Composition for Colloidal Crystal, Laminate, and Method for Manufacturing Laminate

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

Technical Field

[0001] The present invention relates to a composition for colloidal crystals for forming colloidal crystals, and a laminate using the composition.

Background Art

[0002] Photonic crystals are artificial crystals having a nano-periodic structure in which substances with different refractive indices are arranged at intervals on the order of the wavelength of light. They have various interesting optical properties such as reflection of light with a specific wavelength known as Bragg reflection, an optical confinement effect due to a photonic band gap, and an optical amplification effect, and thus have been actively studied in recent years. Among them, colloidal crystals in which colloidal-sized particles are regularly arranged are one type of photonic crystal that can be produced relatively easily. However, due to problems in controlling the particle arrangement and its immobilization, mass production has not been achieved. In addition, although attempts have been made to print colloidal crystals as patterns, the number of such attempts is small, and a pattern print having good color developability, low angle dependence, and various coating film resistances has not been obtained.

[0003] Patent Document 1 discloses a method of printing a pattern by applying a composition for colloidal crystals containing monodisperse resin fine particles onto a substrate in advance, applying an original plate from the back side of the substrate, and then heating in a state where unevenness has occurred to utilize the height difference of the particle layer, that is, the difference in the number of laminations. However, in this method, pattern printing is limited to the colloidal crystal layer. In addition, it is difficult to form a contrast between the printed portion and the non-printed portion, and the visibility of the pattern is poor. Further, the composition for colloidal crystals described in Patent Document 1 is inferior in leveling property to the plate and the substrate, and thus high-quality printed matter cannot be obtained in plate printing such as gravure printing.

[0004] 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 since the solvent rapidly volatilizes from the droplets, the arrangement of the particles is greatly disrupted, the color-developing property as a structural color deteriorates, and the coating film also significantly whitens. Further, even if the composition described in Patent Document 2 is applied to gravure printing, drying defects and leveling defects occur, and a high-quality printed product cannot be obtained.

[0005] From the above, there is a demand for the development of a composition for colloidal crystals and a laminate thereof that achieve both good printing suitability, color-developing property, and low-angle dependence, have good various coating film resistances, and can obtain a high-quality pattern.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] The problem to be solved by the present invention is to provide a composition capable of forming a colloidal crystal layer having good gravure printing suitability and achieving both excellent color-developing property and low-angle dependence, and a laminate including the colloidal crystal layer formed from the composition and achieving both excellent color-developing property and low-angle dependence.

Means for Solving the Problems

[0008] That is, the present invention relates to a composition for colloidal crystals, which contains resin fine particles (A), achromatic black fine particles (B) (excluding the 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 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 and is for gravure printing.

[0009] Further, the present invention relates to the above composition for colloidal crystals, wherein 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.

[0010] Further, the present invention relates to the above composition for colloidal crystals, wherein 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).

[0011] Further, the present invention relates to the above composition for colloidal crystals, wherein 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).

[0012] Further, the present invention relates to the above composition for colloidal crystals, wherein the resin fine particles (A) are contained in an amount of 22.5 to 43.2% by mass based on the composition for colloidal crystals.

[0013] Further, the present invention relates to the above composition for colloidal crystals, 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).

[0014] Further, the present invention relates to the above composition for colloidal crystals, wherein the resin fine particles (A) are core-shell type, the glass transition point of the core part is 60 ° C or higher, and the glass transition point of the shell part is -50 to 20 ° C.

[0015] The present invention also relates to a composition for colloidal crystals, wherein the content of the shell of the resin fine particles (A) is in the range of 10 to 300% by mass based on the total mass of the core.

[0016] The present invention also relates to a laminate comprising a colloidal crystal layer formed from the above composition for colloidal crystals on a substrate.

[0017] The present invention also relates to the above laminate, wherein the substrate has a primer layer, and the glass transition point of the primer layer is -60 to 100°C.

[0018] The present invention also relates to the above laminate, wherein the thickness of the colloidal crystal layer is 1.0 to 20 μm.

[0019] The present invention also relates to a method for producing a laminate comprising a colloidal crystal layer formed from a composition for colloidal crystals on a substrate, which comprises a step of forming a colloidal crystal layer by gravure printing a composition for colloidal crystals containing 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 nonionic surfactant (D) having an HLB value of 10.0 to 19.0 on the substrate, and having a surface tension of 25 to 42 mN / m at 25°C.

Effects of the Invention

[0020] According to the present invention, it is possible to provide a composition capable of forming a colloidal crystal layer having good gravure printing suitability and achieving both excellent color developability and low angle dependence, and a laminate comprising a colloidal crystal layer formed from the composition and achieving both excellent color developability and low angle dependence.

Modes for Carrying Out the Invention

[0021] <Composition for Colloidal Crystals> The composition for colloidal crystal of the present invention is for gravure printing, and contains resin fine particles (A), achromatic black fine particles (B), water, a hydrophilic solvent (C) having a boiling point of 95 to 250 °C per atmospheric pressure and / or a nonionic surfactant (D) having an HLB value of 10.0 to 19.0, and is characterized in that the surface tension at 25 °C is 25 to 42 mN / m. Since the composition of the present invention contains the hydrophilic solvent (C) having a predetermined boiling point and / or the nonionic surfactant (D) having a predetermined HLB value and has a predetermined surface tension, it has excellent gravure printing suitability and exhibits a remarkable effect of enabling high-quality pattern printing that achieves both color development and low-angle dependence. Furthermore, the colloidal crystal formed from the composition of the present invention is excellent in followability to the substrate, abrasion resistance, and solvent resistance. Hereinafter, the requirements constituting the present invention will be described in detail.

[0022] <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 crystal, and in the process of being applied to and dried on the substrate, they are regularly arranged and laminated in a close-packed form due to the advection accumulation phenomenon accompanying the volatilization of water. Then, the void portion is replaced from water to air to form a colloidal crystal layer. The colloidal crystal layer in this specification is a layer that exhibits a structural color derived from Bragg reflection, and by controlling the particle diameter of the resin fine particles (A), the periodic interval can be controlled, and various colors can be developed. The average particle diameter of the resin fine particles (A) is preferably in the range of 180 to 330 nm. When it is in the above range, the color development in the visible light region of the colloidal crystal layer becomes clear, and a colloidal crystal coating film with more excellent color development can be obtained, which is preferable. The average particle diameter in this specification can be measured by the dynamic light scattering method, and the peak of the obtained volume particle size distribution data (histogram) is taken as the average particle diameter.

[0023] [Polymer of ethylenically unsaturated monomer (a)] The type and manufacturing method of the resin fine particles (A) are not particularly limited, and any monodispersible resin fine particles can be used. However, from the viewpoints that it is easy to control the refractive index and monodispersity of the fine particles (A) and that they have excellent color-developing properties, the resin fine particles (A) are preferably polymers of ethylenically unsaturated monomers (a). More preferably, they are resin fine particles composed of an acrylic resin or a styrene-acrylic resin.

