JP7415802B2 - Primer and laminate - Google Patents

Description

The present invention relates to a primer and a laminate for fixing a colloidal crystal layer to a substrate.

A photonic crystal is an artificial crystal with a nano-periodic structure in which materials with different refractive indexes are arranged at intervals similar to the wavelength of light. It has been actively studied in recent years because it has various interesting optical properties such as confinement effect and optical amplification effect. Among them, a colloidal crystal in which colloid-sized particles are arranged regularly is one of the photonic crystals that can be produced relatively easily.However, a layer containing colloidal crystals (a colloidal crystal layer ) to the base material, protect the colloidal crystal layer from ultraviolet light, atmospheric moisture, shock, etc., and maintain it stably for a long period of time. has not yet been reached.

Patent Document 1 discloses a coating film of colloidal crystals in which a resin composition for colloidal crystals to which an aqueous resin as a binder component is added in advance is applied and fixed by drying. However, this fixing method has a problem in that the binder component inhibits the regular arrangement of the particles, which significantly deteriorates the color development of the coating film. Furthermore, since a primer layer is not specially provided, unevenness tends to occur at the interface with the base material, resulting in insufficient adhesion to the base material and coating film durability (insufficient adhesion).

Patent Document 2 discloses a colloidal crystal coating film in which a colloidal crystal layer is bound and fixed on a base material coated with an adhesive component as a primer layer. However, the primer described in Patent Document 2 has a problem in that the strength of the coating film is low and scratches and impressions are easily formed. Furthermore, the primer described in Patent Document 2 has a problem in that the color development of the coating film deteriorates over time because the primer component gradually invades and fills the voids in the colloidal crystals. Furthermore, the primer layer formed by the primer described in Patent Document 2 has low water resistance and solvent resistance and has not reached a practical level (intrusion into voids and insufficient strength).

Patent Document 3 discloses a coating film of colloidal crystals in which colloidal crystals are bound and fixed on a base material coated with polyvinyl alcohol as a primer layer. However, the primer described in Patent Document 3 has low water resistance and solvent resistance, and when the composition for colloidal crystal layer is applied on the primer, the primer component is eluted and mixed into the composition for colloidal crystal layer. There is a problem in that it disrupts the regular arrangement of crystals and deteriorates color development. Furthermore, a primer layer made of polyvinyl alcohol cannot suppress deterioration of the colloidal crystal layer due to long-term outdoor exposure. (Lack of outdoor exposure)

From the above, it is possible to maintain the color development of colloidal crystals over time without disturbing the arrangement of colloidal crystals, and furthermore, by fixing the colloidal crystal layer to the base material, it has excellent outdoor exposure properties and scratch resistance. There is a need for a primer that can provide durability, water resistance, and solvent resistance.

Japanese Patent Application Publication No. 2007-126646 Japanese Patent Application Publication No. 2008-246846 Japanese Patent Application Publication No. 2006-116781

The problem to be solved by the present invention is to be able to maintain the coloring properties of colloidal crystals over a long period of time, and to also maintain outdoor exposure resistance, substrate followability of the coating film, substrate adhesion, water resistance, and resistance. The object of the present invention is to provide a primer for fixing a colloidal crystal layer to a base material, which has excellent solvent properties, and a laminate using the primer.

The present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the present invention.
That is, the present invention provides a primer for fixing a colloidal crystal layer to a base material, wherein the primer contains an aqueous resin (A) and water, and the aqueous resin (A) is represented by the following general formula (1). At least one type of ethylene selected from the group consisting of the ethylenically unsaturated monomer (a-1) represented by the following general formula (2) and the ethylenically unsaturated monomer (a-2) represented by the following general formula (2) The present invention relates to a primer containing a structural unit derived from a sexually unsaturated monomer.

（一般式（１）中、Ｘは水素原子又はメチル基を表す。） General formula (1): Ethylenically unsaturated monomer (a-1)

(In general formula (1), X represents a hydrogen atom or a methyl group.)

General formula (2): Ethylenically unsaturated monomer (a-2)
(In general formula (2), Y and Z each independently represent a hydrogen atom or a methyl group.)

The present invention provides that the total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) is based on the total mass of the aqueous resin (A), 2 to 40% by mass of the above primer.

The present invention relates to the above primer, wherein the aqueous resin (A) has a glass transition point of -60°C to 100°C.

The present invention relates to a laminate comprising a primer layer formed from the above primer and a colloidal crystal layer in this order on a base material.

The present invention relates to the above laminate, wherein the colloidal crystal layer contains core-shell resin fine particles.

The present invention relates to the above laminate, in which the primer layer and the colloidal crystal layer form a crosslink.

According to the present invention, a colloidal crystal layer that can maintain the coloring properties of colloidal crystals over a long period of time and has excellent outdoor exposure properties, substrate followability, substrate adhesion, water resistance, and solvent resistance. A primer for fixing to a base material and a laminate using the primer can be provided.

<Primer>
The present invention provides a primer for fixing a colloidal crystal layer to a base material, wherein the primer contains an aqueous resin (A), and the aqueous resin (A) is represented by the following general formula (1). At least one ethylenically unsaturated monomer selected from the group consisting of the ethylenically unsaturated monomer (a-1) represented by the following general formula (2) and the ethylenically unsaturated monomer (a-2) represented by the following general formula (2). It is characterized by containing a monomer-derived structural unit.
Since the primer has a structural unit derived from the above-mentioned specific ethylenically unsaturated monomer, the colloidal crystal layer and the primer layer are bonded more firmly, and the primer layer has excellent transparency, and is also resistant to water and solvents. It has excellent durability.
Furthermore, the primer layer can protect the colloidal crystal layer from ultraviolet rays of sunlight that enter from the colloidal crystal layer side and are reflected by the base material. Furthermore, when the base material is a transparent base material, the colloidal crystal layer can be protected from ultraviolet rays of sunlight entering from the side of the transparent base material. As a result of the above, the colloidal crystal layer can maintain good color development even when exposed outdoors for a long period of time. And to obtain a laminate having a colloidal crystal layer that can maintain good outdoor exposure properties, substrate followability of the coating film, substrate adhesion, water resistance, and solvent resistance even when exposed outdoors for a long period of time. I can do it.

<Aqueous resin (A)>
First, the aqueous resin (A) used in the present invention will be explained.
The aqueous resin (A) as used herein refers to a resin that can be dispersed or dissolved in an aqueous medium. The aqueous medium herein refers to an aqueous dispersion medium or an aqueous solvent, and includes not only water but also a dispersion medium or a solvent that is miscible with water.
The aqueous resin (A) takes a dispersed or dissolved form in the primer, and after being applied to a substrate or the like, forms a film during the drying process to form a water-insoluble primer layer. Furthermore, a colloidal crystal layer is formed on this primer layer. In this specification, a laminate of a primer layer and a colloidal crystal layer is referred to as a "colloidal crystal coating film."

[Ethylenically unsaturated monomer (a-1), (a-2)]
The aqueous resin (A) consists of an ethylenically unsaturated monomer (a-1) represented by the following general formula (1) and an ethylenically unsaturated monomer (a-1) represented by the following general formula (2). There is no particular restriction as long as it contains a structural unit derived from at least one ethylenically unsaturated monomer selected from the group consisting of 2), and preferably an ethylenically unsaturated monomer represented by general formula (1). A polymer of ethylenically unsaturated monomer (a) containing at least either monomer (a-1) or ethylenically unsaturated monomer (a-2) represented by general formula (2), Alternatively, it is a composite resin having the polymer unit.

General formula (1): Ethylenically unsaturated monomer (a-1)
(In general formula (1), X represents a hydrogen atom or a methyl group.)

General formula (2): Ethylenically unsaturated monomer (a-2)
(In general formula (2), Y and Z each independently represent a hydrogen atom or a methyl group.)

As the ethylenically unsaturated monomer (a-1) represented by the general formula (1), for example, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H- benzotriazole), 2-[2-hydroxy-5-[2-(acryloyloxy)ethyl]phenyl]-2H-benzotriazole).

Examples of the ethylenically unsaturated monomer (a-2) represented by the general formula (2) include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and 1,2 acrylic acid. , 2,6,6-pentamethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidyl acrylate.

