JP2022022095A - Composition for colloidal crystal, laminate, and method for producing laminate - Google Patents

Abstract

To provide a composition that can form a colloidal crystal layer that has excellent gravure printability and achieves both of favorable color development and low angle dependence, and a laminate having a colloidal crystal layer that is formed from the composition and achieves both of favorable color development and low angle dependence.SOLUTION: A composition for colloidal crystal contains fine resin particles (A), achromatic black fine particles (B), water, and at least one selected from the group consisting of a hydrophilic solvent with a boiling point of 95-250°C at 1 atm (C) and a nonionic surfactant with an HLB value of 10.0-19.0 (D). The composition has a surface tension of 25-42 mN/m at 25°C and is used for gravure printing.SELECTED DRAWING: None

Description

The present invention relates to a composition for colloidal crystals for forming colloidal crystals, and a laminate using the composition.

A photonic crystal is an artificial crystal having a nanoperiodic structure in which substances with different refractive indexes are arranged at intervals similar to the wavelength of light. Since it has various interesting optical properties such as confinement effect and photoamplification effect, it has been actively studied in recent years. Among them, colloidal crystals in which colloid-sized particles are regularly arranged are one of the photonic crystals that can be produced relatively easily, but due to problems in controlling the particle arrangement and its immobilization, they can be mass-produced. Has not been reached. Although attempts to print colloidal crystals with a pattern have been studied, the number of them is small, and it has not been possible to obtain a pattern printed matter having good color development property, low angle dependence, and resistance to various coating films.

In Patent Document 1, a composition for colloidal crystals containing monodisperse resin fine particles is applied in advance on a base material, an original plate is applied from the opposite side of the base material, and then heated in a state where irregularities are formed to form a particle layer. A method of printing a pattern by utilizing the difference in height, that is, the difference in the number of laminated particles is disclosed. However, in this method, the printing of the pattern is limited to the colloidal crystal layer. In addition, the contrast between the printed portion and the non-printed portion is difficult to obtain, and the legibility of the pattern is inferior. Further, since the composition for colloidal crystals described in Patent Document 1 is inferior in leveling property to a plate or a base material, a high-quality printed matter cannot be obtained by plate printing such as gravure printing.

Patent Document 2 discloses a composition for colloidal crystals that can be printed by an inkjet method. However, in the inkjet method, the amount that can be ejected at one time is very small, and the solvent rapidly volatilizes from the droplets, so that the arrangement of the particles is greatly disturbed, the color development property as a structural color is deteriorated, and the coating film is remarkably whitened. Further, even if the composition described in Patent Document 2 is applied to gravure printing, poor drying and poor leveling occur, and a high-quality printed matter cannot be obtained.

Based on the above, it is required to develop a composition for colloidal crystals and its laminate, which achieves both good printability, color development, and low angle dependence, good resistance to various coating films, and high-quality patterns. Has been done.

Japanese Unexamined Patent Publication No. 2006-159891 Japanese Unexamined Patent Publication No. 2002-002103

The problem to be solved by the present invention is a composition capable of forming a colloidal crystal layer having good gravure printability and achieving both excellent color development property and low angle dependence, and the composition. It is an object of the present invention to provide a laminate having a colloidal crystal layer having both excellent color development property and low angle dependence.

That is, the present invention comprises resin fine particles (A), achromatic black fine particles (B) (excluding resin fine particles (A)), water, and a hydrophilic solvent (C) having a boiling point of 95 to 250 ° C. at 1 atm. / Or contains a nonionic surfactant (D) having an HLB value of 10.0 to 19.0, a surface tension of 25 to 42 mN / m at 25 ° C., and is characterized by being used for gravure printing. Concerning the composition for colloidal crystals.

Further, in the present invention, the total amount of the hydrophilic solvent (C) and the nonionic surfactant (D) is 0.5 to 20% by mass based on the total amount of the composition for colloidal crystals, for the colloidal crystals. Regarding the composition.

Further, in the present invention, the hydrophilic solvent (C) is at least one selected from the group consisting of a lower monoalcohol solvent (C-1), a glycol solvent (C-2) and a glycol ether solvent (C-3). The present invention relates to the above-mentioned composition for colloidal crystals.

Further, in the present invention, the nonionic surfactant (D) contains at least one selected from the group consisting of polyoxyalkylene alkyl ethers (D-1) and polyglycerin fatty acid esters (D-2). The present invention relates to the above composition for colloidal crystals.

The present invention also relates to the above composition for colloidal crystals containing the resin fine particles (A) in an amount of 22.5 to 43.2% by mass based on the composition for colloidal crystals.

The present invention also relates to the above composition for colloidal crystals, which contains the achromatic black fine particles (B) in an amount of 0.10 to 20% by mass based on the resin fine particles (A).

Further, the present invention is for the colloidal crystal in which the resin fine particles (A) are of the core-shell type, the glass transition point of the core portion is 60 ° C. or higher, and the glass transition point of the shell portion is −50 to 20 ° C. Regarding the composition.

The present invention also relates to a composition for colloidal crystals in which the content of the shell of the resin fine particles (A) is in the range of 10 to 300% by mass with respect to the total mass of the core.

The present invention also relates to a laminate having a colloidal crystal layer formed from the above-mentioned colloidal crystal composition on a substrate.

The present invention also relates to the above-mentioned laminated body in which the substrate has a primer layer and the glass transition point of the primer layer is −60 to 100 ° C.

The present invention also relates to the above-mentioned laminated body in which the thickness of the colloidal crystal layer is 1.0 to 20 μm.

Further, the present invention is a method for producing a laminate having a colloidal crystal layer formed from a composition for colloidal crystals on a substrate.
On the substrate, resin fine particles (A), achromatic black fine particles (B) (excluding resin fine particles (A)), water, and a hydrophilic solvent (C) having a boiling point of 95 to 250 ° C. at 1 atm and / Or a composition for colloidal crystals containing a nonionic surfactant (D) having an HLB value of 10.0 to 19.0 and having a surface tension of 25 to 42 mN / m at 25 ° C. is gravure-printed to form a colloidal crystal. The present invention relates to a method for producing a laminated body, which comprises a step of forming a layer.

INDUSTRIAL APPLICABILITY According to the present invention, a composition having good gravure printability and capable of forming a colloidal crystal layer having both excellent color development property and low angle dependence, and an excellent composition formed from the composition. It is possible to provide a laminate provided with a colloidal crystal layer that achieves both color development and low angle dependence.

<Composition for colloidal crystals>
The composition for colloidal crystals of the present invention is for gravure printing, and is hydrophilic with resin fine particles (A), achromatic black fine particles (B), water, and a boiling point of 95 to 250 ° C. per atmospheric pressure. It contains a solvent (C) and / or a nonionic surfactant (D) having an HLB value of 10.0 to 19.0, and has a surface tension of 25 to 42 mN / m at 25 ° C.
The composition of the present invention contains a hydrophilic solvent (C) having a predetermined boiling point and / or a nonionic surfactant (D) having a predetermined HLB value, and has a predetermined surface tension, whereby excellent gravure is obtained. It has a remarkable effect of having printability and enabling high-quality pattern printing that has both color development and low angle dependence. Further, the colloidal crystals formed from the composition of the present invention are excellent in followability to a substrate, abrasion resistance, and solvent resistance.
Hereinafter, the requirements constituting the present invention will be described in detail.

<Resin fine particles (A)>
The resin fine particles (A) used in the present invention exist in the form of a dispersion in the composition for colloidal crystals, and are densely packed by the advection accumulation phenomenon accompanying the volatilization of water in the process of being applied to the substrate and dried. Arrange and stack regularly in the form. Then, the void portion is replaced with air from water to form a colloidal crystal layer. The colloidal crystal layer in the present specification is a layer that expresses a structural color derived from Bragg reflection, and can develop various colors by controlling the periodic interval by controlling the particle size of the resin fine particles (A). ..
The average particle size of the resin fine particles (A) is preferably in the range of 180 to 330 nm. Within the above range, the color development of the colloidal crystal layer in the visible light region becomes clear, and a colloidal crystal coating film having more excellent color development can be obtained, which is preferable. The average particle size in the present specification can be measured by a dynamic light scattering method, and the peak of the obtained volume particle size distribution data (histogram) is taken as the average particle size.

[Polymer of ethylenically unsaturated monomer (a)]
The type and production method of the resin fine particles (A) are not particularly limited, and any monodispersable resin fine particles can be used, but the refractive index of the fine particles (A) can be easily controlled and the monodispersity can be easily controlled. The resin fine particles (A) are preferably a polymer of the ethylenically unsaturated monomer (a) from the viewpoint of excellent color development. More preferably, it is a resin fine particle made of an acrylic resin or a styrene acrylic resin.