[0024] The resin fine particles that are polymers of ethylenically unsaturated monomers (a) can be produced, for example, by the following emulsion polymerization. First, an aqueous medium and a surfactant are charged into a reaction vessel and heated to a predetermined temperature. On the other hand, water, a surfactant, and an ethylenically unsaturated monomer (a) are charged into a dropping vessel, and stirred to prepare an emulsion of the ethylenically unsaturated monomer (a). Then, under a nitrogen atmosphere, a radical polymerization initiator is added while dropping the prepared emulsion into the reaction vessel. After the reaction starts, polymer particle nuclei are generated, and the particles gradually grow to form resin fine particles.

[0025] Examples of the ethylenically unsaturated monomer (a) include aromatic ethylenically unsaturated monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenyl (meth)acrylate; linear or branched alkyl group-containing ethylenically unsaturated monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate; alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate; fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate; carboxy group-containing ethylenically unsaturated monomers such as (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, succinic acid β-(meth)acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid;Sulfonic acid group-containing ethylenically unsaturated monomers such as sodium 2-acrylamido-2-methylpropanesulfonate, methallylsulfonic acid, methallylsulfonic acid, sodium methallylsulfonate, allylsulfonic acid, sodium allylsulfonate, ammonium allylsulfonate, vinylsulfonic acid; Amide group-containing ethylenically unsaturated monomers such as (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-propoxymethylmethacrylamide, N,N-di(propoxymethyl)acrylamide, N-butoxymethyl-N-(propoxymethyl)methacrylamide, N,N-di(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-di(pentoxymethyl)acrylamide, N-methoxymethyl-N-(pentoxymethyl)methacrylamide, N,N-dimethylaminopropylacrylamide, N,N-diethylaminopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, diacetoneacrylamide; Hydroxyl group-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl alcohol; Polyoxyethylene group-containing ethylenically unsaturated monomers such as methoxypolyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate;Examples include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, etc., and amino group-containing ethylenically unsaturated monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate; epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate; ketone group-containing ethylenically unsaturated monomers such as diacetone (meth)acrylamide, acetoacetoxy (meth)acrylate; 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, rosinyl (meth)acrylate, cinnamyl (meth)acrylate, diallyl maleate, diallyl itaconate, 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 (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylpropane triacrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, diallyl maleate, etc., ethylenically unsaturated monomers having two or more ethylenically unsaturated groups;Alkoxysilyl group-containing ethylenically unsaturated monomers such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane; methylol group-containing ethylenically unsaturated monomers such as N-methylol(meth)acrylamide, N,N-dimethylol(meth)acrylamide, alkyl etherified N-methylol(meth)acrylamide; are mentioned. These monomers may be used alone or in combination of two or more.

[0026] 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 may be used. Since the resin fine particles (A) have a reactive group, a crosslink can be introduced into 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, friction resistance, and solvent resistance are further improved.

[0027] The crosslink 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 crosslinking agent. The crosslink between the colloidal crystal layer and the primer layer described later can be introduced by a method of reacting the reactive group of the resin fine particles (A) with the reactive group of the primer layer, a method of crosslinking the reactive group of the resin fine particles (A) with the reactive group of the primer layer via a polyfunctional crosslinking agent, and the like.

[0028] Examples of the reactive group that the ethylenically unsaturated monomer (a) may have include an epoxy group, a carboxy group, a hydroxy group, a ketone group, a hydrazide group, etc., and a ketone group is more preferable. In particular, when the reactive group is a ketone group and the crosslinking agent is a hydrazide crosslinking agent, a ketone-hydrazide crosslink can be formed. The ketone-hydrazide crosslink is preferably used because it does not adversely affect the various physical properties of the colloidal crystal and can form a crosslink at a low temperature and in a short time due to the volatilization of water, and it is effective when using a film substrate that is easily damaged by heating. Further, since the ketone group has high hydrophilicity, 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, and it is considered that a crosslink can be efficiently formed with the hydrazide crosslinking agent.

[0029] 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, and the substrate followability, abrasion resistance, and solvent resistance are further improved within a range that does not adversely affect the color developability.

[0030] [Radical polymerization initiator] As the radical polymerization initiator used in the polymerization reaction of the ethylenically unsaturated monomer (a), known oil-soluble polymerization initiators or water-soluble polymerization initiators can be used, and these may be used alone or in combination of two or more.

[0031] The oil-soluble polymerization initiator is not particularly limited. For example, organic peroxides such as benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), tert-butyl peroxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide; azobis compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis-cyclohexane-1-carbonitrile; can be mentioned.

[0032] In emulsion polymerization, it is preferable to use a water-soluble polymerization initiator. For example, conventionally known ones such as ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2'-azobis(2-methylpropionamidine) dihydrochloride can be suitably used.

[0033] [Surfactant] In the production of resin fine particles that are polymers of ethylenically unsaturated monomer (a), surfactants such as low molecular weight surfactants and polymer dispersants can be used. By using a surfactant, the stability and monodispersity of the resin fine particles can be improved. From the viewpoint of excellent monodispersity of the resin fine particles, a low molecular weight surfactant is preferably used as the surfactant. Examples of the low molecular weight surfactant include anionic or nonionic ones. More specifically, anionic reactive surfactants, anionic non-reactive surfactants, nonionic reactive surfactants, and nonionic non-reactive surfactants can be mentioned, and an anionic surfactant is preferably used. These surfactants may be used alone or in combination of two or more.

[0034] Here, the reactive surfactant refers to those that can polymerize with the above-mentioned ethylenically unsaturated monomers. More specifically, it means those having a reactive group capable of undergoing a polymerization reaction with an ethylenically unsaturated bond. Here, examples of the reactive group include alkenyl groups such as vinyl group, allyl group, 1-propenyl group, and (meth)acryloyl group. By using the reactive surfactant, the particle arrangement of the colloidal crystal and the free emulsifier components that have an adverse effect on weather resistance (moisture resistance) are reduced, so that the color developability of the colloidal crystal, the color developability after the weather resistance test, the substrate followability, and the pressure indentation resistance are further improved, which is preferable.

[0035] (Anionic surfactant) Examples of anionic reactive surfactants include polyoxyethylene alkyl ether sulfate-based (commercially available products such as Aqualon KH-05, KH-10, KH-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Adekaria Soap SR-10N, SR-20N manufactured by ADEKA Corporation, Latemul PD-104 manufactured by Kao Corporation, etc.); polyoxyalkylene styrenated phenyl ether sulfate ester-based (commercially available products such as Aqualon AR-10, AR-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); sulfosuccinate ester-based (commercially available products such as Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Ereminol JS-2 manufactured by Sanyo Chemical Industries, Ltd., etc.); polyoxyethylene alkyl phenyl ether sulfate-based or polyoxyethylene alkyl phenyl ester sulfate-based (commercially available products such as Aqualon HS-10, HS-20, HS-30, BC-10, BC-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Adekaria Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc. manufactured by ADEKA Corporation); (meth)acrylate sulfate ester-based (commercially available products such as Antox MS-60, MS-2N manufactured by Nippon Surfactant Co., Ltd., Ereminol RS-30 manufactured by Sanyo Chemical Industries, Ltd., etc.); phosphate ester-based (commercially available products such as H-3330PL manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Adekaria Soap PP-70 manufactured by ADEKA Corporation, etc.).