The aqueous resin (A) is an ethylenically unsaturated monomer (a-1) represented by general formula (1) and an ethylenically unsaturated monomer (a-2) represented by general formula (2). It is preferable to include both structural units derived from. That is, the ethylenically unsaturated monomer (a) constituting the aqueous resin (A) contains both the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2). It is preferable to do so. By containing both monomers, the benzotriazole skeleton derived from the ethylenically unsaturated monomer (a-1), which is an ultraviolet absorbing skeleton, and the ethylenically unsaturated monomer (a-1), which is a photostabilizing skeleton, are combined. 2) Due to the interaction with the derived hindered amine skeleton, a synergistic effect is exerted in suppressing the deterioration of the primer layer. Therefore, it is possible to obtain a colloidal crystal coating film with less deterioration in color development, followability, and substrate adhesion even when exposed outdoors for a long period of time.

The total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) is preferably 2 to 2, based on the total mass of the aqueous resin (A). It is 40% by mass. When the content is 2% by mass or more, sufficient light resistance is exhibited, so that a colloidal crystal coating film with good color development, followability, and substrate adhesion even when exposed outdoors for a long time can be obtained. . When the content is 40% by mass or less, the film-forming properties of the aqueous resin (A) will be good, and the adhesiveness between the base material and the primer layer will be further improved. As a result, a colloidal crystal coating film having excellent followability and adhesion to the substrate can be obtained.

[Ethylenically unsaturated monomer (a-3)]
The ethylenically unsaturated monomer (a) forming the polymer may be any other copolymerizable ethylenically unsaturated monomer (a-1) or ethylenically unsaturated monomer (a-2). It may contain an ethylenically unsaturated monomer (a-3).
Examples of such other ethylenically unsaturated monomers (a-3) include 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, phenoxyhexaethylene glycol (meth)acrylate, phenyl (meth)acrylate, etc. Aromatic ethylenically unsaturated bodies of (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, etc. Ethylenically unsaturated monomers containing chain or branched alkyl groups; ethylenically unsaturated monomers containing alicyclic alkyl groups such as cyclohexyl (meth)acrylate and isobonyl (meth)acrylate; trifluoroethyl (meth)acrylate, hepta Ethylenically unsaturated monomers containing fluorinated alkyl groups such as decafluorodecyl (meth)acrylate; (anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, succinic acid β - Carboxy group-containing ethylenically unsaturated monomers such as (meth)acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid; sodium 2-acrylamide 2-methylpropanesulfonate, methallylsulfonic acid , sulfo group-containing ethylenically unsaturated monomers such as methallylsulfonic acid, sodium methallylsulfonate, allylsulfonic acid, sodium allylsulfonate, ammonium allylsulfonate, vinylsulfonic acid; (meth)acrylamide, N-methoxy Methyl-(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-diethyl Ethylenically unsaturated monomers containing amide groups such as acrylamide and diacetone acrylamide; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate Hydroxyl group-containing ethylenically unsaturated monomers such as acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol; polyoxyethylenes such as methoxypolyethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate group-containing ethylenically unsaturated monomer; examples include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, dimethylaminostyrene, diethylaminostyrene, etc. ) acrylate, diethylaminoethyl (meth)acrylate, methylethylaminoethyl (meth)acrylate, and other amino group-containing ethylenically unsaturated monomers; glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and other epoxies Group-containing ethylenically unsaturated monomer; ketone group-containing ethylenically unsaturated monomer 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 ) acrylate, 3-chloroallyl (meth)acrylate, o-allylphenyl (meth)acrylate, 2-(allyloxy)ethyl (meth)acrylate, allyl lactyl (meth)acrylate, citronellyl (meth)acrylate, geranyl (meth)acrylate, rhodinyl (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 (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, maleic acid Ethylenically unsaturated monomers having two or more ethylenically unsaturated groups such as diallyl; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ -Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyl Ethylenically unsaturated monomers containing alkoxysilyl groups such as trimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane; N-methylol ( Methylol group-containing ethylenically unsaturated monomers such as meth)acrylamide, N,N-dimethylol(meth)acrylamide, and alkyl etherified N-methylol(meth)acrylamide; but are not particularly limited to these. do not have.
These monomers may be used alone or in combination of two or more.

Among these, the ethylenically unsaturated monomer (a-3) preferably contains a carboxyl group-containing ethylenically unsaturated monomer. That is, it is preferable that the aqueous resin (A) has a carboxyl group, more preferably the acid value of the aqueous resin (A) is in the range of 5 to 40 mgKOH/g, and more preferably in the range of 5 to 20 mgKOH/g. be. When the acid value is within the above range, the wettability of the primer is improved, and a homogeneous primer layer with little unevenness can be easily formed. Further, hydrogen bonds derived from carboxyl groups are preferable because they further improve the binding property between the primer layer and the colloidal crystal layer. These improve the substrate followability and substrate adhesion of the colloidal crystal coating, suppress peeling and deterioration of the primer layer when exposed outdoors, and suppress deterioration of color development of the colloidal crystal coating. be able to.

In addition, the ethylenically unsaturated monomer (a-3) has a reactive group for the purpose of forming a crosslink in the primer layer and/or for the purpose of forming a crosslink with the fine particles (B) forming colloidal crystals. It may have. By forming a crosslink in the primer layer, it is possible to further suppress the components of the primer layer from being redissolved in water and affecting the colloidal crystals. In addition, by forming a crosslink between the primer layer and the colloidal crystal layer, the bond between the primer layer and the colloidal crystal layer is further strengthened, and the followability and substrate adhesion of the colloidal crystal coating film are further improved. . Furthermore, even when exposed outdoors, the primer layer is less likely to peel off or deteriorate, so even if exposed outdoors for a long time, good color development, trackability, and deterioration of substrate adhesion are more likely to occur. A coating film with fewer colloidal crystals is obtained.
Such crosslinking within the primer layer and between the primer layer and the colloidal crystal layer can be achieved by a method in which the reactive groups of the aqueous resin (A) are reacted with each other, or by a reaction between the aqueous resin (A) and the fine particles (B). a method of reacting the reactive groups of the aqueous resin (A) with each other via a polyfunctional crosslinking agent, a method of reacting the reactive groups of the aqueous resin (A) and the fine particles (B) with each other via a polyfunctional crosslinking agent, It can be introduced by a method of reacting reactive groups with each other.

Examples of the reactive group that the ethylenically unsaturated monomer (a-3) may have include an epoxy group, a carboxy group, a hydroxyl group, a ketone group, a hydrazide group, and more preferably a ketone group. . In particular, when the reactive group is a ketone group and the crosslinker is a hydrazide crosslinker, a ketone-hydrazide crosslink can be formed. Ketone hydrazide crosslinking is preferably used because it does not have a negative effect on the physical properties of colloidal crystals and can form crosslinks at low temperatures and in a short time due to water volatilization, and is useful when using film substrates that are easily damaged by heating. It is valid.
In addition, when the aqueous resin (A) is resin fine particles that can be dispersed in an aqueous medium, if an ethylenically unsaturated monomer having a highly hydrophilic ketone group is used in the copolymerization composition, the ketone group can be dispersed in the resin fine particles. It is thought that the hydrazide crosslinking agent is introduced outside the hydrazide crosslinking agent, that is, near the interface with the aqueous medium, and can efficiently form crosslinks with the hydrazide crosslinking agent.

When the aqueous resin (A) contains a ketone group, the preferred content of the ketone group is in the range of 0.05 to 0.3 mmol/g based on the mass of the aqueous resin (A). By introducing in the range of 0.05 to 0.3 mmol/g, crosslinking is formed without inhibiting the fusion of the aqueous resin (A), thereby further improving the film strength of the primer layer formed. Furthermore, since it has excellent binding with the colloidal crystal layer, the followability and adhesion of the colloidal crystal coating film to the substrate are further improved, and the coating film is less likely to deteriorate when exposed outdoors.

[Manufacture of water-based resin (A)]
Such aqueous resins (A) include, for example, acrylic resins such as acrylic polymers or styrene acrylic polymers; those having an acrylic skeleton and other skeletons such as acrylic/urethane composite resins or acrylic/olefin composite resins; Composite resins; and the method for producing them is not particularly limited.
The aqueous resin (A) in the present invention is preferably an acrylic resin, more preferably acrylic resin fine particles, from the viewpoint of water resistance and alcohol resistance.

(Acrylic resin fine particles)
When the aqueous resin (A) is acrylic resin fine particles, for example, a method of polymerizing the ethylenically unsaturated monomer (a) in an aqueous medium such as emulsion polymerization, or a method of polymerizing in a non-aqueous system and then removing the solvent. Although phase inversion emulsification in which the phase is inverted to an aqueous phase can be mentioned, it is preferable to use emulsion polymerization because it is possible to achieve high molecular weight, low viscosity, and high solid content concentration. In emulsion polymerization, a mixture of monomers is added dropwise in one step, a two-step polymerization in which the monomer composition is changed between the first and second steps, or a monomer mixture is added dropwise in three or more steps. Any multi-stage polymerization in which polymers are added dropwise while changing their composition may be used.