The resin fine particles, which are the polymers of the ethylenically unsaturated monomer (a), can be produced, for example, by the following emulsion polymerization.
First, an aqueous medium and a surfactant are charged in the reaction vessel, and the temperature is raised to a predetermined temperature. On the other hand, water, a surfactant, and the ethylenically unsaturated monomer (a) are charged in the dropping tank and stirred to prepare an emulsion of the ethylenically unsaturated monomer (a). Then, under a nitrogen atmosphere, the radical polymerization initiator is added while dropping the prepared emulsion into the reaction vessel. After the reaction starts, the polymer particle nuclei are generated, and the particles gradually grow to form resin fine particles.

Examples of the ethylenically unsaturated monomer (a) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl (meth) acrylate, and phenoxyethyl (). Aromatic ethylenic properties such as meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, and phenyl (meth) acrylate. Unsaturated: Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (Meta) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl Contains linear or branched alkyl groups such as (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate. Ethylene unsaturated monomer; Alicyclic alkyl group-containing ethylenically unsaturated monomer such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate; trifluoroethyl (meth) acrylate, heptadecafluorodecyl (meth) Fluorinated alkyl group-containing ethylenically unsaturated monomers such as acrylates; (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, β- (meth) acryloxi. Carboxy group-containing ethylenically unsaturated monomers such as ethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and dermal acid; sodium 2-acrylamide 2-methylpropanesulfonic acid, methallylsulfonic acid, metharylsulfonic acid, Acrylate containing sulfo groups such as sodium methallyl sulfonate, allyl sulfonic acid, sodium allyl sulfonate, ammonium allyl sulfonate, vinyl sulfonic acid, etc. Saturated monomer; (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl- N-propoxymethyl metaacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (Methoxymethyl) metaacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide , N, N-dimethylacrylamide, N, N-diethylacrylamide, diacetone acrylamide and other amide group-containing ethylenically unsaturated monomers; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol and other hydroxyl group-containing ethylenically unsaturated monomers; methoxypolyethylene glycol (meth) Polyoxyethylene group-containing ethylenically unsaturated monomers such as acrylates and polyethylene glycol (meth) acrylates; dimethylaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, methylethylaminoethyl (meth) acrylates, dimethylaminostyrene. , Diethylaminostyrene, etc., and amino group-containing ethylenically unsaturated monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and methylethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate, Epoxy group-containing ethylenically unsaturated monomer such as 3,4-epoxycyclohexyl (meth) acrylate; diacetone (meth) acrylamide, acetoacetoxy (meth) acrylate, etc. Acetyl group-containing ethylenically unsaturated monomer; allyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-Butenyl (meth) acrylate, 1,3-methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, 2-( Allyloxy) ethyl (meth) acrylate, allyllactyl (meth) acrylate, citronellyl (meth) acrylate, geranyl (meth) acrylate, loginyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallylitaconic acid, vinyl (meth) Acrylate, vinyl crotonate, vinyl oleate, vinyl linolenate, 2- (2'-vinyloxyethoxy) ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol ( Meta) acrylate, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethanediacrylate, 1,1,1-trishydroxymethylethanetriacrylate, 1,1 , 1-Trishydroxymethylpropantriacrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, diallyl maleate and other ethylenically unsaturated monomers having two or more ethylenically unsaturated groups; γ -Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Propylsilyl group-containing ethylenically unsaturated monomer such as vinyltributoxysilane and vinylmethyldimethoxysilane; N-methylol (meth) Examples thereof include methylol group-containing ethylenically unsaturated monomers such as acrylamide, N, N-dimethylol (meth) acrylamide, and alkyl etherified N-methylol (meth) acrylamide.
These monomers may be used alone or in combination of two or more.

The resin fine particles (A) may have a reactive group for forming a crosslink, and as the ethylenically unsaturated monomer (a), an ethylenically unsaturated monomer having a reactive group is used. May be good.
Since the resin fine particles (A) have a reactive group, cross-linking can be introduced in the colloidal crystal layer, and the friction resistance and solvent resistance of the pattern portion in gravure printing are further improved. Further, since the resin fine particles (A) have a reactive group, a crosslink can be introduced between the colloidal crystal layer and the primer layer described later, and the followability to the substrate, the friction resistance and the solvent resistance can be introduced. Is improved.

Cross-linking of the colloidal crystal layer can be introduced by a method of reacting the reactive groups of the resin fine particles (A) with each other or a method of reacting the reactive groups of the resin fine particles (A) with each other via a polyfunctional cross-linking agent. Cross-linking between the colloidal crystal layer and the primer layer described later is a method of reacting the reactive group of the resin fine particles (A) with the reactive group of the primer layer, and the reaction between the reactive group of the resin fine particles (A) and the primer layer. It can be introduced by a method of cross-linking a sex group via a polyfunctional cross-linking agent or the like.

Examples of the reactive group that the ethylenically unsaturated monomer (a) may have include an epoxy group, a carboxy group, a hydroxyl group, a ketone group, a hydrazide group and the like, and a ketone group is more preferable. In particular, when the reactive group is a ketone group and the cross-linking agent is a hydrazide cross-linking agent, a ketone-hydrazide cross-linking can be formed. Ketone-hydrazide cross-linking is preferably used because it does not adversely affect the physical properties of colloidal crystals and can form cross-links at low temperature and in a short time due to volatilization of water, and when a film substrate that is easily damaged by heating is used. It is valid. Further, since the ketone group is highly hydrophilic, when an ethylenically unsaturated monomer having a ketone group is used in the copolymer composition, the ketone group is introduced outside the resin fine particles (A), that is, near the interface with the aqueous medium. It is considered that the cross-linking can be efficiently formed with the hydrazide cross-linking agent.

When the resin fine particles (A) contain a ketone group, the preferable content of the ketone group is in the range of 0.05 to 0.3 mmol / g based on the mass of the resin fine particles (A). By introducing in the range of 0.05 to 0.3 mmol / g, the film strength of the colloidal crystal layer is further improved within a range that does not adversely affect the color development property, and the substrate followability, abrasion resistance, and solvent resistance are improved. Improve more.

[Radical polymerization initiator]
As the radical polymerization initiator used in the polymerization reaction of the ethylenically unsaturated monomer (a), known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used, and these may be used alone. It may be used, or two or more kinds may be mixed and used.

The oil-soluble polymerization initiator is not particularly limited, and is, for example, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylhydroperoxide, tert-butylperoxy (2-ethylhexanoate), tert-butylper. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4- Examples thereof include dimethylvaleronitrile, azobis compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 1,1'-azobis-cyclohexane-1-carbonitrile;

In emulsion polymerization, it is preferable to use a water-soluble polymerization initiator, for example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2'-azobis (2-methylpropionamidine) dihydro. Conventionally known substances such as chloride can be preferably used.

[Surfactant]
A surfactant such as a low molecular weight surfactant or a polymer dispersant can be used for producing the resin fine particles which are the polymers of the ethylenically unsaturated monomer (a). By using a surfactant, the stability and monodispersity of the resin fine particles can be improved. A low-molecular-weight surfactant is preferable as a surfactant because of its excellent monodispersity of the resin fine particles.
Examples of the low-molecular-weight surfactant include anionic or nonionic ones, and more specifically, anionic reactive surfactants, anionic non-reactive surfactants, nonionic reactive surfactants, and nonions. Examples thereof include non-reactive surfactants, preferably anionic surfactants. These surfactants may be used alone or in combination of two or more.

Here, the reactive surfactant refers to one that can be polymerized with the above-mentioned ethylenically unsaturated monomer. More specifically, it means a substance having a reactive group capable of polymerizing with an ethylenically unsaturated bond. Here, examples of the reactive group include an alkenyl group such as a vinyl group, an allyl group and a 1-propenyl group, a (meth) acryloyl group and the like. By using a reactive surfactant, the particle arrangement of the colloidal crystal and the free emulsifier component that adversely affects the weather resistance (moisture resistance) are reduced, so that the color development property and the color development property after the weather resistance test of the colloidal crystal are reduced. It is preferable because the substrate followability and the pressure resistance are further improved.