[0036] Examples of anionic non-reactive surfactants include higher fatty acid salts such as sodium oleate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate esters such as sodium lauryl sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate (commercially available products include Hitenol LA-10, LA-12, LA-16, etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0037] (Nonionic surfactant) Examples of nonionic reactive surfactants include polyoxyalkylene alkyl ethers (commercially available products include Adekaria Soap ER-10 (HLB 12.3), ER-20 (HLB 15.1), ER-30 (HLB 16.4), ER-40 (HLB 17.1) manufactured by ADEKA Corporation, Latemul PD-420 (HLB 12.6), PD-430 (HLB 14.4), PD-450 (HLB 16.2) manufactured by Kao Corporation, etc.); polyoxyalkylene styrenated phenyl ethers (commercially available products include Aqualon AN-10 (HLB 13.0), AN-20 (HLB 18.0), etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); polyoxyethylene alkyl phenyl ethers (commercially available products include Aqualon RN-20 (HLB 14.2), RN-30 (HLB 16.7), etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0038] Examples of nonionic non-reactive surfactants include polyoxyalkylene alkyl ethers (commercially available products such as Neugen XL-50 (HLB 11.6), XL-100 (HLB 14.7), XL-1000 (HLB 19.3), TDS-50 (HLB 10.5), TDS-70 (HLB 12.1), TDS-80 (HLB 13.3), TDS-120 (HLB 14.8), Neugen TDX-80 (HLB 13.1), TDX-140 (HLB 14.4), Kao's Emulgen 106 (HLB 10.5), 108 (HLB 12.1), 1108 (HLB 13.5), 1135S-70 (HLB 17.9), etc.); polyoxyalkylene styrenated phenyl ethers (commercially available products such as Neugen EA-87 (HLB 10.6), EA-127 (HLB 11.7), EA-157 (HLB 14.3), Kao's Emulgen A-60 (HLB 12.8), A-90 (HLB 14.5), A-500 (HLB 18.0), etc.); polyoxyethylene alkyl phenyl ethers (commercially available products such as Aoki Yushi Kogyo Co., Ltd.'s Branown N-505 (HLB 10.0), Branown NK-8055 (HLB 10.8), etc.); polyglycerin fatty acid esters (commercially available products such as Nikko Chemicals Co., Ltd.'s NIKKOL Hexaglyn1-L (HLB 14.5), Decaglyn-1-L (HLB 15.5), Decaglyn-1-M (HLB 14.0), Decaglyn-1-LN (HLB 12.0), etc.); polyoxyethylene glycerin fatty acid esters (commercially available products such as Nikko Chemicals Co., Ltd.'s NIKKOL TMGS-5V (HLB 9.5), TMGS-15V (HLB 13.5), TMGO-5 (HLB 9.5), TMGO-15 (HLB 14.5), etc.); polyoxyethylene sorbitan fatty acid esters (commercially available products such as Nikko Chemicals Co., Ltd.'s NIKKOL TL-10 (HLB 16.9), TP-10EX (HLB 15.6), TS-10V (HLB 14.9), TS-30V (HLB 10.5), TO-10V (HLB 15.0), TO-106V (HLB 10.0), Kao's Leodol TW-L120 (HLB 16.7), TW-L106 (HLB 13.3), TW-P120 (HLB 15.6), TW-S120V (HLB 14.9), TW-S-106 (HLB 9.5) TW-O-106 (HLB 10.0), etc.; polyoxyethylene sorbitol fatty acid esters (commercially available products include NIKKOL GL-1 (HLB 15.5), GS-460 (HLB 13.0), GO-440V (HLB 12.5), GO-460V (HLB 14.0) manufactured by Nikko Chemicals Co., Ltd., Leodol 430V (HLB 10.5), 440V (HLB 11.8), 460V (HLB 13.8) manufactured by Kao Corporation; polyethylene glycol fatty acid esters (commercially available products include EMALEX-810 (HLB 11.0), 820 (HLB 14.0), 830 (HLB 15.0), 840 (HLB 16.0) manufactured by Nippon Emulsion Co., Ltd., Emanon 1112 (HLB 13.7), Emanon 3199V (HLB 19.4) manufactured by Kao Corporation, etc.; sucrose fatty acid esters (commercially available products include S-970 (HLB 9.0), S-1170 (HLB 11.0), S-1570 (HLB 15.0), S-1670 (HLB 16.0), P = 1570 (HLB 15.0), P-1670 (HLB 16.0), M-1695 (HLB 16.0), O-1570 (HLB 15.0), L-1695 (HLB 16.0), LWA-1570 (HLB 15.0), etc. manufactured by Mitsubishi Chemical Foods Co., Ltd.; polyoxyethylene lanolins (commercially available products include NIKKOL TW-10 (HLB 12.0), TW-20 (HLB 13.0), BWA-5 (HLB 12.5), BWA-10 (HLB 15.5), BWA-20 (HLB 16.0), etc. manufactured by Nikko Chemicals Co., Ltd.; polyoxyethylene hydrogenated castor oils (commercially available products include NIKKOL HCO-20 (HLB 10.5), HCO-30 (HLB 11.0), HCO-40 (HLB - 12.5), HCO-100 (HLB 16.5), etc. manufactured by Nikko Chemicals Co., Ltd.; polyoxyethylene sterols (commercially available products include NIKKOL BPS-5 (HLB 9.5), BPS-10 (HLB 12.5), BPS-20 (HLB - 30), BPSH-25 (HLB 14.5), etc. manufactured by Nikko Chemicals Co., Ltd.) can be mentioned.

[0039] (Polymer dispersant) Examples of the polymer dispersant include polyvinyl alcohol, polyvinyl pyrrolidone, polyoxyethylene-polyoxypropylene block copolymer, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, 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-(meth)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 Tosoh Corporation Polinas PS-1, Polinas PS-5, etc.), styrene sulfonic acid-maleic acid copolymer, polyitaconic acid, polyhydroxyethyl (meth)acrylate, poly(meth)acrylamide, (meth)acrylamide-(meth)acrylic acid copolymer, polyvinyl methyl ether, methyl vinyl ester, water-soluble vinyl copolymers such as carboxyvinyl polymer; urethane resin obtained by the polyaddition reaction of polyisocyanate and polyol, and water-soluble polyurethane resin in which the whole resin is solubilized by the introduction of a hydrophilic group; polyester resin obtained by the polycondensation reaction of polyvalent carboxylic acid and polyol, and water-soluble polyester resin in which the whole resin is solubilized by the introduction of a hydrophilic group; may be mentioned.

[0040] [Core-shell type resin fine particles] The resin fine particles (A) in the present invention preferably have a core-shell structure, more preferably, both the core and the shell are water-insoluble resins and are mutually incompatible. 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. After the core-shell type resin fine particles (A) are applied onto a substrate and drying proceeds, they regularly arrange and stack. At this time, the shells fuse with each other at the contact portions between the core-shell type particles, voids are replaced from the aqueous medium with air, and a colloidal crystal layer is formed. When the resin fine particles (A) are of the core-shell type, the shell can bind the achromatic black fine particles (C) described below and suppress the loss of the achromatic black fine particles (C). Thereby, the substrate followability, abrasion resistance, and solvent resistance of the laminate are further improved. Further, when the substrate has a primer layer described below, the shell also fuses with the resin of the primer layer, so that the colloidal crystal is more firmly fixed.