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 can be used singly. It may be used or a mixture of two or more types may be used.

The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-3,5,5-trimethylhexanoate and di-tert-butyl peroxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4- Examples include azobis compounds such as dimethylvaleronitrile, 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, and examples of the water-soluble polymerization initiator include ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, and 2,2'-azobis( Conventionally known compounds such as 2-methylpropionamidine) dihydrochloride can be suitably used.

Furthermore, in emulsion polymerization, a reducing agent may be used in combination with a polymerization initiator. By using a reducing agent in combination, the rate of emulsion polymerization can be accelerated and emulsion polymerization can be easily carried out at low temperatures. Examples of reducing agents include reducing organic compounds such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, and metal salts such as formaldehyde sulfoxylate; sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. Reducing inorganic compounds such as ferrous chloride, rongalite, and thiourea dioxide may be mentioned.
These reducing agents are preferably used in an amount of 0.05 to 5% by mass based on the ethylenically unsaturated monomer (a).

The polymerization temperature may be at least the polymerization initiation temperature of the polymerization initiator, and for example, in the case of a peroxide-based polymerization initiator, it is usually about 80°C. The polymerization time is not particularly limited, but is usually 2 to 24 hours. Note that the ethylenically unsaturated monomer (a) may be polymerized by photochemical reaction or radiation irradiation without using the above-mentioned polymerization initiator.

In the polymerization of the ethylenically unsaturated monomer (a), a buffer or a chain transfer agent may be further used as necessary. Buffers include, for example, sodium acetate, sodium citrate, and sodium bicarbonate. Examples of the chain transfer agent include mercaptans such as octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan.

In the polymerization of the ethylenically unsaturated monomer (a), a basic compound may be used as a neutralizing agent in order to improve the water dispersion stability of the aqueous resin (A). Examples of basic compounds include various organic amines such as aqueous ammonia, dimethylaminoethanol, diethanolamine, and triethanolamine; inorganic alkaline agents such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; Examples include organic acids and mineral acids.

When obtaining the aqueous resin (A), a low molecular emulsifier or a polymer emulsifier can be used during preparation for the purpose of improving the dispersion stability of the particles, and these may be used alone or Two or more types may be used in combination.
Examples of low-molecular emulsifiers include anionic reactive emulsifiers, anionic non-reactive emulsifiers, nonionic reactive emulsifiers, and nonionic non-reactive emulsifiers, which reduce free components from the primer layer and improve the coating film. From the viewpoint of improving resistance, it is preferable to use a reactive emulsifier that does not easily remain after polymerization as the low-molecular emulsifier.

Examples of anionic reactive emulsifiers include polyoxyethylene alkyl ether sulfate (commercially available products include Aqualon KH-05, KH-10, KH-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and ADEKA Co., Ltd.). Adekaria Soap SR-10N, SR-20N, Kao Latemul PD-104, etc.); polyoxyalkylene styrenated phenyl ether sulfate salts (commercially available products include Aqualon AR-10, Daiichi Kogyo Seiyaku Co., Ltd.); AR-20); sulfosuccinic acid ester type (commercially available products include Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Corporation, Eleminor JS-2 manufactured by Sanyo Chemical Co., Ltd.); Polyoxyethylene alkyl phenyl ether sulfate type or polyoxyethylene alkyl phenyl ester sulfate type (commercially available products include Aqualon HS-10, HS-20, HS-30, BC-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , BC-20, ADEKA Co., Ltd. Adekaria Soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.); (meth)acrylate sulfate ester type (Commercial products include, for example, Antox MS-60, MS-2N manufactured by Nippon Nyukazai Co., Ltd., and Eleminol RS-30 manufactured by Sanyo Chemical Industries, Ltd.); Phosphate ester-based (commercial products such as Daiichi Examples include H-3330PL manufactured by Kogyo Seiyaku Co., Ltd. and Adekaria Soap PP-70 manufactured by ADEKA Co., Ltd.).

Examples of anionic non-reactive emulsifiers include higher fatty acid salts such as sodium oleate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; alkyl sulfate ester salts such as sodium lauryl sulfate; polyexyethylene lauryl ether sulfate. Polyoxyethylene alkyl ether sulfates such as sodium (commercially available products include, for example, Hitenol LA-10, LA-12, and LA-16 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.);

Nonionic reactive emulsifiers include, for example, polyoxyethylene alkyl ethers (commercially available products include ADEKA Co., Ltd.'s Adekaria Soap ER-10, ER-20, ER-30, ER-40, Kao Corporation) Latemul PD-420, PD-430, PD-450, etc.); Polyoxyalkylene styrenated phenyl ether type (commercially available products include Aqualon AN-10, AN-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Polyoxy Ethylene alkyl phenyl ether type or alkyl phenyl ester type (commercially available products include Aqualon RN-10, RN-20, RN-30, RN-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Adekaria Soap NE manufactured by ADEKA Co., Ltd. -10, NE-20, NE-30, NE-40, etc.); (meth)acrylate sulfate ester type (commercially available products include, for example, RMA-564, RMA-568, RMA-1114 manufactured by Nippon Nyukazai Co., Ltd.); Can be mentioned.

Examples of nonionic non-reactive emulsifiers include polyoxyethylene alkylphenyl ethers such as polyoxyethylene lauryl ether (commercially available products include Neugen TDS-120 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); polyoxyethylene sorbitan monomers; Examples include polyoxyethylene sorbitan higher fatty acid esters such as laurate; polyoxyethylene monolaurate, polyoxyethylene higher fatty acid esters;

Examples of the polymer emulsifier include polyvinyl alcohol, polyvinylpyrrolidone, 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, vinylnaphthalene-(meth)acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinylpyrrolidone-(meth)acrylic acid Alkyl ester copolymer, vinylpyrrolidone-styrene copolymer, vinylpyrrolidone-vinyl acetate copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-(meth)acrylic acid copolymer, vinyl acetate-crotonic acid copolymer Polymer, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, polystyrene sulfonic acid, sodium polystyrene sulfonate (Polinus PS-1, Polinus PS-5, etc. manufactured by Tosoh Corporation), styrene sulfonic acid-maleic acid copolymer, polyitaconic acid, Water-soluble vinyl copolymers such as polyhydroxyethyl (meth)acrylate, poly(meth)acrylamide, (meth)acrylamide-(meth)acrylic acid copolymer, polyvinyl methyl ether, methyl vinyl ester, carboxyvinyl polymer; It is a urethane resin obtained by the polyaddition reaction of polyisocyanate and polyol, and is a water-soluble polyurethane resin in which the entire resin is made water-soluble by the introduction of hydrophilic groups; It is a polyester resin obtained by the polycondensation reaction of polyhydric carboxylic acid and polyol. , a water-soluble polyester resin in which the entire resin is made water-soluble by introducing a hydrophilic group.

Commercially available polymer emulsifiers include, for example, BASF JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60JJONCRYL61J, and JONCRYL6. 2J, JONCRYL63J, JONCRYLHPD-96J, JONCRYL501J, JONCRYLPDX-6102B, BYK Chemie DISPERBYK180, DISPERBYK187, DISPERBYK190 , DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, Sartomer, SMA100 Examples include 0H, SMA1440H, SMA2000H, SMA3000H, and SMA17352H.

The average particle diameter of the acrylic resin fine particles is preferably in the range of 30 to 300 nm. The average particle size in this specification is the peak of volume particle size distribution data measured using a dynamic light scattering measurement method.

(Acrylic/urethane composite resin)
When the aqueous resin (A) is an acrylic/urethane composite resin, the acrylic/urethane composite resin may be one having an acrylic polymerization site and a polyurethane site that are a polymer of the ethylenically unsaturated monomer (a). For example, the ethylenically unsaturated monomer represented by the above general formula (1) may be used in an aqueous dispersion in which a urethane resin having a sulfanyl group as a chain transfer agent residue is dispersed at the end. A composite obtained by polymerizing an ethylenically unsaturated monomer (a) containing at least either (a-1) or an ethylenically unsaturated monomer (a-2) represented by general formula (2) Examples include resin.