(Anionic surfactant)
Examples of the anionic reactive surfactant include polyoxyethylene alkyl ether sulfate type (commercially available products include Aqualon KH-05, KH-10, KH-20, and ADEKA Corporation manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Adecaria Soap SR-10N, SR-20N, Kao Latemuru PD-104, etc.); AR-20); Sulfocuccinate-based (commercially available products include Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Eleminor JS-2 manufactured by Sanyo Kasei Corporation, etc.); Polyoxy Ethylenealkylphenyl ether sulfate-based or polyoxyethylene alkylphenyl ester sulfate-based (commercially available products include Aqualon HS-10, HS-20, HS-30, BC-10, BC-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , ADEKA Corporation Adecaria Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.); (Meta) acrylate sulfate ester type (as a commercial product) Is Antox MS-60, MS-2N manufactured by Nippon Surfactant Co., Ltd., Eleminor RS-30 manufactured by Sanyo Kasei Kogyo Co., Ltd.); -3330PL, ADEKA CORPORATION Adecaria Soap PP-70, etc.);

Examples of the anionic non-reactive surfactant include higher fatty acid salts such as sodium oleate; alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate; polyoxyethylene lauryl. Examples thereof include polyoxyethylene alkyl ether sulfates such as sodium ether sulfate (commercially available products include Hytenol LA-10, LA-12, LA-16, etc. manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

(Nonionic surfactant)
Examples of the nonionic reactive surfactant include polyoxyalkylene alkyl ethers (commercially available products include Adecaria Soap ER-10 (HLB12.3) and ER-20 (HLB15.1) manufactured by ADEKA Corporation. ER-30 (HLB16.4), ER-40 (HLB17.1), Kao Co., Ltd. Latemul PD-420 (HLB12.6), PD-430 (HLB14.4), PD-450 (HLB16.2), etc. Polyoxyalkylene styrene phenyl ethers (commercially available products include Aqualon AN-10 (HLB13.0), AN-20 (HLB18.0) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; Polyoxyethylene alkyl phenyl ethers (commercially available products). Examples of commercially available products include Aqualon RN-20 (HLB14.2), RN-30 (HLB16.7), etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

Examples of the nonionic non-reactive surfactant include polyoxyalkylene alkyl ethers (commercially available products are Neugen XL-50 (HLB11.6) and XL-100 (HLB14.7) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ), XL-1000 (HLB19.3), TDS-50 (HLB10.5), TDS-70 (HLB12.1), TDS-80 (HLB13.3), TDS-120 (HLB14.8), Neugen TDX- 80 (HLB13.1), TDX-140 (HLB14.4), Kao Emargen 106 (HLB10.5), 108 (HLB12.1) 1108 (HLB13.5), 1135S-70 (HLB17.9), etc .; Poly Oxyalkylene styrene phenyl ethers (commercially available products include Neugen EA-87 (HLB10.6), EA-127 (HLB11.7), EA-157 (HLB14.3), Kao Emargen A-60 (HLB12). .8), A-90 (HLB14.5), A-500 (HLB18.0), etc .; Polyoxyethylene alkylphenyl ethers (commercially available, Branoun N-505 (HLB10.0) manufactured by Aoki Oil & Fat Industry Co., Ltd. ), Branoun NK-8055 (HLB10.8), etc .; Polyglycerin fatty acid esters (commercially available products include NIKKOL Hexaglin1-L (HLB14.5), Decaglyn-1-L (HLB15.5), Decaglyn manufactured by Nikko Chemicals Co., Ltd. -1-M (HLB14.0), Decaglyn-1-LN (HLB12.0), etc .; Polyoxyethylene glycerin fatty acid esters (commercially available, NIKKOL TMGS-5V (HLB9.5), TMGS manufactured by Nikko Chemicals Co., Ltd.) -15V (HLB13.5), TMGO-5 (HLB9.5), TMGO-15 (HLB14.5), etc .; Polyoxyethylene sorbitan fatty acid esters (commercially available, NIKKOL TL-10 (HLB16) manufactured by Nikko Chemicals Co., Ltd.) .9), TP-10EX (HLB15.6), TS-10V (HLB14.9), TS-30V (HLB10.5), TO-10V (HLB15.0), TO-106V (HLB10.0), Kao Leodore TW-L120 (HLB16.7), TW-L106 (HLB13.3), TW-P120 (HLB15.6), TW-S120V (HLB14.9), TW-S-106 (HLB9.5), manufactured by Leodore Co., Ltd. TW-O-106 (H LB10.0), etc .; Polyoxyethylene sorbitol fatty acid esters (commercially available products include NIKKOL GL-1 (HLB15.5), GS-460 (HLB13.0), GO-440V (HLB12.5) manufactured by Nikko Chemicals Co., Ltd.) , GO-460V (HLB14.0), Kao Leodor 430V (HLB10.5), 440V (HLB11.8), 460V (HLB13.8) polyethylene glycol fatty acid esters (commercially available, manufactured by Nippon Emulsion Co., Ltd.) EMALEX-810 (HLB11.0), 820 (HLB14.0), 830 (HLB15.0), 840 (HLB16.0), Kao Emanon 1112 (HLB13.7) Emanon 3199V (HLB19.4), etc.; Sugar fatty acid esters (commercially available products include S-970 (HLB9.0), S-1170 (HLB11.0), S-1570 (HLB15.0), S-1670 (HLB16.0) manufactured by Mitsubishi Chemical Foods Co., Ltd.) , P = 1570 (HLB15.0), P-1670 (HLB16.0), M-1695 (HLB16.0), O-1570 (HLB15.0), L-1695 (HLB16.0), LWA-1570 ( HLB15.0), etc .; Polyoxyethylene lanolins (commercially available products include NIKKOL TW-10 (HLB12.0), TW-20 (HLB13.0), BWA-5 (HLB12.5), BWA manufactured by Nikko Chemicals Co., Ltd.) -10 (HLB15.5), BWA-20 (HLB16.0), etc .; Polyoxyethylene hydrogenated castor oils (commercially available, NIKKOL HCO-20 (HLB10.5), HCO-30 (HLB11. 0), HCO-40 (HLB-12.5), HCO-100 (HLB16.5), etc .; Polyoxyethylene sterols (commercially available, NIKKOL BPS-5 (HLB9.5), BPS manufactured by Nikko Chemicals Co., Ltd.) -10 (HLB12.5), BPS-20 (HLB-30), BPSH-25 (HLB14.5) and the like;

(Polymer dispersant)
Examples of the polymer dispersant include polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene / polyoxypropylene block copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, and styrene- (meth) acrylic. Acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid copolymer, maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid -(Meta) acrylic acid alkyl ester copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene- (meth) acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl pyrrolidone- (meth) acrylic Acid alkyl ester copolymer, vinyl pyrrolidone-styrene copolymer, vinyl pyrrolidone-vinyl acetate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, vinyl acetate-crotonic acid Copolymer, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, polystyrene sulfonic acid, sodium polystyrene sulfonate (manufactured by Toso Co., Ltd.)
Polynas PS-1, Polynas PS-5, etc.), styrene sulfonic acid-maleic acid copolymer, polyitaconic acid, polyhydroxyethyl (meth) acrylate, poly (meth) acrylamide, (meth) acrylamide- (meth) acrylic acid Water-soluble vinyl-based copolymers such as polymers, polyvinyl methyl ethers, methyl vinyl esters, and carboxyvinyl polymers; urethane resins obtained by the double addition reaction of polyisocyanates and polyols, and the introduction of hydrophilic groups makes the entire resin water-soluble. Examples thereof include a solubilized water-soluble polyurethane resin; a polyester resin obtained by a polycondensation reaction between a polyvalent carboxylic acid and a polyol, and a water-soluble polyester resin in which the entire resin is solubilized by the introduction of a hydrophilic group.

[Core shell type resin fine particles]
The resin fine particles (A) in the present invention are preferably a core-shell type having a structure of a core (inner layer) and a shell (outer layer), and more preferably both the core and the shell are water-insoluble resins. They are incompatible with each other. In the core-shell type resin fine particles, the core plays a role of maintaining a spherical shape, and the shell plays a role of a binding site having fluidity.
The core-shell type resin fine particles (A) are applied onto the base material, and then are regularly arranged and laminated as the drying progresses. At that time, the shells are fused to each other at the contact portion between the core-shell type particles, and the voids are replaced with air from the aqueous medium to form a colloidal crystal layer. When the resin fine particles (A) are of the core-shell type, the shell can bind the achromatic black fine particles (C) described later and suppress the loss of the achromatic black fine particles (C). As a result, the substrate followability, friction resistance, and solvent resistance of the laminated body are further improved. Further, when the base material has a primer layer described later, the shell also fuses with the resin of the primer layer, so that the colloidal crystals are more firmly immobilized.