[0041] In the core-shell type resin fine particles (A), the content of the shell 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 binding between the resin fine particles (A) and between the resin fine particles (A) and the primer layer becomes stronger. Therefore, the substrate followability, abrasion resistance, and solvent resistance of the laminate are further improved. From the viewpoint of color development property, the content of the shell is preferably in the range of 150% by mass or less, more preferably 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 is obtained. In the colloidal crystal, when air exists in the void portion of the core-shell type resin fine particles, the refractive index difference between the particles and the matrix becomes large, so that the color development property of the colloidal crystal is improved. On the one hand, from the perspective of scratch resistance, 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. When the content of the shell is 50% by mass or more, the fusion of the shell further progresses during film drying, and the binding between the core-shell type resin fine particles and between the core-shell type resin fine particles and the substrate becomes stronger, and a colloidal crystal excellent in scratch resistance can be obtained.

[0042] The glass transition point of the core of the core-shell type resin fine particles (A) is preferably 60°C or higher, more preferably in the range of 60 to 150°C. When the glass transition point is 60°C or higher, the deformation of the core shape due to the influence of heat and solvent is suppressed. Thereby, a laminate excellent in color developability, abrasion resistance, and solvent resistance can be obtained.

[0043] The glass transition point of the shell part 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. By being in the above range, the filling of the void part of the colloidal crystal layer by the fusion of the shell is suppressed. Furthermore, the fusion of the shell sufficiently progresses, and the binding between the resin fine particles (A) and between the resin fine particles (A) and the primer layer becomes stronger. Therefore, the substrate followability, abrasion resistance, and solvent resistance of the laminate are further improved.

[0044] Also, the coefficient of variation (Cv value) of the average particle diameter 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 diameter and can be calculated by the following formula. Formula: Coefficient of variation Cv value (%) = standard deviation of particle diameter / average particle diameter × 100 [In the formula, the units of the standard deviation and the average particle diameter are the same] When the coefficient of variation is 30% or less, the regularity of the particle arrangement is improved, and the color developability of the colloidal crystal becomes better.

[0045] 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 still more preferably 1.45 to 2.00. When the refractive index is 1.45 or more, the color development property of the colloidal crystal is improved, which is preferable.

[0046] 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 crystal. When the content of the resin fine particles (A) is 22.5% by mass or more, the leveling property of the composition for colloidal crystal on the substrate during gravure printing is improved, and the disturbance of the particle arrangement is suppressed. Therefore, a gravure laminate excellent in printing suitability and color development property can be obtained. When the content is 43.2% by mass or less, the clogging of the plate of the composition for colloidal crystal and the disturbance of the particle arrangement due to rapid drying are suppressed, and a laminate excellent in printing suitability and color development property can be obtained.

[0047] <achromatic black fine particles (B)> The composition for colloidal crystal of the present invention contains achromatic black fine particles (B) (excluding the resin fine particles (A)). The achromatic black fine particles (B) function to absorb unnecessary scattered light in the colloidal crystal and make the color development of the colloidal crystal clearer in the colloidal crystal layer in which the resin fine particles (A) are regularly arranged. 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. From the viewpoints that the coloring component is hardly eluted in water or a solvent and the durability of the colorant is excellent, carbon black is preferable. Carbon black may be of a dispersion type dispersed in water using a dispersant or a self-dispersing type. However, from the viewpoint that the influence on the particle arrangement by the dispersant does not occur, it is preferable to use a self-dispersing type carbon black. Examples of commercially available products of carbon black aqueous dispersions include, for example, the Lion Pace series (such as W-310A) manufactured by Lion Corporation and the BONJET BLACK CW series (CW-1, CW-2, CW-3, etc.) manufactured by Orient Chemical Industries.

[0048] The average particle diameter of the achromatic black fine particles (B) is preferably in the range of 30 to 300 nm. When it is within the above range, the inhibition to the regular arrangement of the resin fine particles (A) is small, and the achromatic black fine particles (B) are more likely to be immobilized in the colloidal crystal. Therefore, the abrasion resistance and solvent resistance of the colloidal crystal layer are further improved.

[0049] 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). When the content is 0.1% by mass or more, a colloidal crystal with clearer and better color developability can be obtained. When it is 20% by mass or less, a colloidal crystal with better abrasion resistance and solvent resistance can be obtained while maintaining clear color developability.

[0050] <Hydrophilic solvent (C), nonionic surfactant (D)> It is important that the composition for colloidal crystal of the present invention contains a hydrophilic solvent (C) having a boiling point of 95 to 250 °C per atmospheric pressure and / or a nonionic surfactant (D) having an HLB value of 10.0 to 19.0. By including these, it has excellent gravure printing suitability and enables high-quality pattern printing that combines color developability and low-angle dependence.

[0051] [Hydrophilic solvent (C)] The above hydrophilic solvent (C) is a solvent having a boiling point of 95 to 250 °C per atmospheric pressure. When the boiling point is 95 °C or higher, during gravure printing, it prevents rapid drying of the composition for colloidal crystal and at the same time improves the leveling property on the substrate. Thereby, excellent printing suitability is exhibited. Also, when the boiling point of the hydrophilic solvent (C) is 95 °C or higher, the central part of the pattern is suppressed from rapid drying, so a regularly arranged colloidal crystal layer can be obtained. Therefore, when the pattern layer is viewed from the front, it has no whitening and excellent color developability. On the other hand, in gravure printing, since water and solvent volatilize from the end face of the pattern, the arrangement of the colloidal crystal layer at the end of the pattern becomes slightly disordered due to rapid drying. Generally, a colloidal crystal film with a regular arrangement of the entire surface has a large angle dependence due to Bragg reflection. However, the film obtained by gravure printing the composition of the present invention has different arrangements at the center and the edge of the pattern. By disturbing some of the arrangements in this way, clear color development of RGB can be obtained, and at the same time, a pattern with low angle dependence where the color tone does not change significantly when viewed from anywhere can be obtained.

[0052] Since the boiling point of the hydrophilic solvent (C) is 250°C or lower, the residual solvent is reduced, and adverse effects on color development such as swelling of particles due to the residual solvent and deterioration of the film resistance do not occur, and colloidal crystals excellent in color development, abrasion resistance, and solvent resistance can be obtained. The boiling point of the hydrophilic solvent (C) is preferably in the range of 100 to 240°C.