Examples of polyols that can be used in the synthesis of urethane resins include polyether polyols such as polyethylene glycol, polypropylene glycol, poly(ethylene/propylene) glycol, and polytetramethylene glycol; Ethylene glycol, butylene glycol, 1,2-propanediol, 1,3-propanediol, pentanediol, 1,4-butylene diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2- Butyl-2-ethyl-1,3-propanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, Octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, dihydroxypropionic acid, dihydroxybenzoic acid, dihydroxysuccinic acid, sorbitol, and N,N-bis(2- difunctional diols such as dimethylolalkanoic acids such as hydroxypropyl)aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, and/or Trifunctional diols such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and 1,2,6-butanetriol, and terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, and phthalic anhydride. A polyester polyol obtained by reacting an acid, a dibasic acid such as isophthalic acid or trimellitic acid; A polycarbonate polyol obtained by reacting the aforementioned difunctional diol with a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate; A hydroxyl group Polyolefin polyols such as polybutadiene containing acid groups, hydrogenated polybutadiene containing acid groups, polyisoprene containing hydroxyl groups, hydrogenated polyisoprene containing hydroxyl groups, chlorinated polypropylene containing hydroxyl groups, and chlorinated polyethylene containing hydroxyl groups; Castor oil polyols made from vegetable-derived oil; Can be mentioned.

Examples of polyisocyanates that can be used to synthesize urethane resins include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate. Isocyanate, lysine diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate and 1,5-tetrahydronaphthalene diisocyanate; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate, 1,4-cyclohexocyanate Examples include alicyclic polyisocyanates such as silane diisocyanate and 4,4'-dicyclohexylmethane diisocyanate.

As the polyol, a low molecular weight diol having a molecular weight of 500 or less may be used for the purpose of adjusting the urethane bond concentration and introducing various functional groups.
Examples of low-molecular diols with a molecular weight of 500 or less include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, Hexanediol, octanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butylene diol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-butanetriol , pentaerythritol, sorbitol, N,N-bis(2-hydroxypropyl)aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, etc. Examples include methylolalkanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, and dihydroxybenzoic acid.

Further, the urethane resin may be terminal-modified or chain-extended.
Examples of compounds that can be used in terminal modification and chain extension reactions include hydrazine, ethylenediamine, propylene diamine, hexamethylene diamine, nonamethylene diamine, xylylene diamine, isophorone diamine, piperazine and its derivatives, phenylene diamine, tolylene diamine, and xylene diamine. Diamines such as diamine and N-(β-aminoethyl)ethanolamine; dihydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide;

In the synthesis of urethane resins, a chain transfer agent may be used for molecular weight adjustment and terminal modification. As the chain transfer agent, a compound having a sulfanyl group is preferably used, such as 2-hydroxyethanethiol, 3-hydroxypropyl-1-thiol, 1-hydroxypropyl-2-thiol, 4-hydroxy-1-butane. Hydroxy alkanethiols such as thiol; dithiols such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 2-amino Aminoalkanethiols such as ethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-amino-1-butanethiol; 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol; Examples include aminobenzenethiols such as aminothiophenol.

Commercially available products may be used as the water dispersion of urethane resin, and examples of the commercially available products include Superflex series (SF-170, SF-210, etc.) manufactured by Daiichi Kogyo Seiyaku, Ucoat manufactured by Sanyo Chemical Co., Ltd., and Permarin. series (UX-310, UX-3945, etc.), Arakawa Chemical's Yuriano series (W-600, W-321, etc.), ADEKA's ADEKA Pont titer series (HUX-420A, HUX-386), Ube Industries' UW series ( UW-5002, UW-5020, etc.) and Taisei Fine Chemical's Akrit series (WBR2000U, WBR2101, WEM-200U, etc.).

(Acrylic/olefin composite resin)
When the aqueous resin (A) is an acrylic/olefin composite resin, the acrylic/olefin composite resin may be one having an acrylic polymerization site and a polyolefin site, which are polymers of the ethylenically unsaturated monomer (a). For example, acid-modified polyolefins such as maleic acid-modified ethylene-propylene copolymer, maleic acid-modified propylene-1-butene copolymer, or maleic acid-modified ethylene-propylene-1-butene copolymer are not particularly limited. At least one of the ethylenically unsaturated monomer (a-1) represented by general formula (1) or the ethylenically unsaturated monomer (a-2) represented by general formula (2) is added to Examples include composite resins grafted with an acrylic polymer, which is a polymer of ethylenically unsaturated monomer (a).

The glass transition point (Tg) of the aqueous resin (A) is preferably in the range of -60 to 100°C, more preferably in the range of -30 to 70°C, even more preferably in the range of -25 to 45°C. The temperature is particularly preferably in the range of -20 to 20°C. When the Tg is -60°C or higher, it is possible to prevent the resin component of the primer layer from flowing excessively and entering the voids of the colloidal crystal layer, thereby suppressing deterioration of color development of the colloidal coating film over time. can. Furthermore, since the strength of the bonded portion can be ensured, the substrate followability, substrate adhesion, water resistance, and solvent resistance of the coating film are also improved. On the other hand, when Tg is 100°C or less, the film-forming properties of the aqueous resin (A) are sufficiently ensured, and a colloidal crystal coating film with excellent substrate followability, substrate adhesion, water resistance, and solvent resistance can be obtained. It will be done.
The above glass transition point can be determined using DSC (differential scanning calorimeter).

<Other ingredients>
The primer of the present invention contains an aqueous resin (A) and water, and is coated onto a base material and dried to form a film to form a primer layer. The primer may contain additives such as hydrophilic solvents and crosslinking agents for the purpose of improving the film-forming properties of the primer and the various resistances of the primer layer, as long as they do not adversely affect the physical properties of the colloidal crystals. good.

(hydrophilic solvent)
Examples of hydrophilic solvents include monohydric alcohol solvents such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol; ethylene Glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentylene glycol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, Glycol solvents such as tetraethylene glycol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol Monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, Glycol ether solvents such as diethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether; Lactam solvents such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, and ε-caprolactam; formamide, N-methylformamide, N,N-dimethylformamide, Equamide M-100 manufactured by Idemitsu , amide solvents such as Equamid B-100, etc. These can be used alone or in combination of two or more.

(Crosslinking agent)
As described above, the primer of the present invention may form a crosslink within the primer layer or between the primer layer and the colloidal crystal layer, and may contain a crosslinking agent. As the crosslinking agent, the description of the crosslinking agent in the colloidal crystal layer described below can be referred to.

<Colloid crystal layer>
The colloidal crystal layer is not particularly limited as long as it is a layer that expresses structural color derived from Bragg reflection. The colloidal crystal layer can develop various colors by controlling the periodic interval by controlling the particle diameter of the fine particles (B) contained therein. The average particle diameter of the fine particles (B) is preferably in the range of 180 to 330 nm. The above range is preferable because the colloidal crystal layer develops clear color in the visible light region and a colloidal crystal coating film with better coloring can be obtained.
The method for forming the colloidal crystal layer is not particularly limited, but for example, after applying a colloidal crystal layer composition containing monodisperse fine particles (B) and water onto the primer layer, the particles are advected by volatilization of the water. It can be formed by accumulating and regularly arranging.

(Fine particles (B))
Examples of the fine particles (B) include inorganic fine particles such as silica, and organic fine particles such as resin fine particles, and either synthetic products or commercially available products may be used. Commercially available monodispersed silica particles include, for example, Houtform Silbol 210, Silbol Ex260, Silbol S260, and Silbol 300 manufactured by Fuji Chemical.
As the fine particles (B), resin fine particles are preferable because they have good adhesion with the primer, are excellent in followability and abrasion resistance of the colloidal crystal coating, and have good coloring properties of the colloidal crystal coating. More preferred are resin particles made of acrylic resin or styrene acrylic resin.

The average particle diameter of the fine particles (B) is preferably 150 to 350 nm. It is preferable that the average particle diameter is 150 nm or more because the color development of the colloidal crystal in the visible light region becomes good. When the average particle diameter is 400 nm or less, the colloidal crystal will have good color development in the visible light region, and scattering by the particles will be suppressed, resulting in good color development.
The average particle size can be measured by a dynamic light scattering method (the measuring device is manufactured by Nanotrac UPA Co., Ltd. and Microtrac Bell Co., Ltd.), and the peak of the obtained volumetric particle size distribution data (histogram) is calculated as the average particle size. The diameter shall be the diameter.