The content of the shell in the core-shell type resin fine particles (A) is preferably 10 to 300% by mass, more preferably 10 to 150% by mass, based on the mass of the core. When the content of the shell is 10% by mass or more based on the mass of the core, the fusion of the shell proceeds sufficiently, and the bonding between the resin fine particles (A) and between the resin fine particles (A) and the primer layer is formed. It will be stronger. Therefore, the substrate followability, friction resistance, and solvent resistance of the laminated body are further improved.
From the viewpoint of color development, the content of the shell is preferably in the range of 150% by mass or less, and more preferably in the range of 50% by mass or less. When the content of the shell is 150% by mass or less, it is preferable because the shell is suppressed from being excessively fused by heat or a solvent and a sufficient void portion can be obtained. In the colloidal crystal, when air is present in the void portion of the core-shell type resin fine particles, the difference in refractive index between the particles and the matrix becomes large, so that the color development property of the colloidal crystal is improved.
On the other hand, the content of the shell is preferably in the range of 50 to 300% by mass, more preferably in the range of 50 to 200% by mass, from the viewpoint of scratch resistance. When the content of the shell is 50% by mass or more, the fusion of the shell further progresses when the coating film is dried, and the bonding between the core-shell type resin fine particles and between the core-shell type resin fine particles and the base material is stronger. A colloidal crystal having excellent scratch resistance can be obtained.

The glass transition point of the core of the core-shell type resin fine particles (A) is preferably 60 ° C. or higher, and more preferably 60 to 150 ° C. When the glass transition point is 60 ° C. or higher, the core shape is suppressed from being deformed by the influence of heat or a solvent. This makes it possible to obtain a laminate having more excellent color development property, abrasion resistance, and solvent resistance.

The glass transition point of the shell portion of the core-shell type resin fine particles (A) is preferably in the range of −50 to 20 ° C, more preferably in the range of −30 to 10 ° C. Within the above range, it is possible to prevent the void portion of the colloidal crystal layer from being filled by the fusion of the shell. Further, the fusion of the shell is sufficiently advanced, and the bonding between the resin fine particles (A) and between the resin fine particles (A) and the primer layer becomes stronger. Therefore, the substrate followability, friction resistance, and solvent resistance of the laminated body are further improved.

Further, the coefficient of variation (Cv value) of the average particle size in the core-shell type resin fine particles is preferably 30% or less. The coefficient of variation is a numerical value representing the uniformity of the particle size and can be calculated by the following formula.
Equation: Coefficient of variation Cv value (%) = standard deviation of particle size / average particle size x 100
[In the equation, the unit of standard deviation and average particle size is the same]
When the coefficient of variation is 30% or less, the regularity of the particle arrangement is improved and the color-developing property of the colloidal crystal is improved.

The refractive index of the core-shell type resin fine particles is preferably 1.45 or more, more preferably 1.45 to 3.00, and further preferably 1.45 to 2.00. When the refractive index is 1.45 or more, the color-developing property of the colloidal crystal is improved, which is preferable.

The content of the resin fine particles (A) is preferably 22.5 to 43.2% by mass, more preferably 31.5 to 41.9% by mass, based on the composition for colloidal crystals.
When the content of the resin fine particles (A) is 22.5% by mass or more, the leveling property of the composition for colloidal crystals on the substrate is improved during gravure printing, and the disorder of the particle arrangement is suppressed. Further, it is possible to obtain a gravure laminate having excellent printability and color development. When the content is 43.2% by mass or less, the disorder of the particle arrangement due to plate clogging or rapid drying of the composition for colloidal crystals is suppressed, and a laminate having excellent printability and color development can be obtained. ..

<Achromatic black fine particles (B)>
The composition for colloidal crystals of the present invention contains achromatic black fine particles (B) (excluding resin fine particles (A)). The achromatic black fine particles (B) act to absorb extra scattered light in the colloidal crystals in the colloidal crystal layer in which the resin fine particles (A) are regularly arranged to make the color development of the colloidal crystals clearer.
As the achromatic black fine particles (B), any black fine particles such as carbon black and resin fine particles colored with a black dye can be used. Carbon black is preferable because the coloring component is difficult to elute into water or a solvent and the durability of the coloring agent is excellent. As the carbon black, either a dispersion type dispersed in water using a dispersant or a self-dispersion type may be used, but the self-dispersion type carbon black is used from the viewpoint that the dispersant does not affect the fine particle arrangement. Is preferable. Examples of commercially available carbon black aqueous dispersions include Lion Paste series (W-310A, etc.) manufactured by Lion Co., Ltd. and BONJET BLACK CW series (CW-1, CW-2, CW-3, etc.) manufactured by Orient Chemical Co., Ltd. ..

The average particle size of the achromatic black fine particles (B) is preferably in the range of 30 to 300 nm. Within the above range, the inhibition of the resin fine particles (A) to the ordered arrangement is small, and the achromatic black fine particles (B) are easily immobilized in the colloidal crystals. Therefore, the friction resistance and solvent resistance of the colloidal crystal layer are further improved.

The content of the achromatic black fine particles (B) is preferably in the range of 0.10 to 20% by mass, more preferably in the range of 0.5 to 5.0% by mass, based on the resin fine particles (A). be. When the content is 0.1% by mass or more, a colloidal crystal that is clearer and has excellent color development can be obtained. When it is 20% by mass or less, a colloidal crystal having more excellent friction resistance and solvent resistance can be obtained while maintaining clear color development.

<Hydrophilic solvent (C), nonionic surfactant (D)>
The composition for colloidal crystals of the present invention contains a hydrophilic solvent (C) having a boiling point of 95 to 250 ° C. and / or a nonionic surfactant (D) having an HLB value of 10.0 to 19.0. It is important to include them, and by including these, it has excellent gravure printability and enables high-quality pattern printing that achieves both color development and low angle dependence.

[Hydrophilic solvent (C)]
The hydrophilic solvent (C) is a solvent having a boiling point of 95 to 250 ° C. per 1 atm.
When the boiling point is 95 ° C. or higher, the colloidal crystal composition is prevented from being rapidly dried during gravure printing, and at the same time, the leveling property to the substrate is improved. As a result, excellent printability is exhibited. Further, when the boiling point of the hydrophilic solvent (C) is 95 ° C. or higher, rapid drying is suppressed in the central portion of the pattern, so that a regularly arranged colloidal crystal layer can be obtained. Therefore, when the pattern layer is viewed from the front, there is no whitening and the color development is excellent. On the other hand, in gravure printing, water and a solvent volatilize from the end face of the pattern, so that the arrangement of the colloidal crystal layer is slightly disturbed at the end of the pattern due to rapid drying.
Normally, a colloidal crystal coating film having a regular arrangement on the entire surface has a large angle dependence due to Bragg reflection, but a coating film obtained by gravure printing the composition of the present invention has an arrangement at the center and edges of the pattern. different. By disturbing a part of the arrangement in this way, it is possible to obtain a clear color of RGB, and at the same time, to obtain a low-angle-dependent pattern in which the color tone does not change significantly from any angle.

When the boiling point of the hydrophilic solvent (C) is 250 ° C. or lower, the residual solvent is reduced, and the residual solvent does not adversely affect the color development property such as swelling of particles and the coating film resistance does not deteriorate, and the color development property and abrasion resistance do not occur. Colloidal crystals with excellent properties and solvent resistance can be obtained.
The boiling point of the hydrophilic solvent (C) is preferably in the range of 100 to 240 ° C.

Examples of the hydrophilic solvent (C) that can be used in the present invention include 1-propanol (bp 97 ° C), 1-butanol (bp 118 ° C), and 2-methyl-1-propanol (b.p. 118 ° C). B.p. 108 ° C.), 2-butanol (b.p. 100 ° C.) and other monovalent lower monoalcohol solvents (C-1); ethylene glycol (b.p. 197.0 ° C.), 1,3 -Propane diol (bp 230 ° C), propylene glycol (bp 188 ° C 1,2-butane diol (bp 192 ° C), 1,4-butane diol (bp 230 ° C)) , Pentylene glycol (bp.188 ° C.), 1,2-hexanediol (bp.230 ° C.), 1,6-hexanediol (bp.208 ° C.), Diethylene glycol (b.p.245 ° C.) Glycol-based solvent (C-2) such as (° C.); ethylene glycol monomethyl ether (b.p.124 ° C.), diethylene glycol monomethyl ether (bp.194 ° C.), triethylene glycol monoethyl ether (b.p.249). ° C.), ethylene glycol monoethyl ether (b.p.134 ° C.), diethylene glycol monoethyl ether (b.p.202 ° C.), ethylene glycol monoisopropyl ether (b.p.144 ° C.), diethylene glycol monoisopropyl ether (b. .P.230 ° C.), ethylene glycol monobutyl ether (b.p.171 ° C.), diethylene glycol monobutyl ether (b.p.230 ° C.), ethylene glycol monoisobutyl ether (b.p.160 ° C.), ethylene glycol monohexyl Ether (bp 208 ° C), diethylene glycol dimethyl ether (bp 162 ° C), triethylene glycol dimethyl ether (bp 216 ° C), propylene glycol monomethyl ether (b p 120 ° C), dipropylene glycol Glycol ether solvent (C-3) such as monomethyl ether (b.p. 194 ° C.), dipropylene glycol dimethyl ether (b.p. 175 ° C.), tripropylene glycol monomethyl ether (b.p. 243 ° C.); N. Lactam solvents such as -methyl-2-pyrrolidone (b.p.202 ° C.), N-hydroxyethyl-2-pyrrolidone (b.p.175 ° C.), 2-pyrrolidone (b.p.245 ° C.); formamide (B.p. 210 ° C.), 3-methoxy-N, N-dimethylpropionamide (b.p. 210 ° C.) b. p. 215 ° C.), 3-butoxy-N, N-dimethylpropanamide (bp 252 ° C.) and other amide-based solvents;
These hydrophilic solvents (C) may be used alone or in combination of two or more.