[0053] Examples of the hydrophilic solvent (C) that can be used in the present invention include monohydric lower monoalcohol solvents (C-1) such as 1-propanol (b.p. 97 °C), 1-butanol (b.p. 118 °C), 2-methyl-1-propanol (b.p. 108 °C), 2-butanol (b.p. 100 °C); glycol solvents (C-2) such as ethylene glycol (b.p. 197.0 °C), 1,3-propanediol (b.p. 230 °C), propylene glycol (b.p. 188 °C), 1,2-butanediol (b.p. 192 °C), 1,4-butanediol (b.p. 230 °C), pentylene glycol (b.p. 188 °C), 1,2-hexanediol (b.p. 230 °C), 1,6-hexanediol (b.p. 208 °C), diethylene glycol (b.p. 245 °C); glycol ether solvents (C-3) such as ethylene glycol monomethyl ether (b.p. 124 °C), diethylene glycol monomethyl ether (b.p. 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 (b.p. 208 °C), diethylene glycol dimethyl ether (b.p. 162 °C), triethylene glycol dimethyl ether (b.p. 216 °C), propylene glycol monomethyl ether (b.p. 120 °C), dipropylene glycol monomethyl ether (b.p. 194 °C), dipropylene glycol dimethyl ether (b.p. 175 °C), tripropylene glycol monomethyl ether (b.p. 243 °C); lactam solvents such as N-methyl-2-pyrrolidone (b.p. 202 °C), N-hydroxyethyl-2-pyrrolidone (b.p. 175 °C), 2-pyrrolidone (b.p. 245 °C); formamide (b.p.amide solvents such as 3-methoxy-N,N-dimethylpropionamide (b.p. 210 °C), 3-butoxy-N,N-dimethylpropanamide (b.p. 252 °C), etc.; are exemplified. These hydrophilic solvents (C) may be used alone or in combination of two or more.

[0054] Preferably, the hydrophilic solvent (C) is at least one selected from the group consisting of lower monoalcohol solvents (C-1), glycol solvents (C-2), and glycol ether solvents (C-3). By containing such a hydrophilic solvent, the leveling property of the composition for colloidal crystals and the control of the regular arrangement of particles are improved, and further excellent printing suitability is exhibited. In addition, colloidal crystals excellent in color developability, low angle dependence, substrate followability, abrasion resistance, and solvent resistance can be obtained.

[0055] [Nonionic surfactant (D)] The above 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. Also, adverse effects such as disturbing the regular arrangement of the resin fine particles (A) or swelling of the resin fine particles (A) by the surfactant do not occur. As a result, colloidal crystals exhibiting excellent printing suitability and color developability and excellent substrate followability, abrasion resistance, and solvent resistance with respect to the substrate can be obtained. When the HLB value is 19.0 or less, the surface tension of the composition for colloidal crystals decreases to an appropriate range. As a result, the composition for colloidal crystals has improved leveling property, exhibits excellent printing suitability, and colloidal crystals excellent in color developability, abrasion resistance, and solvent resistance can be obtained.

[0056] The HLB value is a numerical representation of the hydrophilic-lipophilic nature of a material, and the smaller the HLB value, the higher the lipophilicity. In this specification, the HLB value is calculated by the Griffin's method calculation formula represented by the following formula (1). Formula (1) HLB value = 20 × (sum of formula weights of hydrophilic moieties) ÷ (molecular weight of the material)

[0057] As the nonionic surfactant (D), those having an HLB value of 10.0 to 19.0 listed in the above item (nonionic surfactant) can be used. Preferably, the nonionic surfactant (D) is 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 colloidal crystal composition and the control of the regular arrangement of particles are improved, and further excellent printing suitability is exhibited. In addition, colloidal crystals excellent in color developability, 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.

[0058] The colloidal crystal composition of the present invention only needs to contain at least one selected from the group consisting of the above hydrophilic solvent (C) and the above nonionic surfactant (D). Whether it contains only the hydrophilic solvent (C), only the nonionic surfactant (D), or both the hydrophilic solvent (C) and the nonionic surfactant (D), the excellent effects of the present invention are similarly exhibited. The total content of the above hydrophilic solvent (C) and nonionic surfactant (D) is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 15% by mass, and still more preferably in the range of 1 to 10% by mass based on the total amount of the colloidal crystal composition. By being in such a range, the leveling property to the substrate is improved without affecting the regular arrangement of the resin fine particles (A), and excellent printing suitability is exhibited. In addition, colloidal crystals more excellent in color developability and low-angle dependence can be obtained. Furthermore, since there is no risk of deteriorating the coating film resistance, it is also excellent in substrate followability, abrasion resistance, and solvent resistance.

[0059] <Properties of the colloidal crystal composition> The composition for colloidal crystals of the present invention has a surface tension at 25 °C of 25 to 42 mN / m. By having a surface tension of 25 mN / m or more, the disorder of the regular arrangement of the resin fine particles (A) is suppressed, and even in gravure printing, a printed matter having excellent printability and clear color developability and including colloidal crystals can be obtained. By having a surface tension of 42 mN / m or less, the leveling property on the substrate is excellent, and even in gravure printing, a printed matter having excellent printability and clear color developability and including colloidal crystals can be obtained. Furthermore, this printed matter is excellent in substrate followability, abrasion resistance, and solvent resistance.

[0060] The surface tension at 25 °C of the composition for colloidal crystals is preferably 26 to 40 mN / m. The surface tension in this specification can be measured by the plate method (Wilhelmy method) using a surface tensiometer.

[0061] <Crosslinking agent> As described above, the composition for colloidal crystals of the present invention may contain a crosslinking agent in order to form crosslinks within the colloidal crystal layer and between the colloidal crystal layer and the primer layer. The crosslinking agent is not particularly limited and can be appropriately selected according to the reactive groups of the colloidal crystal layer and the primer layer. For example, a hydrazide compound (polyhydrazide) having two or more hydrazino groups that react with an active carbonyl group to form a keto-hydrazide crosslink; an isocyanate compound that reacts with a hydroxyl group or an amino group to form a urethane bond or a urea bond; an epoxy compound that reacts with a carboxy group, an amino group, etc. can be mentioned, and it can be appropriately selected according to the use. More specifically, for example, when the resin fine particles (A) or the primer component has a carboxy group, crosslinks can be formed via an epoxy crosslinking agent. Also, for example, when the resin fine particles (A) or the primer component has a hydroxyl group, crosslinks can be formed via a polyisocyanate crosslinking agent. Also, for example, when the resin fine particles (A) or the primer component has a ketone group, crosslinks can be formed via a hydrazide crosslinking agent. As the crosslinking agent, as described above, in order to form a ketone-hydrazide crosslink, it is preferable to use a hydrazide crosslinking agent. Examples of the hydrazide crosslinking agent include adipic acid dihydrazide and a water-soluble resin modified with a polyfunctional hydrazide group.

[0062] The composition for colloidal crystals may contain various additives as long as the effects of the present invention are not impaired. For example, a leveling agent, a thickening agent, and a preservative can be blended.

[0063] <Laminate> The composition for colloidal crystals of the present invention is for gravure printing, and can be transferred from a plate made on a cylinder to a substrate and printed by the gravure printing method of an intaglio plate. By forming a colloidal crystal layer by gravure printing the composition for colloidal crystals on the substrate, the laminate of the present invention can be obtained.

[0064] Gravure printing can transfer more composition for colloidal crystals from the plate to the substrate in one printing, and suppresses a significant disturbance in the particle arrangement due to rapid drying. Therefore, it is possible to obtain a pattern printed matter with excellent color development, which was difficult with letterpress printing or inkjet methods. For gravure plate making, various cell shapes (conventional type, screen gravure type, laser type, etc.) produced by engraving or etching methods can be used. The composition for colloidal crystals applied on the substrate by transfer dries to form a colloidal crystal layer. The drying method is not particularly limited, and examples include a heat drying method, a hot air drying method, an infrared drying method, a microwave drying method, and a drum drying method. From the viewpoints of the influence on the regular arrangement of the resin fine particles (A) and productivity, the drying temperature is preferably in the range of 20 to 80°C.

