JP7324108B2 - Coating liquid, base material with film, and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coating liquid for forming a releasable film on a substrate and a film-coated substrate.

Conventionally, a releasing film has been produced by coating and forming a film on a film substrate such as PET using an ultraviolet curable or thermosetting silicone compound as a releasing agent. Such a releasable film has excellent releasability, but does not have sufficient adhesion between the film and the substrate. For example, when a release film is used as a protective film for electronic parts, the silicone compound in the film may transfer to the electronic parts when the protective film is peeled off from the electronic parts. Therefore, a release film containing no silicone compound as a release agent has been developed. For example, a release film using an acrylic resin as a release agent (see Patent Document 1) and a release film using a fluororesin as a release agent (see Patent Document 2) are known.

JP-A-2004-079567 Japanese Patent Application Laid-Open No. 2001-129940

The releasability film of Patent Document 1 has low releasability because an acrylic resin is used for the release layer. The releasable film of Patent Literature 2 uses a fluororesin as a release agent, and therefore has higher releasability than acrylic resin. However, since the fluororesin is difficult to dissolve in the solvent, the adhesiveness between the release agent (film) and the substrate is low. In addition, since it is difficult to form irregularities on the surface of the fluororesin, it is difficult to improve the releasability.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a coating liquid capable of forming a film having excellent releasability and adhesion to a substrate.

In order to achieve the above object, the coating liquid of the present invention comprises an ultraviolet curable first composition containing elemental fluorine, an ultraviolet curable second composition not containing elemental fluorine, and a first inorganic oxide It contains first particles whose surfaces are treated with a surfactant, second particles whose surfaces are second inorganic oxide particles treated with a silane coupling agent, a cluster forming agent, and an organic solvent. The first composition and the second composition have a weight average molecular weight of 1000 or more and contain a carbon skeleton. Fluorine is bound to some of the carbons of the first composition. The particle size of the first particles is smaller than 300 nm, and the particle size of the second particles is smaller than the first particles. When the first particles and the second particles are respectively dispersed in water, the ζ potential of the first particles is positive and the ζ potential of the second particles is negative. With such a coating liquid, a film having excellent releasability and adhesion to the substrate can be obtained.

The coating liquid according to the present invention comprises an ultraviolet curable first composition containing elemental fluorine, a second ultraviolet curable composition not containing elemental fluorine, first particles surface-treated with a surfactant, and silane. It contains second particles surface-treated with a coupling agent, a clustering agent, and an organic solvent.

The first composition has a weight-average molecular weight of 1,000 or more and has fluorine in the molecule, so that the surface tension is low. Therefore, when the coating liquid is dried, the first composition tends to move to the surface of the film due to convection caused by volatilization of the organic solvent. As a result, the first composition is unevenly distributed on the surface of the film, and high releasability is obtained. On the other hand, the second composition, which has a relatively higher surface tension than the first composition, is present on the substrate interface side of the film. Since this second composition has ultraviolet curability and is easily soluble in solvents, it has sufficient bonding strength with the substrate when cured. Therefore, the adhesion between the film and the substrate is excellent. At this time, if the molecular weight of the first composition is less than 1000, the first composition will be dispersed in the second composition, making it difficult for the first composition to be unevenly distributed on the surface of the film.

With the particles dispersed in water, the ζ potential of the first particle is positive and the ζ potential of the second particle is negative. Further, the first particles are particles obtained by treating the surface of the first inorganic oxide particles with a surfactant, and the coating liquid contains a cluster forming agent. Thereby, in the process of drying the coating liquid, the first particles interact with each other to form aggregates (primary clusters) of the first particles. The primary clusters and secondary particles then interact in a heteroaggregative manner to form secondary clusters. Convection generated in the film during drying of the coating liquid forms irregularities on the surface of the film starting from the secondary clusters. If secondary clusters are not formed, the unevenness is assumed to be low. At this time, if the molecular weight of the second composition is less than 1000, the compatibility between the second composition and the first particles may be high. This disperses the particles in the film and makes it difficult for the primary particles to form primary clusters. Therefore, the unevenness formed on the surface of the film is reduced, and the releasability is deteriorated. The second particles are particles obtained by treating the surfaces of the second inorganic oxide particles with a silane coupling agent.