The hydrophilic solvent (C) is preferably at least one selected from the group consisting of a lower monoalcohol solvent (C-1), a glycol solvent (C-2), and a glycol ether solvent (C-3). By containing such a hydrophilic solvent, the leveling property of the composition for colloidal crystals and the control of the ordered arrangement of particles are improved, and further excellent printability is exhibited. Further, a colloidal crystal having excellent color development property, low angle dependence, substrate followability, abrasion resistance and solvent resistance can be obtained.

[Nonionic surfactant (D)]
The nonionic surfactant (D) has an HLB value in the range of 10.0 to 19.0.
When the HLB value of the nonionic surfactant (D) is 10.0 or more, it has excellent solubility in water and excellent leveling property with respect to the substrate. Further, there is no adverse effect such as disturbing the ordered arrangement of the resin fine particles (A) or swelling of the resin fine particles (A) due to the surfactant. As a result, a colloidal crystal that exhibits excellent printability and color development property and has excellent substrate followability, abrasion resistance, and solvent resistance to the substrate can be obtained. When the HLB value is 19.0 or less, the surface tension of the composition for colloidal crystals is lowered and falls within an appropriate range. As a result, the composition for colloidal crystals has improved leveling property, exhibits excellent printability, and can obtain colloidal crystals having excellent color development property, abrasion resistance, and solvent resistance.

The HLB value is a numerical value representing the hydrophilicity and lipophilicity of the material, and the smaller the HLB value, the higher the lipophilicity. In the present specification, the HLB value is calculated by the calculation formula of the Griffin method represented by the following formula (1).
Equation (1)
HLB value = 20 × (sum of formulas of hydrophilic part) ÷ (molecular weight of material)

As the nonionic surfactant (D), those having an HLB value of 10.0 to 19.0 mentioned in the above-mentioned (Nonionic surfactant) section can be used.
The nonionic surfactant (D) is preferably at least one selected from the group consisting of polyoxyalkylene alkyl ethers (D-1) and polyglycerin fatty acid esters (D-2). By containing such a surfactant, the leveling property of the composition for colloidal crystals and the control of the ordered arrangement of particles are improved, and further excellent printability is exhibited. Further, a colloidal crystal having excellent color development property, low angle dependence, substrate followability, abrasion resistance and solvent resistance can be obtained.
The HLB value of the nonionic surfactant (D) is preferably 12.0 to 19.0, more preferably 12.0 to 17.0.

The composition for colloidal crystals of the present invention may contain at least one selected from the group consisting of the hydrophilic solvent (C) and the nonionic surfactant (D), and the hydrophilic solvent (C) may be contained. In any case of containing only the nonionic surfactant (D), or containing both the hydrophilic solvent (C) and the nonionic surfactant (D), the present invention also applies. Demonstrates excellent effects.
The total content of the hydrophilic solvent (C) and the nonionic surfactant (D) is preferably in the range of 0.5 to 20% by mass, more preferably, based on the total amount of the composition for colloidal crystals. Is in the range of 1 to 15% by mass, more preferably in the range of 1 to 10% by mass. Within such a range, the leveling property to the substrate is improved without affecting the ordered arrangement of the resin fine particles (A), and excellent printability is exhibited. In addition, excellent colloidal crystals can be obtained due to color development and low angle dependence. Further, since there is no risk of deteriorating the coating film resistance, it is also excellent in followability to the substrate, abrasion resistance, and solvent resistance.

<Characteristics of composition for colloidal crystals>
The composition for colloidal crystals of the present invention has a surface tension of 25 to 42 mN / m at 25 ° C. When the surface tension is 25 mN / m or more, the disorder of the ordered arrangement of the resin fine particles (A) is suppressed, and even in gravure printing, a printed matter having colloidal crystals having excellent printability and clear color development can be obtained. Can be done. When the surface tension is 42 mN / m or less, it is possible to obtain a printed matter having colloidal crystals having excellent leveling property on a substrate, excellent printability in gravure printing, and clear color development. Further, this printed matter is excellent in substrate followability, abrasion resistance, and solvent resistance.

The surface tension of the composition for colloidal crystals at 25 ° C. is preferably 26 to 40 mN / m. The surface tension in the present specification can be measured by a plate method (Wilhelmy method) using a surface tension meter.

<Crosslinking agent>
As described above, the composition for colloidal crystals of the present invention may contain a cross-linking agent in order to form cross-links in the colloidal crystal layer and between the colloidal crystal layer and the primer layer.
The cross-linking agent is not particularly limited and may be appropriately selected depending on the reactive group of the colloidal crystal layer or the primer layer. For example, two or more hydrazino groups that react with an active carbonyl group to form a keto-hydrazide cross-linking are used. Hydrazide compound (polyhydrazide); isocyanate compound that reacts with a hydroxyl group or amino group to form a urethane bond or urea bond; epoxy compound that reacts with a carboxy group, amino group, etc.; be able to.
More specifically, for example, when the resin fine particles (A) and the primer component have a carboxy group, cross-linking can be formed via an epoxy cross-linking agent. Further, for example, when the resin fine particles (A) and the primer component have a hydroxyl group, cross-linking can be formed via a polyisocyanate cross-linking agent. Further, for example, when the resin fine particles (A) and the primer component have a ketone group, they can be crosslinked via a hydrazide crosslinking agent.
As the cross-linking agent, as described above, it is preferable to use a hydrazide cross-linking agent in order to form a ketone / hydrazide cross-linking. Examples of the hydrazide cross-linking agent include adipic acid dihydrazide and a water-soluble resin in which a polyfunctional hydrazide group is modified.

The composition for colloidal crystals may contain various additives as long as the effects of the present invention are not impaired, and for example, a leveling agent, a thickener, and a preservative can be blended.

<Laminated body>
The composition for colloidal crystals of the present invention is for gravure printing, and can be transferred from a plate made in a cylinder to a substrate for printing by a concave gravure printing method, and is printed on the substrate as described above. The laminate of the present invention can be obtained by gravure printing the composition for colloidal crystals to form a colloidal crystal layer.

Gravure printing is difficult with letterpress printing and inkjet printing because more colloidal crystal compositions can be transferred from the plate to the substrate in a single print, and significant disturbance of the particle arrangement due to rapid drying is suppressed. , It is possible to obtain a printed matter having an excellent color development property. For gravure plate making, various cell types (conventional type, net gravure type, laser type, etc.) produced by an engraving method or a corrosion method can be used. The composition for colloidal crystals applied on the substrate by transfer is dried to form a colloidal crystal layer. The drying method is not particularly limited, and examples thereof include a heat drying method, a hot air drying method, an infrared drying method, a microwave drying method, and a drum drying method. The drying temperature is preferably in the range of 20 to 80 ° C. from the viewpoint of the influence on the ordered arrangement of the resin fine particles (A) and the productivity.

The thickness of the colloidal crystal layer in the laminate of the present invention is preferably in the range of 1.0 to 20 μm. Within the above range, excellent printability and color development property are sufficiently ensured, and a laminate having excellent substrate followability, abrasion resistance, and solvent resistance can be obtained.

<Base material>
The base material is not particularly limited and may be appropriately selected depending on the intended use, such as a polyvinyl chloride sheet, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, a nylon film, a polystyrene film, and a polyvinyl alcohol film. Thermoplastic resin base material; metal base material such as aluminum foil; glass base material, paper base material such as coated paper, and the like.