Further, the coefficient of variation (Cv value) of the average particle diameter of the fine particles (B) is preferably 30% or less. The coefficient of variation is a numerical value representing the degree of uniformity of particle diameters, and can be calculated using the following formula.
Formula: Coefficient of variation Cv value (%) = standard deviation of particle diameter/average particle diameter x 100
[In the formula, the units of standard deviation and 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 coloring properties of the colloidal crystals are improved.

When the fine particles (B) are resin fine particles made of an acrylic resin or a styrene acrylic resin, the method for producing the resin fine particles is not particularly limited, but can be produced, for example, by the emulsion polymerization described below.
First, an aqueous medium and an emulsifier are charged into a reaction tank, and the temperature is raised to a predetermined temperature. On the other hand, water, an emulsifier, and an ethylenically unsaturated monomer (b) are placed in a dropping tank and stirred to prepare an emulsion of the ethylenically unsaturated monomer (b). Thereafter, a radical polymerization initiator is added while dropping the prepared emulsion into the reaction tank under a nitrogen atmosphere. After the reaction starts, polymer particle nuclei are generated, the particles gradually grow, and the desired fine particles (B) can be obtained.

As the ethylenically unsaturated monomer (b) that can be used in the fine particles (B), the description of the ethylenically unsaturated monomer (a) exemplified in the aqueous resin (A) can be cited. Further, the colloidal crystal layer preferably forms a crosslink with the primer layer as described above, and it is preferable that the fine particles (B) have a reactive group that forms a crosslink with the primer layer. .

Examples of reactive groups that can be introduced into the fine particles (B) include the reactive groups exemplified for the aqueous resin (A), but these groups do not adversely affect the regular arrangement of colloidal crystals and form crosslinks at relatively low temperatures. From this point of view, a ketone group that forms a ketone-hydrazide crosslink is preferable. The ketone group can be introduced into the fine particles (B) in the same manner as in the aqueous resin (A) described above.

The content of ketone groups contained in the fine particles (B) is preferably in the range of 0.05 to 0.3 mmol/g based on the mass of the fine particles (B). Within the above range, the bonding between the fine particles (B) and between the primer layer and the colloidal crystal layer can be strengthened without deteriorating the water resistance, and the followability of the colloidal crystal coating film can be improved. This is preferable because it further improves adhesion.

Preferably, the fine particles (B) are resin fine particles having a core-shell structure. Core-shell type resin particles have a core and a shell made of a water-insoluble polymer, and have a structure of a core part (inner layer) and a shell part (outer layer) that are incompatible with each other.
The core part maintains a spherical shape, and the shell part has fluidity and functions as a binding site. The core-shell type fine particles (B) are applied onto the primer layer, and as drying progresses, they are regularly arranged and stacked to form colloidal crystals. At this time, the shell portions are fused together at the contact portions between the core-shell particles, forming a colloidal crystal layer in which the aqueous medium is replaced by air in the voids. Furthermore, since the shell portion is also fused to the resin of the primer layer, a colloidal crystal layer in which colloidal crystals are more firmly fixed is formed. Further, when the colloidal crystal contains achromatic black fine particles described below, the shell portion binds the achromatic black fine particles and can suppress chipping. Therefore, the followability of the colloidal crystal coating film and the adhesion to the substrate are further improved. Furthermore, even if exposed outdoors for a long period of time, the primer layer is unlikely to peel off or deteriorate, and deterioration of the color development, followability, and substrate adhesion of the colloidal crystal coating film can be suppressed.

In the core-shell type resin fine particles, the content of the shell is preferably 10 to 50% by mass based on the mass of the core. By being within the above range, filling of voids in the colloidal crystal layer due to fusion of the shell portion is suppressed. Furthermore, the fusion of the shells progresses sufficiently, and the bonds between the core-shell fine particles and between the primer layer and the core-shell fine particles become stronger. Therefore, it is possible to obtain a colloidal crystal coating film that is excellent in color development, followability, and adhesion to substrates.

The Tg of the core portion of the core-shell resin fine particles is preferably 60°C or higher, more preferably in the range of 60°C to 150°C. When Tg is 60° C. or higher, deformation of the core shape due to the influence of heat or solvent is suppressed. Therefore, it is possible to obtain a colloidal crystal coating film that is superior in color development and rubbing resistance.
The Tg of the shell portion of the core-shell type resin fine particles is preferably in the range of -50 to 20°C. By being within the above range, filling of voids in the colloidal crystal layer due to fusion of the shell portion is suppressed. Further, the fusion of the shells progresses sufficiently, and the bonding between the core-shell fine particles and between the core-shell fine particles and the primer layer becomes stronger. Therefore, a coating film having excellent followability and adhesion to the substrate can be obtained.

Furthermore, it is preferable that the shell of the core-shell type resin fine particles has a reactive group that forms a crosslink with the aqueous resin (A). Examples of the reactive groups that can be introduced include the reactive groups exemplified in the aqueous resin (A). Due to the synergistic effect of the formation of crosslinks in the shell part and the above-mentioned fusion of the shell part, the bond between the primer layer and the colloidal crystal layer is further strengthened, and the followability of the colloidal crystal coating film and the adhesion to the substrate are further improved. do. Deterioration of the physical properties of the coating film during outdoor exposure can also be further suppressed.

The composition for the colloidal crystal layer is an achromatic black color for the purpose of improving color development, coating properties, and coating film resistance, as long as it does not adversely affect the particle arrangement during drying or the physical properties of the colloidal crystal coating film. Additives such as fine particles, hydrophilic solvents and crosslinking agents can be used.
As the achromatic black particles, any black particles such as carbon black or resin particles colored with black dye can be used. Carbon black is preferred because the coloring component is difficult to dissolve into water or solvents and the colorant has excellent durability. Carbon black may be either a dispersion type that is dispersed in water using a dispersant, or a self-dispersion type, but a self-dispersion type carbon black is used from the viewpoint that the dispersant does not affect the arrangement of fine particles. It is preferable. Commercially available carbon black water dispersions include, for example, the Lion Paste series (W-310A, etc.) manufactured by Lion Corporation, and the CW series (CW-1, CW-2, CW-3, etc.) manufactured by Orient Chemical.
As the hydrophilic solvent and crosslinking agent, those exemplified for the primer can be used.

The composition for a colloidal crystal layer may contain a crosslinking agent in order to form a crosslink between the primer layer and the colloidal crystalline layer. The crosslinking agent is not particularly limited and can be appropriately selected depending on the reactive groups possessed by the primer layer and the colloidal crystal layer, and includes, for example, an epoxy crosslinking agent, a polyisocyanate crosslinking agent, and a hydrazide crosslinking agent.
More specifically, for example, when the aqueous resin (A) or the fine particles (B) have a carboxyl group, a hydroxyl group, or an amino group, crosslinking can be formed via an epoxy crosslinking agent.
Further, for example, when the aqueous resin (A) or the fine particles (B) have a hydroxyl group, crosslinking can be formed via a polyisocyanate crosslinking agent. Further, for example, when the aqueous resin (A) or the fine particles (B) have a ketone group, they can be crosslinked via a hydrazide crosslinking agent.
As the crosslinking agent, it is preferable to use a hydrazide crosslinking agent in order to form a ketone hydrazide crosslinking as described above. Examples of the hydrazide crosslinking agent include adipic acid dihydrazide and water-soluble resins modified with polyfunctional hydrazide groups.

<Laminated body>
The laminate of the present invention includes the above colloidal crystal coating film on a base material, and includes a primer layer and a colloidal crystal layer in this order on the base material.

(Base material)
The base material is not particularly limited and can be selected as appropriate depending on the application, such as polyvinyl chloride sheet, polyethylene terephthalate (PET) film, polypropylene film, polyethylene film, nylon film, polystyrene film, polyvinyl alcohol film, etc. Examples include thermoplastic resin base materials; metal base materials such as aluminum foil; glass base materials, and coated paper base materials.
The coated surface of the base material may be smooth or may have an uneven surface. Further, the base material may be transparent, translucent, or opaque, and in order to make the coloring of the colloidal crystal coating film more clear, a base material that has been previously colored black or the like may be used. Moreover, the base material may be used alone or may be a laminate made by bonding two or more base materials together.

(Formation of primer layer)
The primer layer is provided between the base material and the colloidal crystal layer for the purpose of improving the coating film resistance of the colloidal crystal, and a primer containing water and a water-based resin (A) is applied onto the base material. Can be dried and formed. The method of applying the primer is not particularly limited, and examples include printing methods that do not use a plate such as inkjet, spray, dipping, and spin coating, or offset gravure coater, gravure coater, doctor coater, bar coater, blade coater, flexo coater, Examples include plate printing methods such as a roll coater. The method for drying the primer is preferably a hot air drying method from the viewpoint of reducing damage to the base material and drying efficiently, and the drying temperature is preferably in the range of 50 to 120°C.
From the viewpoint of performance such as substrate followability, substrate adhesion, water resistance, and solvent resistance, and productivity, the thickness of the primer layer is preferably in the range of 0.5 to 20 μm.