The particle diameter (D ₁ ) of the first particles and the particle diameter (D ₂ ) of the second particles have a relationship of D ₂ <D ₁ <300 nm. Since the particle size of the first particles is smaller than 300 nm, the interaction between the first particles is strong. Therefore, primary clusters are likely to be formed. Also, since the second particles are smaller than the first particles, the interaction between the primary clusters and the second particles is strong. Therefore, they tend to interact in a heteroaggregative manner, and tend to form secondary clusters.

As described above, according to the coating liquid of the present invention, it is possible to form a film having both releasability and adhesion to a substrate. Each component contained in the coating liquid will be described in detail below.

[First particle, second particle]
The difference between the ζ potentials of the first particles and the second particles is preferably 20-60 mV. If the ζ potential difference is less than 20 mV, the electrostatic attraction between the first particles and the second particles is small, so the interaction between the primary clusters and the second particles weakens when the coating liquid dries, and they interact in a heteroaggregative manner. difficult to do. As a result, unevenness on the surface of the film is reduced, making it difficult to obtain sufficient releasability. If it is more than 60 mV, the first particles and the second particles tend to aggregate in the coating liquid because the electrostatic attraction between the first particles and the second particles is large. The ζ potential difference is more preferably 30 to 50 mV.

The particle diameter _D1 of the first particles is preferably 10 to 160 nm. If it is smaller than 10 nm, the surface energy of the first particles is high, so the first particles tend to aggregate in the coating liquid. If it is larger than 160 nm, interaction between the first particles becomes insufficient during drying of the coating liquid, making it difficult to form primary clusters. As a result, unevenness on the surface of the film is reduced, making it difficult to obtain sufficient releasability. The particle diameter of the first particles is more preferably 20 to 160 nm, still more preferably 45 to 120 nm. If it is in the range of 45 to 120 nm, the cluster-forming agent interacts with the first particles, so that primary clusters of sufficient size can be obtained as starting points for forming irregularities on the surface of the film. Therefore, excellent releasability is likely to be obtained.

The particle diameter _D2 of the second particles is preferably 9 to 100 nm. If it is smaller than 9 nm, the surface energy of the second particles is high, so the second particles tend to aggregate in the coating liquid. If it is larger than 100 nm, the ζ potential of the second particles becomes small, so that the second particles and the primary clusters are less likely to interact in a heteroaggregative manner during the drying of the coating liquid. Therefore, secondary clusters are less likely to be formed. As a result, unevenness on the surface of the film is reduced, making it difficult to obtain sufficient releasability. The particle diameter of the second particles is more preferably 9 to 80 nm, still more preferably 9 to 45 nm. If it is in the range of 9 to 45 nm, heteroaggregation-like interactions are likely to occur due to the difference in particle size between the primary clusters and the secondary particles and the difference in surface potential, so that sufficient unevenness is formed on the surface of the film. Therefore, excellent releasability is likely to be obtained.

The particle size ratio (D ₁ /D ₂ ) is preferably 2-18. Within this range, the secondary clusters are likely to form because the secondary particles are likely to interact with the primary clusters in a heteroaggregating manner. As a result, the unevenness of the film is increased, and excellent releasability can be obtained. This ratio (D ₁ /D ₂ ) is more preferably 6-14. Particle size is measured by dynamic light scattering using a Malvern Zetasizer Nano ZS.

The first particles are preferably contained in an amount of 1 to 30% by mass in the solid content of the coating liquid. If the amount of the first particles is less than 1%, primary clusters having a size sufficient to form unevenness are not formed, and thus high unevenness is not formed on the surface of the film. Therefore, excellent releasability cannot be obtained. If the proportion of the first particles exceeds 30%, the amount of the second particles that can be blended in the coating liquid is relatively small, making it difficult to obtain secondary clusters. As a result, unevenness on the surface of the film is reduced, so that releasability is enhanced. Moreover, it is more preferable to contain 3 to 20% by mass. It is more preferably contained in an amount of 5 to 10% by mass.

The second particles are preferably contained in an amount of 15 to 65% by mass in the solid content of the coating liquid. Within this range, the second particles interact with the primary clusters in a hetero-aggregating manner, resulting in the formation of secondary clusters large enough to form irregularities. As a result, the irregularities on the surface of the film are increased, and the releasability is improved. Moreover, it is more preferable to contain 20 to 60% by mass. More preferably, it is contained in an amount of 30 to 50% by mass.