The base material may have a smooth coated surface or may have irregularities. Further, the base material may be transparent, translucent, or opaque, and in order to make the color development of the colloidal crystal coating film clearer, a base material previously colored in black or the like may be used. Further, the base material may be one type alone or a laminated body in which two or more types of base materials are bonded together.

The substrate preferably has a primer layer in order to further enhance the fixability of the colloidal crystal layer on the substrate. The primer layer can be formed by applying a primer component in advance on the substrate. The primer component is not particularly limited, and examples thereof include an acrylic resin, a styrene acrylic resin, a urethane resin, an olefin resin, a polyester resin, and a composite resin obtained by combining these resins. One of these primer components may be used alone, or two or more thereof may be used in combination.
As the primer component, it is preferable to use an acrylic resin, a styrene acrylic resin, or a urethane resin from the viewpoint of excellent binding property to a substrate or a colloidal crystal layer, resistance of the primer layer, and the like.

The glass transition point of the resin constituting the primer layer is preferably in the range of −60 to 100 ° C. When the glass transition point is in the above range, blocking between the primer layer and the gravure plate making in the non-printed portion is suppressed during gravure printing. In addition, it is possible to prevent the primer component from invading the colloidal crystal layer and adversely affecting the color development of the colloidal crystal layer. As a result, a colloidal crystal having more excellent printability and color development property, and excellent substrate followability, abrasion resistance, and solvent resistance can be obtained.

The primer layer may contain additives as long as the effects of the present invention are not impaired. Examples of such additives include surfactants and achromatic black particles, and the above description can be incorporated.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. “Parts” and “%” in Examples and Comparative Examples mean “parts by mass” and “% by mass” unless otherwise specified.

[Average particle size, Cv value]
The average particle size was measured by diluting the fine particle dispersion 500 times with water and measuring about 5 ml of the diluted solution by a dynamic light scattering measurement method (measurement device was manufactured by Nanotrack UPA Co., Ltd. Microtrac Bell Co., Ltd.). The peak of the volume particle size distribution data (histogram) obtained at this time was taken as the average particle size. In addition, the coefficient of variation Cv value representing the uniformity of the particle size was calculated by the following formula.
Formula: Cv value (%) = standard deviation of particle size / average particle size x 100
[In the equation, the unit of standard deviation and average particle size is the same]

[Glass transition point (Tg)]
The glass transition point was measured by DSC (differential scanning calorimeter manufactured by TA Instrument). Specifically, about 2 mg of a sample obtained by drying the resin fine particle dispersion is weighed on an aluminum pan, the aluminum pan is set in a DSC measurement holder, and a DSC curve obtained under a heating condition of 5 ° C./min is obtained. The baseline shift (inflection point) to the endothermic side was read to obtain the glass transition point.

[Surface tension γ]
The surface tension γ was measured by a plate method (Wilhelmy method) under the condition of 25 ° C. using a surface tension meter (automatic surface tension meter DY-300) manufactured by Kyowa Interface Co., Ltd.

<Preparation of resin fine particles (A) dispersion>
[Manufacturing Example 1]
68.9 parts of water was charged in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer. Then, separately, 80.0 parts of methyl methacrylate, 9.0 parts of n-butyl methacrylate, 8.0 parts of 2-ethylhexyl acrylate, 1.0 part of acrylic acid, 1.0 part of diacetone acrylamide, and 3-methacryloxypropyltri. 1.0 part of ethoxysilane, 5.0 parts of 20% aqueous solution of Aqualon KH-10 (Daiichi Kogyo Seiyaku, polyoxyethylene alkyl ether sulfate-based anionic reactive surfactant), 40.4 parts of water in advance. 3% of the emulsion of the ethylenically unsaturated monomer prepared by mixing and stirring was further added to the reaction vessel.
After raising the internal temperature of the reaction vessel to 70 ° C. and sufficiently substituting with nitrogen, 2.0 parts of a 5% aqueous solution of potassium persulfate was added as an initiator to initiate emulsion polymerization. While raising the internal temperature to 80 ° C. and maintaining the temperature, the rest of the emulsion of the ethylenically unsaturated monomer and 2.0 parts of a 5% aqueous solution of potassium persulfate were added dropwise over 3 hours, and the mixture was further reacted for 4 hours. The solid content concentration was adjusted to 45.0% with water to obtain an aqueous dispersion of resin fine particles (A-1).
The average particle size of the obtained resin fine particles was 226 nm, the coefficient of variation Cv value was 27.5%, and the Tg was 71.6 ° C.

[Manufacturing Example 2]
An aqueous dispersion of resin fine particles (A-2) having a solid content concentration of 45.0% was prepared by the same method as in Production Example 1 except that the composition was changed to that shown in Table 1. For the obtained resin fine particles, the average particle size, Cv value, and Tg were measured in the same manner as in Production Example 1.

[Manufacturing Example 3]
95.0 parts of water was charged in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer. Next, separately, 97.0 parts of styrene, 2.0 parts of acrylic acid, 1.0 part of 3-methacryloxypropyltrimethoxysilane, 5.0 parts of a 20% aqueous solution of Aqualon KH-10, and 39.1 parts of water were added separately. 1.5% of the emulsion of the first-stage ethylenically unsaturated monomer prepared by mixing and stirring was further added to the reaction vessel.
After raising the internal temperature of the reaction vessel to 70 ° C. and sufficiently substituting with nitrogen, 5.7 parts of a 2.5% aqueous solution of potassium persulfate was added as an initiator to initiate polymerization. While maintaining the temperature by raising the internal temperature to 80 ° C, the rest of the emulsion of the ethylenically unsaturated monomer in the first stage and 4.0 parts of a 2.5% aqueous solution of potassium persulfate were added dropwise over 2 hours. The reaction was carried out to synthesize core particles. The average particle size of the produced core particles was 205 nm.
Twenty minutes after the completion of the first step, 15.0 parts of methyl methacrylate, 23.1 parts of n-butyl acrylate, 0.9 parts of acrylic acid, 2.1 parts of a 20% aqueous solution of Aqualon KH-10, and 16 parts of water. 8. Dropping of the emulsion of the ethylenically unsaturated monomer in the second stage prepared by mixing and stirring 8 parts was started. While keeping the internal temperature at 80 ° C., the second stage ethylenically unsaturated monomer emulsion and 2.1 parts of a 2.5% aqueous solution of potassium persulfate were added dropwise over 2 hours to further proceed with the reaction, and water was added. Was added to adjust the solid content concentration to 45.0%, and an aqueous dispersion of core-shell type resin fine particles (A-3) was obtained.
The average particle size of the obtained core-shell type resin fine particles was 255 nm, the Cv value was 26.1%, the Tg of the core portion was 100.1 ° C, and the Tg of the shell portion was -4.0 ° C.

[Manufacturing Examples 4 to 10]
An aqueous dispersion of core-shell type fine particles (A-3 to A-10) was prepared by the same method as in Production Example 3 except that the composition was changed to that shown in Table 2-1. At the time of synthesis, the emulsion of the ethylenically unsaturated monomer is made of water so that the concentration of the ethylenically unsaturated monomer in the emulsion is 69.0% and the concentration of the surfactant is 0.69%. Was added and prepared. After the synthesis, the solid content concentration of the aqueous dispersion of the core-shell type resin fine particles was adjusted to 45.0% by adding water or dehydrating by vacuum stripping. The average particle size, Cv value, and Tg of the obtained core-shell type resin fine particles were measured in the same manner as in Production Example 3.

[Manufacturing Examples X-1 to X-5]
An aqueous dispersion of core-shell type fine particles (X-1 to X-5) was prepared by the same method as in Production Example 3 except that the composition was changed to that shown in Table 2-2. At the time of synthesis, the emulsion of the ethylenically unsaturated monomer is made of water so that the concentration of the ethylenically unsaturated monomer in the emulsion is 69.0% and the concentration of the surfactant is 0.69%. Was added and prepared. After the synthesis, the solid content concentration of the aqueous dispersion of the core-shell type resin fine particles was adjusted to 45.0% by adding water or dehydrating by vacuum stripping. The average particle size, Cv value, and Tg of the obtained core-shell type resin fine particles were measured in the same manner as in Production Example 3.

The obtained resin fine particles (A) are shown in Table 1 and Tables 2-1 to 2-2 (hereinafter referred to as Table 2). The numerical values in Tables 1 and 2 represent "parts" unless otherwise specified, and blanks mean that they are not blended.