(Formation of colloidal crystal layer)
As described above, the colloidal crystal layer can be formed by applying a composition for a colloidal crystal layer containing fine particles (B) and water onto the primer layer. The coating method is not particularly limited, and for example, the description in the section on forming the primer layer can be used.
After applying the composition for a colloidal crystal layer onto a substrate, the applied product 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. From the viewpoint of influence on regular arrangement and productivity, the drying temperature is preferably in the range of 25 to 80°C.
From the viewpoint of color development and productivity of the colloidal crystal layer, the thickness of the colloidal crystal layer is preferably in the range of 5 to 20 μm.

The laminate of the present invention may have an overcoat layer on the colloidal crystal layer for the purpose of improving the coating film resistance of the colloidal crystal. The overcoat layer is not particularly limited and can be appropriately selected from known materials depending on the intended use, and the primer of the present invention may be used as the overcoat resin composition.
The method of applying and drying the resin composition for overcoat is not particularly limited, and the description in the section on formation of primer and colloidal crystal layer can be referred to. The thickness of the overcoat layer is preferably in the range of 2 to 20 μm.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the following Examples do not limit the scope of the present invention in any way. In addition, unless otherwise specified, "parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.

[Glass transition point (Tg)]
The glass transition point was measured by DSC (differential scanning calorimeter manufactured by TA Instruments). Approximately 2 mg of a sample obtained by drying the resin fine particle dispersion was weighed on an aluminum pan, the aluminum pan was set in a DSC measurement holder, and the endothermic peak on the chart obtained under the temperature increase condition of 5°C/min was read. Obtained a transition point.

[Average particle diameter, Cv value]
The average particle diameter was determined by diluting the fine particle dispersion 500 times with water, and measuring about 5 ml of the diluted solution using a dynamic light scattering measurement method (measuring device manufactured by Nanotrac UPA Corporation, 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. Further, the coefficient of variation Cv value representing the degree of uniformity of particle diameter was calculated using the following formula.
Cv value % = standard deviation of particle diameter / average particle diameter × 100

[Weight average molecular weight (Mw)]
The weight average molecular weight is a polystyrene equivalent value measured by GPC (gel permeation chromatography), and was measured by dissolving the dried resin in tetrahydrofuran to prepare a 0.1% solution and using the following equipment and measurement conditions. .
Equipment: HLC-8320-GPC system (manufactured by Tosoh Corporation)
Column; TSKgel-Super Multipore HZ-M0021488
4.6mmI. D x 15cm x 3 (molecular weight measurement range 2,000 to approximately 2 million)
Elution solvent; Tetrahydrofuran standard substance; Polystyrene (manufactured by Tosoh Corporation)
Flow rate: 0.6 mL/min, sample solution usage: 10 μL, column temperature: 40°C

[Acid value (AV)]
The acid value is the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. It was calculated by performing potentiometric titration with the solution.

<Preparation of primer>
[Example 1] Acrylic resin fine particle primer (P1)
68.9 parts of water was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux device.
Separately, 19.0 parts of methyl methacrylate, 2.0 parts of n-butyl methacrylate, 3.0 parts of 2-ethylhexyl acrylate, 18.5 parts of n-butyl acrylate, 1.0 part of methacrylic acid, 1.0 part of acrylic acid, 3-methacryloxypropyltriethoxysilane 0.5 parts, RUVA-093 (manufactured by Otsuka Chemical Co., Ltd. 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole) 5.0 parts , 2.5 parts of a 20% aqueous solution of KH-10 ( _{anionic reactive emulsifier} Aquaron KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 20.2 parts of water are mixed in advance, stirred, and ethylenically unsaturated is added dropwise to the first stage. A monomer emulsion was prepared.
7.0% of this emulsion was added to the reaction vessel, the internal temperature of the reaction vessel was raised to 70°C, and after sufficient nitrogen substitution, 2.0 parts of a 5% aqueous solution of potassium persulfate was used as an initiator. was added to start emulsion polymerization. The internal temperature was raised to 80° C., and while the temperature was maintained, the remainder of the ethylenically unsaturated monomer emulsion dropwise added in the first stage and 1.0 part of a 5% aqueous solution of potassium persulfate were added dropwise over 2 hours.
After completing the dropping of the first stage ethylenically unsaturated monomer emulsion, 19.0 parts of methyl methacrylate, 2.0 parts of n-butyl methacrylate, 3.0 parts of 2-ethylhexyl acrylate, and n-butyl acrylate were added continuously. 18.5 parts, 0.5 parts of 3-methacryloxypropyltriethoxysilane, 5.0 parts of RUVA-093, ADEKA STAB LA-82 (manufactured by ADEKA 1,2,2,6,6-pentamethyl-4-methacrylate) piperidyl), 2.5 parts of a 20% aqueous solution of KH-10, and 20.2 parts of water. 1.0 part of a 5% aqueous solution of potassium sulfate was added dropwise over 2 hours.
After completion of the dropping, the reaction was further carried out for 4 hours to obtain an aqueous dispersion of aqueous resin (A1).
After neutralizing the obtained aqueous dispersion by adding 25% ammonia water to the equivalent molar amount to the carboxyl group in the resin, water was further added to make the solid content concentration 45.0%. Adjusted to.
Next, 4.0 parts of isopropyl alcohol was added to prepare a primer (P1).
The aqueous resin (A1) had an average particle diameter of 160 nm, a Tg of 8.5°C, and an acid value of 14.3 mgKOH/g.

[Examples 2 to 14, Comparative Examples 1 and 2] Acrylic resin fine particle primer (P2 to 14, P17, P18)
Aqueous dispersions of aqueous resins (A2 to A14, A17, A18) were prepared using the formulations shown in Tables 1 to 3 in the same manner as the primer (P1).
To the obtained aqueous dispersion, 25% ammonia water was added to make the molar equivalent to the carboxyl group in the resin to neutralize it, and water was further added to bring the solid content concentration to 45.0%. It was adjusted.
Next, 4.0 parts of isopropyl alcohol and 1.0 part of adipic acid dihydrazide were added to prepare primers (P2-14, P17, P18).
Regarding the obtained aqueous resins (A2 to A14, A17, A18), Tg, acid value, and average particle diameter were measured in the same manner as in Example 1.

The obtained primers are shown in Tables 1 to 3. The numerical values in Tables 1 to 3 represent "parts" unless otherwise specified, and a blank column means that it is not blended.

The abbreviations in Tables 1 to 3 are shown below.
RUVA-093: Otsuka Chemical 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole ADEKA STAB LA-82: ADEKA methacrylic acid 1,2,2,6, 6-Pentamethyl-4-piperidyl Adekastab LA-87: ADEKA 2,2,6,6-tetramethyl-4-piperidyl methacrylate

[Example 15] Acrylic/urethane composite resin primer (P15)
(Manufacture of urethane resin U1)
First, in a reaction vessel equipped with a stirrer, a thermometer, and a reflux device, 14.6 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical, functional group number 2, hydroxyl value 57.0 mgKOH/g) as a polyol, and polyester polyol. (P-2011 manufactured by Kuraray, number of functional groups 2, hydroxyl value 56.0 mgKOH/g) 20.2 parts, polycarbonate polyol (C-2090 manufactured by Kuraray, number of functional groups 2, hydroxyl value 56.3 mgKOH/g) 48.6 parts, dimethylol 4.3 parts of butanoic acid, 0.1 part of neopentyl glycol, and 9.7 parts of isophorone diisocyanate as a polyisocyanate were charged, and the temperature was raised to 80° C. with stirring under a nitrogen atmosphere. Next, 0.02 part of titanium diisopropoxy bis(ethyl acetoacetate) was added, the temperature was raised to 110°C, the mixture was reacted for 5 hours, and then the temperature was lowered to 80°C. At this time, the weight average molecular weight of the urethane prepolymer produced was 32,100.
Next, 40.0 parts of methyl ethyl ketone and 2.4 parts of 2-aminoethanethiol were added and reacted at 75°C for 2 hours. The end point of the reaction was confirmed by FT-IR by the disappearance of the peak derived from the isocyanate group (around 2270 cm ^-1 ). Furthermore, methyl ethyl ketone was added to adjust the solid content concentration to 70% to obtain a solution of urethane resin U1 having sulfanyl groups at both ends.