[0065] 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. By being in the above range, excellent printing suitability and color development are sufficiently ensured, and a laminate with excellent substrate followability, abrasion resistance, and solvent resistance can be obtained.

[0066] <Substrate> The substrate is not particularly limited and can be appropriately selected according to the use. For example, thermoplastic resin substrates such as polyvinyl chloride sheets, polyethylene terephthalate (PET) films, polypropylene films, polyethylene films, nylon films, polystyrene films, and polyvinyl alcohol films; metal substrates such as aluminum foils; glass substrates, and paper substrates such as coated papers.

[0067] The surface of the substrate on which the coating is applied may be smooth or may have irregularities. The substrate may be transparent, translucent, or opaque, and a substrate pre-colored with black or the like may be used to make the color development of the colloidal crystal coating film clearer. Further, the substrate may be used alone or may be a laminate in which two or more substrates are laminated.

[0068] In order to further improve the fixing property of the colloidal crystal layer on the substrate, it is preferable that the substrate has a primer layer. The primer layer can be formed by previously applying a primer component on the substrate. The primer component is not particularly limited, and examples thereof include acrylic resins, styrene acrylic resins, urethane resins, olefin resins, polyester resins, and composite resins obtained by compounding these resins. These primer components may be used alone or in combination of two or more. From the viewpoints of excellent binding properties to the substrate and the colloidal crystal layer, and the resistance of the primer layer, etc., it is preferable to use an acrylic resin, a styrene acrylic resin, or a urethane resin as the primer component.

[0069] 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 within the above range, during gravure printing, blocking between the primer layer and the gravure plate making in the non-printing part is suppressed. Further, it is suppressed that the primer component penetrates into the colloidal crystal layer and adversely affects the color development of the colloidal crystal layer. Thereby, a colloidal crystal excellent in printing suitability, color development property, substrate followability, friction resistance, and solvent resistance can be obtained.

[0070] The primer layer may contain additives as long as the effects of the present invention are not impaired. Examples of such additives include surfactants or achromatic black particles, and the above description can be incorporated by reference.

Examples

[0071] The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" mean "parts by mass" and "mass %" unless otherwise specified.

[0072] [Average particle size, Cv value] The average particle size was measured by diluting the fine particle dispersion 500-fold with water and measuring about 5 ml of the diluted solution by dynamic light scattering measurement method (the measuring device is NanoTrack UPA (manufactured by 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 × 100 [In the formula, the units of the standard deviation and the average particle size are the same]

[0073] [Glass transition point (Tg)] The glass transition point was measured by DSC (differential scanning calorimeter manufactured by TA Instruments). Specifically, about 2 mg of a dried sample of the resin fine particle dispersion was weighed on an aluminum pan, the aluminum pan was set in a DSC measurement holder, and the baseline shift (inflection point) on the endothermic side of the DSC curve obtained under the temperature rising condition of 5 °C / min was read to obtain the glass transition point.

[0074] [Surface tension γ] The surface tension γ was the value measured by the plate method (Wilhelmy method) using a surface tension meter (automatic surface tension meter DY-300) manufactured by Kyowa Interface Science Co., Ltd. under the condition of 25 °C.

[0075] <Preparation of resin fine particle (A) dispersion> [Production Example 1] 68.9 parts of water was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Subsequently, 3% of an emulsion of ethylenically unsaturated monomers, which was separately prepared by mixing and stirring 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, 1.0 part of 3-methacryloxypropyltriethoxysilane, 5.0 parts of a 20% aqueous solution of Aqualon KH-10 (Dai-ichi Kogyo Seiyaku Co., Ltd., an anionic reactive surfactant of the polyoxyethylene alkyl ether sulfate type), and 40.4 parts of water, was further added to the reaction vessel. After raising the internal temperature of the reaction vessel to 70 °C and sufficiently purging 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 temperature by raising the internal temperature to 80 °C, the remainder of the emulsion of ethylenically unsaturated monomers and 2.0 parts of a 5% aqueous solution of potassium persulfate were added dropwise over 3 hours, and the reaction was continued for another 4 hours. Then, 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 diameter 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.

[0076] [Production Example 2] An aqueous dispersion of resin fine particles (A-2) with a solid content concentration of 45.0% was prepared in the same manner as in Production Example 1, except that the composition shown in Table 1 was changed. For the obtained resin fine particles, the average particle diameter, Cv value, and Tg were measured in the same manner as in Production Example 1.

[0077] [Production Example 3] 95.0 parts of water was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Subsequently, 1.5% of a first-stage emulsion of ethylenically unsaturated monomers, which was separately prepared by mixing and stirring 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, was further added to the reaction vessel. After raising the internal temperature of the reaction vessel to 70 °C and sufficiently purging with nitrogen, 5.7 parts of a 2.5% aqueous solution of potassium persulfate was added as an initiator to start the polymerization. While raising the internal temperature to 80 °C and maintaining the temperature, the remainder of the emulsion of the first-stage ethylenically unsaturated monomer and 4.0 parts of a 2.5% aqueous solution of potassium persulfate were added dropwise over 2 hours while reacting to synthesize core particles. The average particle diameter of the produced core particles was 205 nm. Twenty minutes after completion of the first-stage dropping, separately, 15.0 parts of methyl methacrylate, 23.1 parts of n-butyl acrylate, 0.9 part of acrylic acid, 2.1 parts of a 20% aqueous solution of Aqualon KH-10, and 16.8 parts of water were mixed and stirred to prepare the second-stage ethylenically unsaturated monomer emulsion for dropping. While maintaining 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, water 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 diameter of the obtained core-shell type resin fine particles was 255 nm, the Cv value was 26.1%, the Tg of the core part was 100.1 °C, and the Tg of the shell part was -4.0 °C.

[0078] [Production Examples 4 to 10] An aqueous dispersion of core-shell type fine particles (A-3 to A-10) was prepared in the same manner as in Production Example 3, except that the composition was changed to that shown in Table 2-1. During the synthesis, the emulsion of the ethylenically unsaturated monomer was prepared by adding water so that the concentration of the ethylenically unsaturated monomer in the emulsion was 69.0% and the concentration of the surfactant was 0.69%. 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. For the obtained core-shell type resin fine particles, the average particle diameter, Cv value, and Tg were measured in the same manner as in Production Example 3.

[0079] [Production Examples X-1 to X-5] Aqueous dispersions of core-shell type fine particles (X-1 to X-5) were prepared in the same manner as in Production Example 3, except that the composition shown in Table 2-2 was changed. At the time of synthesis, water was added to the emulsion of ethylenically unsaturated monomers to prepare an emulsion in which the concentration of ethylenically unsaturated monomers in the emulsion was 69.0% and the concentration of surfactant was 0.69%. After synthesis, the solid content concentration of the aqueous dispersion of core-shell type resin fine particles was adjusted to 45.0% by adding water or dehydrating by vacuum stripping. For the obtained core-shell type resin fine particles, the average particle diameter, Cv value, and Tg were measured in the same manner as in Production Example 3.