<Preparation of composition for colloidal crystals>
[Example 1]
BONJET BLACK CW-1 manufactured by Orient Chemical Industry Co., Ltd. (surface-modified carbon black, average particle diameter 62 nm, pigment content 20.0%) in 100 parts of the aqueous dispersion of the resin fine particles (A-1) of Production Example 1 as achromatic black fine particles. 3.8 parts, 5 parts of diethylene glycol monobutyl ether, 1.0 part of Emulgen 1108 manufactured by Kao Co., Ltd. and 1.0 part of adipic acid dihydrazide were added and stirred to prepare a composition for colloidal crystals.

[Examples 2 to 37, Comparative Examples 1 to 7]
The compositions for colloidal crystals were prepared by the same method as in Example 1 except that the composition was changed to the composition shown in Tables 3-1 to 3-3.

[Examples Y-1 to Y-5]
The compositions for colloidal crystals were prepared by the same method as in Example 1 except that the composition was changed to the composition shown in Table 3-4.

The properties of the obtained colloidal crystal layer forming composition are shown in Tables 3-1 to 3-4 (hereinafter referred to as Table 3). The numerical values in Table 3 represent "parts" unless otherwise specified, and blanks mean that they are not mixed.

<Preparation of primer solution>
[Manufacturing Example 11]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer was charged with 68.9 parts of water and 0.25 parts of a 20% aqueous solution of Aqualon KH-10 as a reactive surfactant. Then, separately, 18.0 parts of styrene, 25.0 parts of methyl methacrylate, 16.0 parts of 2-ethylhexyl acrylate, 35.0 parts of n-butyl acrylate, 2.0 parts of acrylic acid, and 3-methacryloxypropyltriethoxysilane. Reaction of 1.0 part, 4.8 parts of 20% aqueous solution of Aquaron KH-10, and 40.4 parts of water in advance, and 3% of the emulsion of ethylenically unsaturated monomer prepared by mixing and stirring. Further added to the container.
After raising the internal temperature of the reaction vessel to 80 ° C. and sufficiently substituting with nitrogen, 2.0 parts of a 5% aqueous solution of potassium persulfate was added as an initiator to initiate emulsion polymerization. While maintaining the internal temperature at 80 ° C., the rest of the emulsion of the ethylenically unsaturated monomer and 2.0 parts of a 5% aqueous solution of potassium persulfate were added dropwise over 3 hours and further reacted for 4 hours to obtain resin fine particles. An aqueous dispersion was obtained.
After the reaction was completed, 1.9 parts of 25% aqueous ammonia was added for neutralization, and water was added to adjust the solid content concentration of the resin fine particle aqueous dispersion to 40.0%. The Tg of the resin fine particles was -3.2 ° C.
To the obtained resin fine-grained aqueous dispersion, 2.0 parts of n-propyl alcohol and 10 parts of BONJET BLACK CW-1 (surface-modified carbon black, average particle size 62 nm, pigment content 20.0%) manufactured by Orient Chemical Industries, Ltd. were added. The mixture was stirred and mixed to obtain a primer solution.

[Manufacturing Examples 12 to 14]
Primer solutions were prepared by the same method as in Production Example 11 except that the composition was changed to that shown in Table 4.

[Manufacturing Example 15]
185.0 parts of water in a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a recirculator, JONCRYL67 as a polymer dispersant (BASF styrene acrylic resin Mw12500, acid value 213 mgKOH / g) 42.6 11.1 parts of 25% ammonia water was charged, and the temperature was raised while stirring to dissolve the polymer dispersant. Further, after raising the temperature to 80 ° C. under nitrogen reflux, using two dropping funnels, 14.0 parts of styrene, 15.0 parts of n-butyl methacrylate, and 30.0 parts of 2-ethylhexyl acrylate were used from one dropping funnel. A mixed solution of 10.0 parts of cyclohexyl acrylate and 1.0 part of 2-hydroxyethyl methacrylate was added dropwise over 2 hours. From the other dropping funnel, 3.6 parts of a 20% ammonium persulfate aqueous solution was added dropwise over 2 hours. After the dropping was completed, the reaction was further carried out for 5 hours to obtain an aqueous dispersion of resin fine particles. After the reaction was completed, water was added to adjust the solid content concentration of the resin fine particle aqueous dispersion to 40.0%. The Tg of the obtained resin fine particles was -3.4 ° C.
To the obtained resin fine particle aqueous dispersion, 2.0 parts of n-propyl alcohol and 10 parts of BONJET BLACK CW-1 (surface-modified carbon black average particle diameter 62 nm pigment content 20.0%) manufactured by Orient Chemical Industry Co., Ltd. were added. The mixture was stirred and mixed to obtain a primer solution.

[Manufacturing Examples 16 and 17]
Primer solutions were prepared by the same method as in Production Example 15 except that the composition was changed to that shown in Table 5.

[Manufacturing Example 18]
PTG-2000SN (polytetramethylene glycol manufactured by Hodoya Chemical Industry Co., Ltd. (number of functional groups 2, hydroxyl value 57.0, molecular weight 2,000)) 19 as a polyol in a reaction vessel equipped with a stirrer, thermometer, and recirculator. .6 parts, P-2011 (3-methyl-1,5-pentanediol / adipic acid / terephthalic acid polyester polyol (functional group number 2, hydroxyl value 55.0, molecular weight 2,000) manufactured by Kuraray Co., Ltd.) 20.3 parts , C-2090 (Polyolpolyol manufactured by Kuraray Co., Ltd. (number of functional groups 2, hydroxyl value 56.0, molecular weight 2,000)) 91.6 parts, dimethylol butanoic acid 19.7 parts, isophorone diisocyanate 48.8 parts as polyisocyanate. , 40.0 parts of methyl ethyl ketone and 10.0 parts of dipropylene glycol dimethyl ether were charged as a solvent, and the temperature was raised to 78 ° C. while stirring in a nitrogen atmosphere. 0.02 part of titanium diisopropoxybiz (ethylacetacetate) was added thereto as a catalyst, and the mixture was reacted for 7 hours to obtain a urethane prepolymer having isocyanate groups at both ends. After adding 13.5 parts of triethylamine as a neutralizing agent, 400 parts of water and 2.4 parts of ethylenediamine as a chain extender were added, and the phase was changed to the aqueous phase while removing the solvent under reduced pressure conditions. rice field. After promoting the chain extension reaction of the isocyanate group in an aqueous medium, an aqueous dispersion of a urethane resin having a solid content concentration of 30.0% was prepared.
2.0 parts of diethylene glycol monobutyl ether, 1.0 part of n-propyl alcohol, BONJET BLACK CW-1 (surface-modified carbon black, average particle size 62 nm, pigment content 20.0) manufactured by Orient Chemical Industry Co., Ltd. in the prepared resin aqueous dispersion %) Was added, and the mixture was stirred and mixed to obtain a primer solution.

[Manufacturing Example 19]
A primer solution was prepared by the same method as in Production Example 18 except that the composition was changed to that shown in Table 6.

The abbreviations in Table 6 are shown below.
PTG-2000SN: Polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd. (number of functional groups 2, hydroxyl value 57.0, molecular weight 2,000)
P-2011: Kuraray 3-methyl-1,5-pentanediol / adipic acid / terephthalic acid polyester polyol (number of functional groups 2, hydroxyl value 55.0, molecular weight 2,000)
C-2090: Polycarbonate polyol manufactured by Kuraray (number of functional groups 2, hydroxyl value 56.0, molecular weight 2,000)

<Making a laminate by gravure printing>
[Example 38]
The primer solution prepared in Production Example 12 is coated on the corona-treated surface of a biaxially stretched polypropylene (OPP) film (FOR made by Futamura, thickness 20 μm) with a bar coater so that the thickness after drying becomes 2 μm, and then an oven. The primer layer was formed by drying at 80 ° C. for 3 minutes. Further, a simple gravure coating machine (GRAVO-PROOF MINI manufactured by Nissho Gravure Co., Ltd.) is set with a gravure cylinder manufactured by Toyo FPP (engraving method: Helio, cell shape: compressed, number of lines: 70 lines / cm), and Example 1 The composition for colloidal crystals prepared in 1 above was printed on a primer layer of a film substrate having a primer layer, and dried in an oven at 50 ° C. for 3 minutes to obtain a laminate on which a pattern was printed. The thickness of the colloidal crystal layer was 5 μm.