(Manufacture of acrylic/urethane composite resin primer)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux device, 50 parts of the solution of the urethane resin U1 obtained above, 5.0 parts of styrene, 13.0 parts of methyl methacrylate, and 9.0 parts of n-butyl acrylate were added. 1 part, 2.0 parts of methacrylic acid, 1.0 parts of diacetone acrylamide, 18.0 parts of RUVA-093, 2.0 parts of Adekastab LA-82, and 35.0 parts of n-propanol, and in a nitrogen atmosphere. The temperature was raised to 75° C. while stirring. A dropping funnel was charged with 20.0 parts of methyl ethyl ketone and 0.35 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as an initiator, and the mixture was dropped into the reaction tank over 5 hours. The reaction was carried out at 78° C. for 8 hours to complete the grafting reaction of the acrylic resin portion. After the reaction, 10 parts of water was added, and 25% ammonia water was added to the equivalent molar ratio to the carboxyl groups in the resin to neutralize it, and the solvent was removed to remove water from the aqueous resin (A15). A dispersion was obtained. Ion-exchanged water was added to the obtained water dispersion to adjust the solid content concentration to 25.0%.
Next, 4.0 parts of isopropyl alcohol was added to prepare a primer (P15).
The water-based resin (A15) had a Tg of 44.8°C and an acid value of 18.3mgKOH/g.

The numerical values in Tables 4 and 5 represent "parts" unless otherwise specified, and a blank column means that it is not blended.

[Example 16] Acrylic/olefin composite resin primer (P16)
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux device, 20.0 parts of Auroren 350S (maleic anhydride-modified polypropylene-polyethylene copolymer manufactured by Nippon Paper Industries), 54.7 parts of toluene, and 20.0 parts of solid olefin resin were added. 20.0 parts of isopropyl alcohol was charged, and the temperature was raised to 70°C while stirring under a nitrogen atmosphere to dissolve the resin.
6.4 parts of t-butylperoxy-2-ethylhexanoate was charged into the first dropping funnel and dropped over 1 hour, and 31.0 parts of methyl methacrylate and 25 parts of n-butyl methacrylate were added to the other dropping funnel. .9 parts of n-butyl acrylate, 10.5 parts of acrylic acid, 5.0 parts of RUVA-093, and 1.0 part of Adekastab LA-82 were added dropwise over 1 hour.
After the addition was completed, the reaction was further carried out at 80° C. for 2 hours to obtain an acrylic/olefin composite resin in which acrylic was grafted onto the olefin skeleton. After the reaction is complete, 20 parts of ion-exchanged water and 25% ammonia water are added to the equivalent molar ratio to the carboxyl groups in the resin to neutralize it, and the solvent is removed to form an aqueous dispersion of the aqueous resin (A16). I got a body. Ion-exchanged water was added to the obtained water dispersion to adjust the solid content concentration to 25.0%.
Next, 4.0 parts of isopropyl alcohol was added to prepare a primer (P16).
The Tg of the aqueous resin (A16) was 30.5°C.

The numerical values in Table 6 represent "parts" unless otherwise specified, and a blank column means that it is not blended.

<Preparation of fine particle (B) dispersion for colloidal crystal layer>
[Production Example 1] Fine particles (B1)
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux device, 68.9 parts of water were charged, and separately 85.0 parts of styrene, 5.0 parts of benzyl methacrylate, 7.0 parts of 2-ethylhexyl acrylate, Ethylenically unsaturated product prepared by premixing and stirring 2.0 parts of acrylic acid, 1.0 part of 3-methacryloxypropyltriethoxysilane, 5.0 parts of a 20% aqueous solution of KH-10, and 40.4 parts of water. An additional 3% of the monomer emulsion was added.
After raising the internal temperature to 70°C and thoroughly purging with nitrogen, 2.0 parts of a 5% aqueous solution of potassium persulfate was added as an initiator to initiate emulsion polymerization. The internal temperature was raised to 80°C, and while maintaining the temperature, the remainder of the ethylenically unsaturated monomer emulsion and 2.0 parts of a 5% aqueous solution of potassium persulfate were added dropwise over 3 hours, and the mixture was allowed to react for an additional 4 hours. An aqueous dispersion of fine particles (B1) with a solid content concentration of 45.0% was obtained.
The obtained fine particles (B1) had a Tg of 76.9°C, an average particle diameter of 201 nm, and a coefficient of variation Cv of 25.8%.

[Production Example 2] Fine particles (B2)
An aqueous dispersion of fine particles (B2) having a solid content concentration of 45.0% was prepared in the same manner as fine particles (B1) except that the formulation shown in Table 7 was changed. Regarding the obtained fine particles, Tg, average particle diameter, and Cv value were measured in the same manner as in Production Example 1.

[Production Example 3] Fine particles (B3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux device, add 95.0 parts of water and separately 97.0 parts of styrene, 2.0 parts of acrylic acid, and 1.0 parts of 3-methacryloxypropyltrimethoxysilane. of the first-stage ethylenically unsaturated monomer emulsion prepared by mixing and stirring 5.0 parts of a 20% aqueous solution of Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and 39.1 parts of water. An additional 1.5% was added. After raising the internal temperature of the reaction vessel to 70°C and thoroughly purging with nitrogen, 5.7 parts of a 2.5% aqueous solution of potassium persulfate was added as an initiator to initiate polymerization. The internal temperature was raised to 80°C, and while the temperature was maintained, the remainder of the emulsion of the ethylenically unsaturated monomer from the first stage and 4.0 parts of a 2.5% aqueous solution of potassium persulfate were added dropwise over 2 hours. A reaction was performed to synthesize core particles. The average particle diameter of the generated core particles was 205 nm.
20 minutes after the completion of the first drop, add 15.0 parts of methyl methacrylate, 26.1 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. Dropwise addition of the second emulsion of ethylenically unsaturated monomer prepared by mixing and stirring .8 parts was started. While maintaining the internal temperature at 80°C, the second stage emulsion of ethylenically unsaturated monomer and 2.1 parts of a 2.5% aqueous solution of potassium persulfate were added dropwise over 2 hours to further advance the reaction and form a solid. An aqueous dispersion of core-shell type fine particles (B3) with a concentration of 45.0% was obtained.
The obtained core-shell resin fine particles had an average particle diameter of 253 nm, a Cv value of 25.7%, a Tg of the core part of 100.1°C, and a Tg of -12.5°C of the shell part.

[Production Example 4] Fine particles (B4)
An aqueous dispersion of core-shell type fine particles (B4) was prepared in the same manner as for fine particles (B3) except that the formulation shown in Table 8 was changed. During synthesis, water is added to the ethylenically unsaturated monomer emulsion so that the concentration of the ethylenically unsaturated monomer in the emulsion becomes 69.0% and the concentration of the emulsifier becomes 0.69%. It was prepared by After the synthesis, the solid content concentration of the aqueous dispersion of resin particles was adjusted to 45.0% by adding water or dehydrating by vacuum stripping.
Regarding the obtained core-shell resin fine particles, the average particle diameter, Cv value, and Tg were measured in the same manner as in Production Example 3.

The obtained fine particle (B) dispersion is shown in Tables 7 and 8. The numerical values in Tables 7 and 8 represent "parts" unless otherwise specified, and a blank column means that it is not blended.

<Preparation of composition for colloidal crystal layer>
[Production Example 5] Composition for colloidal crystal layer (C1)
To 100 parts of an aqueous dispersion of fine particles (B1), 2.3 parts of BONJET BLACK CW-1 (surface-modified carbon black, average particle diameter 62 nm, pigment content 20.0%) manufactured by Orient Kagaku Kogyo Co., Ltd. was added as achromatic black fine particles. The mixture was stirred to prepare a composition for colloidal crystal layer (C1).

[Production Examples 6-9] Composition for colloidal crystal layer (C2-C5)
Colloidal crystal layer compositions (C2 to C5) were prepared in the same manner as in (C1) except that the compositions shown in Table 9 were changed.

Table 9 shows the resulting colloidal crystal layer composition. The numerical values in Table 9 represent "parts" unless otherwise specified, and a blank column means that it is not blended.