[0080] 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 Table 1 and Table 2 represent "parts" unless otherwise specified, and blanks mean that they are not blended.

[0081] [Table 1]

[0082] [Table 2-1]

[0083] [Table 2-2]

[0084] [Preparation of Composition for Colloidal Crystal] [Example 1] To 100 parts of the aqueous dispersion of the resin fine particles (A-1) of Production Example 1, 3.8 parts of BONJET BLACK CW-1 (surface-modified carbon black, average particle diameter 62 nm, pigment content 20.0%) manufactured by Orient Chemical Industries Co., Ltd. as colorless black fine particles, 5 parts of diethylene glycol monobutyl ether, 1.0 part of Emulgen 1108 manufactured by Kao Corporation, and 1.0 part of adipic acid dihydrazide were added and stirred to prepare a composition for colloidal crystal.

[0085] [Examples 2 to 37, Comparative Examples 1 to 7] Colloidal crystal compositions were each prepared in the same manner as in Example 1, except that the composition was changed to that shown in Tables 3-1 to 3-3.

[0086] [Examples Y-1 to Y-5] Colloidal crystal compositions were each prepared in the same manner as in Example 1, except that the composition was changed to that shown in Table 3-4.

[0087] The properties of the obtained compositions for forming a colloidal crystal layer 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 a blank means that it is not blended.

[0088]

Table 3-1

[0089]

Table 3-2

[0090]

Table 3-3

[0091]

Table 3-4

[0092] <Preparation of primer solution> [Production Example 11] Into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 68.9 parts of water and 0.25 part of a 20% aqueous solution of Aqualon KH-10 as a reactive surfactant were charged. Subsequently, 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, 1.0 part of 3-methacryloxypropyltriethoxysilane, 4.8 parts of a 20% aqueous solution of Aqualon KH-10, and 40.4 parts of water were mixed and stirred in advance to prepare an emulsion of ethylenically unsaturated monomers. Then, 3% of the prepared emulsion was further added to the reaction vessel. After raising the internal temperature of the reaction vessel to 80 °C and thoroughly purging with nitrogen, 2.0 parts of a 5% aqueous solution of potassium persulfate as an initiator were added to initiate emulsion polymerization. While maintaining the internal temperature at 80 °C, the remaining emulsion of ethylenically unsaturated monomers and 2.0 parts of a 5% aqueous solution of potassium persulfate were added dropwise over 3 hours, and the reaction was continued for another 4 hours to obtain an aqueous dispersion of resin fine particles. After completion of the reaction, 1.9 parts of 25% aqueous ammonia were added for neutralization, and water was added to adjust the solid content concentration of the aqueous dispersion of resin fine particles to 40.0%. The Tg of the resin fine particles was -3.2 °C. To the obtained aqueous dispersion of resin fine particles, 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 Industries Co., Ltd. were added and stirred and mixed to obtain a primer solution.

[0093] [Production Examples 12 to 14] Primer solutions were prepared in the same manner as in Production Example 11, except that the composition was changed to that shown in Table 4.

[0094] [Production Example 15] Into a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a reflux condenser, 185.0 parts of water, 42.6 parts of JONCRYL 67 (styrene acrylic resin manufactured by BASF, Mw 12,500, acid value 213 mgKOH / g) as a polymer dispersant, and 11.1 parts of 25% aqueous ammonia were charged, and the temperature was raised with stirring to dissolve the polymer dispersant. After further raising the temperature to 80 °C under nitrogen reflux, using two dropping funnels, from one dropping funnel, a mixed solution of 14.0 parts of styrene, 15.0 parts of n-butyl methacrylate, 30.0 parts of 2-ethylhexyl acrylate, 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% aqueous solution of ammonium persulfate was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 5 hours to obtain an aqueous dispersion of resin fine particles. After completion of the reaction, water was added to adjust the solid content concentration of the aqueous dispersion of resin fine particles to 40.0%. The Tg of the obtained resin fine particles was -3.4 °C. To the obtained aqueous dispersion of resin fine particles, 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 Industries Co., Ltd. were added and stirred and mixed to obtain a primer solution.

[0095] [Production Examples 16, 17] Primer solutions were prepared in the same manner as in Production Example 15, except that the composition was changed to that shown in Table 5.

[0096] [Production Example 18] Into a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, as polyols, 19.6 parts of PTG-2000SN (polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd. (functional group number 2, hydroxyl value 57.0, molecular weight 2,000)), 20.3 parts of P-2011 (3-methyl-1,5-pentanediol / adipic acid / terephthalic acid-based polyester polyol manufactured by Kuraray Co., Ltd. (functional group number 2, hydroxyl value 55.0, molecular weight 2,000)), 91.6 parts of C-2090 (polycarbonate polyol manufactured by Kuraray Co., Ltd. (functional group number 2, hydroxyl value 56.0, molecular weight 2,000)), 19.7 parts of dimethylolbutanoic acid, as a polyisocyanate, 48.8 parts of isophorone diisocyanate, as a solvent, 40.0 parts of methyl ethyl ketone, and 10.0 parts of dipropylene glycol dimethyl ether were charged, and the temperature was raised to 78 °C while stirring under a nitrogen atmosphere. 0.02 part of titanium diisopropoxybis(ethylacetoacetate) 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 phase inversion was carried out into the aqueous phase while removing the solvent under reduced pressure conditions. After promoting the chain extension reaction of the isocyanate groups in the aqueous medium, an aqueous dispersion of a urethane resin having a solid content concentration of 30.0% was prepared. To the prepared resin aqueous dispersion, 2.0 parts of diethylene glycol monobutyl ether, 1.0 part 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 Industries Co., Ltd. were added and stirred and mixed to obtain a primer solution.

[0097] [Production Example 19] A primer solution was prepared in the same manner as in Production Example 18, except that the composition shown in Table 6 was changed.

[0098]

Table 4

[0099]

Table 5

[0100]

Table 6

[0101] 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: 3-Methyl-1,5-pentanediol / adipic acid / terephthalic acid-based polyester polyol manufactured by Kuraray Co., Ltd. (number of functional groups: 2, hydroxyl value: 55.0, molecular weight: 2,000) C-2090: Polycarbonate polyol manufactured by Kuraray Co., Ltd. (number of functional groups: 2, hydroxyl value: 56.0, molecular weight: 2,000)

[0102] <Production of Laminated Body by Gravure Printing> [Example 38] On the corona-treated surface of a biaxially stretched polypropylene (OPP) film (FOR manufactured by Futamura, thickness: 20 μm), the primer solution prepared in Production Example 12 was coated with a bar coater so that the dried thickness would be 2 μm, and then dried in an oven at 80°C for 3 minutes to form a primer layer. Further, a gravure cylinder (engraving method: heliotype, cell shape: compressed, number of lines: 70 lines / cm) manufactured by Toyo FPP was set on a simple gravure coater (GRAVO-PROOF MINI manufactured by Nissho Gravure Co., Ltd.), and the composition for colloidal crystal prepared in Example 1 was printed on the primer layer of the film substrate having the primer layer, and dried in an oven at 50°C for 3 minutes to obtain a laminated body with a pattern printed thereon. The thickness of the colloidal crystal layer was 5 μm.