[Examples 39 to 86, Comparative Examples 10 to 16]
The composition for colloidal crystals is placed on the primer layer of the substrate having the primer layer in the same manner as in Example 38, except that the primer solution, the composition for colloidal crystals, and the thickness of the colloidal crystal layer are changed to the contents shown in Table 7-1. The material was printed to obtain a laminate.
In Examples 83 to 86, the gravure cylinder was changed to the following, and the thickness of the colloidal crystal layer was adjusted.
Example 83: Toyo FPP gravure cylinder (engraving method: helio, cell shape: compressed, number of lines: 175 lines / cm)
Example 84: Toyo FPP gravure cylinder (engraving method: helio, cell shape: compressed, number of lines: 200 lines / cm)
Example 85: Toyo FPP gravure cylinder (engraving method: corrosion, cell capacity: 60 μm) Example 86: Toyo FPP gravure cylinder (engraving method: corrosion, cell capacity: 100 μm)

[Examples Z-1 to Z-5]
The composition for colloidal crystals is placed on the primer layer of the substrate having the primer layer in the same manner as in Example 38, except that the primer solution, the composition for colloidal crystals, and the thickness of the colloidal crystal layer are changed to the contents shown in Table 7-2. The material was printed to obtain a laminate.

<Evaluation of laminated body>
The obtained laminate was evaluated as follows. The results are shown in Table 7-1 and Table 7-2 (hereinafter referred to as Table 7).

[Printability]
The pattern part of the laminated body was visually observed for the presence or absence of swimming such as the outline of the pattern and streaks, and evaluated according to the following criteria.
S: The outline of the pattern is clear and no swimming has occurred (extremely good).
A: The outline of the pattern is clear, but there is a slight swim (good).
B: The outline of the pattern is slightly blurred (usable)
C: The outline of the pattern is blurred and swimming is occurring (cannot be used)

[Color development (△ R, whitening)]
The reflection spectrum of the picture portion of the laminate was measured in the wavelength range of 250 to 850 nm using an ultraviolet-visible near-infrared spectrophotometer (V-770D manufactured by JASCO Corporation, integrating sphere unit ISN-923). The reflectance at each wavelength is a relative reflectance measured using a standard white plate (SRS-99-010 manufactured by Lovesphere Co., Ltd.) having a known reflectance as a reference. For the obtained reflection spectrum, the difference (ΔR) between the maximum value of the reflectance derived from the colloidal crystal and the reflectance of the baseline not due to the colloidal crystal was calculated. The larger the ΔR, the better the color development. In addition, the degree of whitening of the pattern part was visually confirmed. Based on ΔR and the bleaching situation, the evaluation was made according to the following criteria.
S: ΔR is 10% or more and there is no whitening (extremely good)
A: ΔR is 10% or more, and there is slight whitening (good).
B: ΔR is 5% or more and less than 10% (usable)
C: △ R is less than 5% (cannot be used)

[Angle dependence]
With the printed surface of the laminate as a reference, changes in the color of the pattern portion at angles of 15 °, 45 °, and 90 ° were visually observed and evaluated according to the following criteria. The angle dependence is so excellent that the color does not change from any angle. S: The color does not change at any angle (extremely good)
A: The color of 15 ° and the color of 90 ° are slightly different (good).
B: The color of 45 ° and the color of 90 ° are slightly different (usable).
C: The color is clearly different at each angle (cannot be used)

[Base material followability]
The laminate was cut into a size of 10 cm × 10 cm to prepare a test piece. This test piece was rubbed 30 times, and the appearance of peeling and scratches on the pattern portion was visually observed and evaluated according to the following criteria.
S: No peeling or scratches, and no change in color development (extremely good)
A: The area of peeling and scratches is less than 5% of the test piece, and there is no change in color development (good).
B: The area of peeling and scratches is 5% or more and less than 15% of the test piece, and there is no change in color development (usable).
C: The area of peeling or scratches is 15% or more of the test piece, or the color is fading (cannot be used).

[Abrasion resistance]
The laminate was cut into a size of 10 cm × 10 cm to prepare a test piece. The pattern portion of this test piece was rubbed 20 times with the pad of a finger, and the state of peeling and scratches was visually observed and evaluated according to the following criteria.
S: No peeling or scratches (extremely good)
A: The area of peeling and scratches is less than 5% of the rubbed area (good)
B: The area of peeling or scratches is 5% or more and less than 15% of the rubbed area (usable)
C: The area of peeling or scratches is 15% or more of the rubbed area (cannot be used)

[Solvent resistance]
After dripping an ethanol solution on the pattern portion of the laminate, the mixture was dried at 50 ° C. for 3 minutes, and the reflection spectrum was measured in the same manner as in the [color development] evaluation. The rate of change (decrease rate) of the maximum value of the reflectance was calculated by comparing the reflected light spectra before and after the test. The larger the rate of change, the more the colloidal crystals are fading. Based on the obtained reduction rate, evaluation was made according to the following criteria.
S: The rate of change of the maximum value of reflectance is less than 2% (extremely good)
A: The rate of change of the maximum value of reflectance is 2% or more and less than 15% (good).
B: The rate of change of the maximum value of reflectance is 15% or more and less than 30% (usable)
C: The rate of change of the maximum value of reflectance is 30% or more (cannot be used)

According to Table 7, the composition of the present invention containing a hydrophilic solvent (C) having a predetermined boiling point and / or a nonionic surfactant (D) having a predetermined HLB value and having a predetermined surface tension was excellent. The printed layer having gravure printability and formed by the composition exhibits excellent color development property and low angle dependence, and further has excellent trackability to a substrate, abrasion resistance, and solvent resistance. Was there.
In particular, those using the core-shell type resin fine particles of Production Examples 3 and 4 in which the glass transition point of the shell is in the range of -30 to 10 ° C. have very good gravure printability and color development, and are low-angle dependent. Was also excellent. In addition, it was also excellent in various coating film resistances such as followability to a substrate, abrasion resistance, and solvent resistance (eg, Examples 40, 41, 80, etc.).
On the other hand, many of the compositions of the comparative examples are inferior in gravure printability, and even if they have gravure printability, none of the obtained laminates can achieve both color development and low angle dependence. rice field.

Claims (12)

Resin fine particles (A), achromatic black fine particles (B) (excluding resin fine particles (A)), water, and a hydrophilic solvent (C) having a boiling point of 95 to 250 ° C. at 1 atm and / or an HLB value. A composition for colloidal crystals, which contains 10.0 to 19.0 of a nonionic surfactant (D), has a surface tension of 25 to 42 mN / m at 25 ° C., and is for gravure printing. thing. The colloidal crystal according to claim 1, wherein the total of the hydrophilic solvent (C) and the nonionic surfactant (D) is 0.5 to 20% by mass based on the total amount of the composition for colloidal crystals. Composition. Claimed that the hydrophilic solvent (C) contains at least one selected from the group consisting of a lower monoalcohol solvent (C-1), a glycol solvent (C-2), and a glycol ether solvent (C-3). Item 2. The composition for colloidal crystals according to Item 1 or 2. Claim 1 that the nonionic surfactant (D) contains at least one selected from the group consisting of polyoxyalkylene alkyl ethers (D-1) and polyglycerin fatty acid esters (D-2). 3. The composition for colloidal crystals according to any one of the above items. The composition for colloidal crystals according to any one of claims 1 to 4, which contains the resin fine particles (A) in an amount of 22.5 to 43.2% by mass based on the composition for colloidal crystals. The composition for colloidal crystals according to any one of claims 1 to 5, wherein the achromatic black fine particles (B) are contained in an amount of 0.10 to 20% by mass based on the resin fine particles (A). Any one of claims 1 to 6, wherein the resin fine particles (A) are of the core-shell type, the glass transition point of the core portion is 60 ° C. or higher, and the glass transition point of the shell portion is −50 to 20 ° C. The composition for colloidal crystals according to. The composition for colloidal crystals according to claim 7, wherein the content of the shell of the resin fine particles (A) is in the range of 10 to 300% by mass with respect to the total mass of the core. A laminate comprising a colloidal crystal layer formed from the composition for colloidal crystals according to any one of claims 1 to 8 on a substrate. The laminate according to claim 9, wherein the substrate has a primer layer, and the glass transition point of the primer layer is −60 to 100 ° C. The laminate according to claim 9 or 10, wherein the colloidal crystal layer has a thickness of 1.0 to 20 μm. A method for producing a laminate having a colloidal crystal layer formed of a colloidal crystal composition on a substrate.
On the substrate, resin fine particles (A), achromatic black fine particles (B) (excluding resin fine particles (A)), water, and a hydrophilic solvent (C) having a boiling point of 95 to 250 ° C. at 1 atm and / Or a composition for colloidal crystals containing a nonionic surfactant (D) having an HLB value of 10.0 to 19.0 and having a surface tension of 25 to 42 mN / m at 25 ° C. is gravure-printed to form a colloidal crystal. A method for producing a laminate, which comprises a step of forming a layer.