The abbreviations in Table 9 are shown below.
Silbol 210: Monodispersed silica fine particle aqueous dispersion manufactured by Fuji Chemical, average particle diameter 218 nm, Cv value 20.8%, solid content concentration 32.3%)

<Preparation of laminate>
[Example 17]
Plasma treatment was performed on the corona-treated surface of a biaxially oriented polypropylene (OPP) film (FOR manufactured by Futamura, film thickness 20.0 μm) using PIB-20 manufactured by Vacuum Devices. The processing conditions are shown below.
Atmosphere gas: Air Atmosphere gas pressure: 20Pa
Discharge current: 20mA
Treatment time: 1 minute Primer (P1) was coated on the plasma-treated base material surface using a bar coater so that the thickness after drying was 9 μm, and dried at 70°C for 3 minutes. A primer layer was formed. Next, the colloidal crystal layer composition (C1) was applied onto the primer layer using a bar coater so that the thickness after drying was 7 μm, and dried at 50° C. for 3 minutes to form a colloidal crystal layer. did. In this way, a laminate having a colloidal crystal coating on the base material was obtained.

[Examples 18 to 35, Comparative Examples 3 to 6]
Using the combinations shown in Table 10, a primer layer and a colloidal crystal layer were formed on a base material in the same manner as in Example 17 to obtain a laminate having a colloidal crystal coating film.

<Evaluation of laminate>
The obtained laminate and colloidal crystal coating film were evaluated as follows. The results are shown in Table 10.

[Color development (△R, rate of change)]
The reflection spectrum of the colloidal crystal coating film 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 Labsphere) with a known reflectance as a reference. Regarding the obtained reflection spectrum, the difference (ΔR) between the maximum value of the reflectance derived from the structural color and the baseline reflectance independent of the structural color was calculated. The larger ΔR is, the better the color development is.
In addition, a laminate in which a colloidal crystal layer was formed without a primer layer was separately prepared, and ΔR was similarly determined for this colloidal crystal layer, and the rate of change (rate of decrease) in ΔR due to the primer layer was calculated. The larger the rate of decline, the more discolored the colloidal crystal coating is. The obtained ΔR and the rate of decrease in ΔR were evaluated based on the following criteria.
◎; △R is 15% or more, and the rate of decrease in △R is less than 2% (very good)
○; △R is 15% or more, and the rate of decrease in △R is 2% or more and less than 5% (good)
△; △R is 15% or more, and the rate of decrease in △R is 5% or more and less than 30% (defective)
×; △R is 15% or more, and the rate of decrease in △R is 30% or more,
Or △R is less than 15% (very poor)

[Followability]
A 5 cm x 5 cm test piece was cut out from the laminate and bent 180 degrees 10 times. The state after bending was visually observed and evaluated based on the following criteria.
◎; No peeling or scratches (extremely good)
○: Area of peeling or scratches is less than 5% of the test piece (good)
△; Area of peeling or scratches is 5% or more and less than 10% of the test piece (defective)
×; Area of peeling and scratches is 10% or more of the test piece (extremely poor)

[Substrate adhesion]
A 5 cm x 5 cm test piece was cut out from the laminate, and cellophane tape (18 mm width, manufactured by Nichiban Co., Ltd.) was pasted on the colloidal crystal coating film, and it was slowly peeled off in the vertical direction, and the whole area to which the tape was attached was peeled off. Base material adhesion was evaluated based on the ratio of peeled area. The evaluation criteria are as follows.
◎; No peeling (extremely good)
○: Peeling area is less than 15% of the test piece (good)
△; Peeling area is 15% or more and less than 25% of the test piece (defective)
×; Peeling area is 25% or more of the test piece (extremely poor)

[Water resistance and solvent resistance]
After water or ethanol was dripped onto the colloidal crystal coating film, it was re-dried at 50° C. for 3 minutes, and then the reflection spectrum was measured in the same manner as in the color development evaluation described above. The change (decrease rate) in the maximum value of reflectance was evaluated by comparing the reflected light spectra before and after the test. The lower the maximum value of the reflectance, the more the colloidal crystal coating is discolored. The evaluation criteria are as follows.
◎; Maximum value of reflectance does not change (extremely good)
○: Decrease rate of maximum reflectance value is less than 15% (good)
△; Decrease rate of maximum value of reflectance is 15% or more and less than 30% (defective)
×; Decrease rate of maximum value of reflectance is 30% or more (very poor)

<Evaluation of laminate after outdoor exposure>
The resulting laminate was fixed to a board with the colloidal crystal coating facing outward, and then exposed outdoors for 6 months. The laminate and colloidal crystal coating film after outdoor exposure were evaluated as follows. The results are shown in Table 10.

[Color development after outdoor exposure]
After the exposure test, the reflection spectrum of the colloidal crystal coating film was measured in the same manner as the color development evaluation. The reflectance spectra before and after exposure were compared, and the rate of change (rate of decrease) in the maximum value of reflectance was calculated. The larger the rate of decline, the more discolored the colloidal crystal coating is. The obtained reduction rate was evaluated based on the following criteria.
◎; Rate of change in maximum reflectance value is less than 2% (extremely good)
○: Rate of change in maximum value of reflectance is 2% or more and less than 10% (good)
△; Rate of change in maximum value of reflectance is 10% or more and less than 30% (defective)
×; Rate of change in maximum value of reflectance is 30% or more (extremely poor)

[Followability after outdoor exposure]
Using the laminate after the exposure test, it was evaluated according to the following criteria in the same manner as in the above-mentioned [Followability].
◎; No peeling or scratches (extremely good)
○: Area of peeling or scratches is less than 5% of the test piece (good)
△; Area of peeling or scratches is 5% or more and less than 10% of the test piece (defective)
×; Area of peeling and scratches is 10% or more of the test piece (extremely poor)

[Substrate adhesion after outdoor exposure]
A test piece of 5 cm x 5 cm was cut out from the exposed laminate and evaluated according to the following criteria in the same manner as in the above-mentioned [Substrate Adhesion].
◎; No peeling (extremely good)
○: Peeling area is less than 15% of the test piece (good)
△; Peeling area is 15% or more and less than 25% of the test piece (defective)
×; Peeling area is 25% or more of the test piece (extremely poor)

[Water resistance and solvent resistance after outdoor exposure]
Using the exposed laminate, it was evaluated using the following criteria in the same manner as in the above-mentioned [Water resistance and solvent resistance].
◎; Maximum value of reflectance does not change (extremely good)
○: Decrease rate of maximum reflectance value is less than 15% (good)
△; Decrease rate of maximum value of reflectance is 15% or more and less than 30% (defective)
×; Decrease rate of maximum value of reflectance is 30% or more (very poor)

According to the results in Table 10, the colloidal crystal coating film having the primer layer made of the primer of the present invention maintains the color development derived from the vivid structural color even after outdoor exposure, and has excellent trackability and substrate adhesion. It had excellent paint film resistance. In particular, Example 31 used the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) in combination to form a crosslink with the core-shell type resin fine particles in the colloidal crystal layer. , excellent adhesion after outdoor exposure compared to Examples 19 and 20 in which the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) were not used together. It exhibited water resistance and solvent resistance. In addition, Example 31 had excellent followability after outdoor exposure, substrate adhesion, water resistance, and solvent resistance compared to Example 17, which did not form crosslinks with the non-core-shell type resin fine particles in the colloidal crystal layer. showed his sexuality.
On the other hand, in the colloidal crystal coating film using the primer of the comparative example, the physical properties of the coating film were significantly reduced after being exposed outdoors.

Claims (6)

A primer for fixing a colloidal crystal layer to a base material,
The primer contains an aqueous resin (A) and water,
The aqueous resin (A) contains an ethylenically unsaturated monomer (a-1) represented by the following general formula (1) and an ethylenically unsaturated monomer (a-1) represented by the following general formula (2). -2) A primer comprising a structural unit derived from at least one ethylenically unsaturated monomer selected from the group consisting of:
General formula (1): Ethylenically unsaturated monomer (a-1)
(In general formula (1), X represents a hydrogen atom or a methyl group.)

General formula (2): Ethylenically unsaturated monomer (a-2)
(In general formula (2), Y and Z each independently represent a hydrogen atom or a methyl group.) The total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) is 2 to 40 mass based on the total mass of the aqueous resin (A). %. The primer according to claim 1 or 2, wherein the aqueous resin (A) has a glass transition point of -60°C to 100°C. A laminate comprising a primer layer formed from the primer according to any one of claims 1 to 3 and a colloidal crystal layer on a base material in this order. The laminate according to claim 4, wherein the colloidal crystal layer contains core-shell type resin particles. The laminate according to claim 4 or 5, wherein the primer layer and the colloidal crystal layer form a crosslink.