[0103] [Examples 39 to 86, Comparative Examples 10 to 16] A laminated body was obtained in the same manner as in Example 38, except that the primer solution, the composition for colloidal crystal, and the thickness of the colloidal crystal layer were changed to the contents shown in Table 7-1, and the composition for colloidal crystal was printed on the primer layer of the substrate having the primer layer. 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: Gravure cylinder made by Toyo FPP (Engraving method: Helio, Cell shape: Compressed, Line count: 175 lines / cm) Example 84: Gravure cylinder made by Toyo FPP (Engraving method: Helio, Cell shape: Compressed, Line count: 200 lines / cm) Example 85: Gravure cylinder made by Toyo FPP (Engraving method: Etching, Cell capacity: 60 μm) Example 86: Gravure cylinder made by Toyo FPP (Engraving method: Etching, Cell capacity: 100 μm)

[0104] [Examples Z-1 to Z-5] A primer solution, a composition for colloidal crystals, and the thickness of the colloidal crystal layer were changed to the contents shown in Table 7-2. Otherwise, in the same manner as in Example 38, a composition for colloidal crystals was printed on the primer layer of a substrate having a primer layer to obtain a laminate.

[0105] [Evaluation of laminate] 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).

[0106] [Printing suitability] Regarding the pattern part of the laminate, the presence or absence of bleeding such as the outline and lines of the pattern entering was visually observed and evaluated according to the following criteria. S: The outline of the pattern is clear and no bleeding has occurred (extremely good) A: The outline of the pattern is clear, but slight bleeding has occurred (good) B: The outline of the pattern is slightly blurred (usable) C: The outline of the pattern is blurred and bleeding has occurred (unusable)

[0107] [Color development (ΔR, whitening)] Regarding the pattern part of the laminate, a reflection spectrum 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 the relative reflectance measured using a standard white plate with a known reflectance (SRS-99-010 manufactured by Labsphere) 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 ΔR is, the better the color development. Also, the degree of whitening of the pattern part was visually confirmed. Based on ΔR and the whitening situation, the following criteria were used for evaluation. 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: ΔR is less than 5% (not usable)

[0108] [Angle dependence] With reference to the printed surface of the laminate, the change in the hue of the pattern part at angles of 15°, 45°, and 90° was visually observed and evaluated according to the following criteria. The better the angle dependence, the less the hue changes when viewed from any angle. S: The hue does not change at any angle (extremely good) A: The hue at 15° and the hue at 90° are slightly different (good) B: The hue at 45° and the hue at 90° are slightly different (usable) C: The hues are clearly different at each angle (not usable)

[0109] [Substrate followability] The laminate was cut into a size of 10 cm × 10 cm to prepare test pieces. These test pieces were rubbed 30 times, and the appearance of peeling and scratches on the pattern part was visually observed and evaluated according to the following criteria. S: There is no peeling or scratches and no change in color development (extremely good) A: The area of peeling or scratches is less than 5% of the test piece and there is no change in color development (good) B: The area of peeling or 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 it is faded (not usable).

[0110] [Abrasion resistance] The laminate was cut into test pieces with a size of 10 cm × 10 cm. The pattern part of this test piece was rubbed 20 times back and forth with the pulp of the finger, and the peeling and scratch conditions were visually observed and evaluated according to the following criteria. S: There is no peeling or scratches (extremely good). A: The area of peeling or 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 (not usable).

[0111] [Solvent resistance] After dropping an ethanol solution on the pattern part of the laminate, it was dried at 50 °C for 3 minutes, and the reflection spectrum was measured in the same manner as the [color development property] evaluation. By comparing the reflection light spectra before and after the test, the change rate (decrease rate) of the maximum value of the reflectance was calculated. The larger the change rate, the more the colloidal crystal is faded. Based on the obtained decrease rate, the following criteria were used for evaluation. S: The change rate of the maximum value of the reflectance is less than 2% (extremely good). A: The change rate of the maximum value of the reflectance is 2% or more and less than 15% (good). B: The change rate of the maximum value of the reflectance is 15% or more and less than 30% (usable). C: The change rate of the maximum value of the reflectance is 30% or more (not usable).

[0112]

Table 7-1

[0113]

Table 7-2

[0114] According to Table 7, the composition of the present invention containing the hydrophilic solvent (C) having a predetermined boiling point and / or the nonionic surfactant (D) having a predetermined HLB value and having a predetermined surface tension has excellent gravure printing suitability, and the printed layer formed by the composition exhibits excellent color developability and low angle dependence. Furthermore, it was excellent in followability to the substrate, abrasion resistance, and solvent resistance. 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 had very good gravure printing suitability and color developability, and were also excellent in low angle dependence. They were also excellent in various coating film resistances such as followability to the substrate, abrasion resistance, and solvent resistance (for example, Examples 40, 41, 80, etc.). On the other hand, many of the compositions of the comparative examples were inferior in gravure printing suitability, and even if they had gravure printing suitability, none of the obtained laminates could achieve both color developability and low angle dependence.

Claims

1. A composition for colloidal crystals, comprising resin fine particles (A), colorless black fine particles (B) (excluding the 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 nonionic surfactant (D) having an HLB value of 10.0 to 19.0, having a surface tension at 25°C of 25 to 42 mN / m, wherein the content of the resin fine particles (A) is 22.5 to 43.2% by mass based on the total amount of the composition for colloidal crystals, and the total content 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, and being for gravure printing.

2. The composition for colloidal crystals according to claim 1, wherein 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).

3. The composition for colloidal crystals according to claim 1 or 2, wherein 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).

4. The composition for colloidal crystals according to any one of claims 1 to 3, wherein the colorless black fine particles (B) are contained in an amount of 0.10 to 20% by mass based on the resin fine particles (A).

5. The composition for colloidal crystals according to any one of claims 1 to 4, wherein the resin fine particles (A) are core-shell type, the glass transition point of the core part is 60°C or higher, and the glass transition point of the shell part is -50 to 20°C.

6. The composition for colloidal crystals according to claim 5, wherein the content of the shell of the resin fine particles (A) is in the range of 10 to 300% by mass based on the total mass of the core.

7. A laminate comprising a colloidal crystal layer formed from the composition for colloidal crystals according to any one of claims 1 to 6 on a substrate.

8. The laminate according to claim 7, wherein the substrate has a primer layer, and the glass transition point of the primer layer is -60 to 100°C.

9. The laminate according to claim 7 or 8, wherein the thickness of the colloidal crystal layer is 1.0 to 20 μm.

10. A method for producing a laminate comprising a colloidal crystal layer formed from a composition for colloidal crystals on a substrate, On a substrate, there are resin fine particles (A), achromatic black fine particles (B) (excluding the 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 nonionic surfactant (D) having an HLB value of 10.0 to 19.

0. It has a surface tension of 25 to 42 mN / m at 25°C. The content of the resin fine particles (A) is 22.5 to 43.2% by mass based on the total amount of the composition for colloidal crystal. The total content 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 crystal. A method for manufacturing a laminate, which includes a step of forming a colloidal crystal layer by gravure printing the composition for colloidal crystal.

Images