manner as described in Example 1. The volume average particle diameter of the slurry liquid after synthesis was 100 nm.

[Comparative Example 4]
The hue is the same as the method described in Example 1 except that 0.0004 g of D-1165 (manufactured by Nemoto Lumi Material Co., Ltd.), which is an inorganic phosphor (luminescent material), is used instead of the particles for adjusting the hue. An adjustment sheet was prepared.

<Evaluation>
The following evaluation was performed about the obtained particles for hue adjustment and the sheet for hue adjustment. The obtained results are shown in Table 1.
[Evaluation 1: Refractive index measurement of hue adjusting particles and hue adjusting sheet]
An Abbe refractometer (“2T” manufactured by Atago Co., Ltd.) was used to measure the refractive index of the hue adjusting sheet at 25 ° C.
The refractive index of the hue adjusting particles was measured by an immersion method in an environment of 25 ° C. using an Abbe refractometer (“2T” manufactured by Atago Co., Ltd.).

[Evaluation 2: Evaluation of heat resistance of hue adjusting particles]
The hue adjusting particles were stored in a drier at 200 ° C. for 10 hours, the emission intensity retention before and after storage was determined, and used as an index of heat resistance of the hue adjusting particles. The higher the emission intensity retention rate, the better the heat resistance. The emission intensity was measured using a fluorescence spectrophotometer (F-2700, manufactured by Hitachi High-Technologies Corporation), and with an ethyl acetate dispersion (concentration 0.1%). The light emission intensity retention rate is calculated based on the following formula.
(Emission intensity after storage / Emission intensity before storage) × 100 (%)

[Evaluation 3: Evaluation of chemical resistance of hue adjusting particles]
The hue adjusting particles are immersed in a 0.1N hydrochloric acid aqueous solution and stored for 24 hours, and the emission intensity retention before and after storage is obtained in the same manner as in the heat resistance evaluation, and used as an index of chemical resistance of the hue adjusting particles. . The higher the emission intensity retention rate, the better the chemical resistance.

[Evaluation 4: Evaluation of light resistance of hue adjusting particles]
The hue adjusting particles are stored in a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours, and the emission intensity retention before and after storage is obtained in the same manner as in the heat resistance evaluation, and the light resistance of the hue adjusting particles is determined. It was used as an index. The higher the emission intensity retention rate, the better the light resistance.

[Evaluation 5: Measurement of total light transmittance of hue adjusting sheet]
The transmittance of the hue adjusting sheet at a wavelength of 500 nm was measured with a transmittance meter (manufactured by JASCO Corporation). In measuring the transmittance, the release film was removed. A PET film was used as a reference.

[Evaluation 6: Measurement of Luminous Intensity of Hue Adjustment Sheet]
The excitation peak intensity when the emission wavelength is set according to each luminescent substance after mounting the hue adjustment sheet prepared on a fluorescence spectrophotometer (manufactured by Hitachi High-Technologies Corporation) with the release film removed. It was measured. The emission wavelength was 600 nm for R-400 and 520 nm for D1165.

[Evaluation 7: Measurement of Adhesive Strength of Hue Adjustment Sheet]
The produced hue adjusting sheet was cut into a size of 20 mm × 100 mm, and then the release separator on one side was peeled off and laminated on glass to obtain a test piece. The test piece was attached to a tensile tester (manufactured by Shimadzu Corporation, Autograph AG-X / R), and the peel strength at a peeling angle of 180 ° and a peeling speed of 300 mm / min was measured in an environment of 23 ° C.

[Evaluation 8: Measurement of glass transition temperature of hue adjusting particles]
With a differential scanning calorimeter, 10 mg of the sample was put in an aluminum pan, and Tg was measured under the temperature rising condition of 5 ° C./min in the range of −100 ° C. to 100 ° C.
The glass transition temperature of the hue adjusting particles was regarded as the glass transition temperature of the polymer.

(Abbreviations in the table)
BA: butyl acrylate, MA: methyl acrylate, HEA: 2-hydroxyethyl acrylate, MMA: methyl methacrylate, FA-121M: ethylene glycol dimethacrylate, FA-711MM: 1,2,2,6,6-penta Methyl piperidyl methacrylate

  In the present disclosure, as shown in Examples 1 and 2, the hue adjusting particles retain heat resistance, chemical resistance and light resistance, and the hue adjusting sheet has total light transmittance (transparency) and light emission. Excellent strength. The reason why the transparency is excellent is considered to be that the difference in refractive index between the hue adjusting particles as the light emitting material and the pressure-sensitive adhesive is 0.01 or less. Further, as shown in Example 2, by adding a small amount of a monomer having a hydroxy group to the monomer composition of the hue adjusting particle, the same adhesiveness as that in the case where no particle is added as shown in Comparative Example 1 is shown. It was.

  On the other hand, as shown in Comparative Example 2, when the rare earth metal complex was used without using the hue adjusting particles, the heat resistance, chemical resistance and light resistance were not maintained and decreased. Further, as shown in Comparative Examples 3 and 4, when the glass transition temperature of the hue adjusting particles is 0 ° C. or higher, or when the inorganic phosphor is used without using the hue adjusting particles, the entire hue adjusting sheet is used. The light transmittance was small and the tackiness was further lowered.

Claims (12)

  A hue adjusting particle comprising a luminescent material and a polymer having a glass transition temperature of 0 ° C. or lower.   The hue adjusting particles according to claim 1, wherein the average particle diameter is 1 μm or less.   The hue adjusting particles according to claim 1, wherein the polymer contains a (meth) acrylic resin.   The hue adjusting particle according to any one of claims 1 to 3, wherein the luminescent material contains at least one selected from organic phosphors and rare earth metal complexes.   The hue adjusting particles according to any one of claims 1 to 4, comprising a step of emulsion polymerization or suspension polymerization of a monomer composition containing a luminescent substance and a polymerizable monomer having an unsaturated ethylene group. Production method.   A hue-adjusting resin composition comprising the hue-adjusting particles according to any one of claims 1 to 4 and a transparent resin.   The hue adjusting resin composition according to claim 6, wherein a difference between a refractive index of a cured product of the transparent resin and a refractive index of the hue adjusting particles is within 0.01.   The resin composition for hue adjustment according to claim 6 or 7, wherein the glass transition temperature of the transparent resin is 0 ° C or lower.   The resin composition for hue adjustment according to any one of claims 6 to 8, wherein the transparent resin contains a (meth) acrylic resin.   The hue adjusting resin composition according to any one of claims 6 to 9, further comprising an ultraviolet absorber.   A hue adjusting sheet obtained by curing the hue adjusting resin composition according to any one of claims 6 to 10. A substrate;
A hue adjustment layer provided on at least one surface of the base material and obtained by curing the hue adjustment resin composition according to any one of claims 6 to 10,
A hue adjusting sheet having