It is preferable that the total amount of the first particles and the second particles is 20 to 70% by mass in the solid content of the coating liquid. If it is less than 20% by mass, secondary clusters having a size sufficient to form unevenness on the surface of the film cannot be obtained, resulting in a decrease in releasability of the film. If it is more than 70% by mass, the film is likely to crack because it contains many particles. Moreover, adhesion may fall. 30 to 65% by mass is more preferable, and 40 to 60% by mass is even more preferable.

The weight ratio of the first particles to the second particles (the weight of the second particles/the weight of the first particles) contained in the coating liquid is preferably in the range of 1-10. This makes it easier for the secondary particles to interact with the primary clusters in a heteroaggregating manner. As a result, the unevenness of the surface of the film is increased, so that the releasability of the film is improved. 2 to 9 are more preferred, and 3 to 8 are even more preferred.

The first inorganic oxide particles and the second inorganic oxide particles may have a known shape (spherical, rod-like, chain-like, fibrous, confetti-like, hollow, etc.). In particular, spherical particles are preferred. Moreover, the first inorganic oxide particles and the second inorganic oxide particles preferably contain at least one element selected from silicon, aluminum, zirconium, titanium, antimony, tin, and indium as a component. In particular, particles containing silica as a main component are more preferable. At this time, the shape of the first inorganic oxide particles may be the same as or different from that of the second inorganic oxide particles. Also, the element contained in the first inorganic oxide particles may be the same as or different from the element contained in the second inorganic oxide particles.

The first particles are preferably surface-treated with 1 to 30 parts by mass of a surfactant per 100 parts by mass of the first inorganic oxide particles. If the amount is less than 1 part by mass, the dispersibility of the first particles in the coating liquid is poor, so the first particles tend to aggregate and the storage stability of the coating liquid may deteriorate. If the amount is more than 30 parts by mass, a large amount of the surfactant that has not interacted with the first inorganic oxide particles is present in the coating liquid, so that it tends to bleed out to the surface of the film. Therefore, when a protective film or the like is attached to the surface of the film, the surfactant may be transferred to the protective film, which may adversely affect the process after mold release. 3 to 10 parts by mass is more preferable. Within this range, the dispersion stability of the first particles in the coating liquid is maintained. In addition, in the film-forming process, due to the interaction between the first particles and the cluster-forming agent, primary clusters of sufficient size are formed as starting points for the formation of irregularities on the surface of the film, so that excellent releasability can be easily obtained. .

Cationic, nonionic and anionic surfactants can be used as surfactants. Among these, cationic and nonionic surfactants are preferred. When such a surfactant is used, the .zeta.-potential of the first particles tends to become positive. Nonionic surfactants are particularly preferred. Aggregation is suppressed when the surface of negatively charged particles is treated with a surfactant. Among nonionic surfactants, amine surfactants are more preferable. When the first particles are dispersed in water, the ζ potential of the first particles tends to be positively charged. Further, when the first particles are dispersed in an organic solvent such as MIBK, the ζ potential of the first particles tends to be negatively charged. Specific examples of surfactants include Amiradin (registered trademark) C-1802, Plysurf (registered trademark) A-212E, and Plysurf AL manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Amirazine C-1802 is an amine-based nonionic surfactant.

The second particles are preferably surface-treated with 1 to 50 parts by mass of a silane coupling agent per 100 parts by mass of the second inorganic oxide particles. If it is less than 1 part by mass, the dispersibility of the second particles in the coating liquid is poor, and the second particles tend to aggregate, resulting in poor storage stability of the coating liquid. In addition, when the second particles have an acryloyl group or a methacryloyl group, the second particles are less likely to bond with the first composition or the second composition, resulting in lower hardness and abrasion resistance of the film. If the amount is more than 50 parts by mass, a large amount of the silane coupling agent that is not bound to the particles is present in the coating liquid, so that it is likely to bleed out to the surface of the film. Therefore, when a protective film or the like is attached to the surface of the film, the silane coupling agent is transferred to the protective film, which may adversely affect the process after mold release. 5 to 30 parts by mass is more preferable, and 10 to 20 parts by mass is particularly preferable. Within this range, the dispersion stability of the second particles in the coating liquid is maintained. Further, in the film-forming process, the primary clusters and the second particles are likely to cause potential heteroaggregation interaction, so that unevenness of a sufficient size is formed on the surface of the film. Therefore, excellent releasability is likely to be obtained.

The silane coupling agent preferably has a functional group containing a double bond such as a vinyl group, an acryloyl group or a methacryloyl group. As a result, the silane coupling agent in the second particles chemically bonds with the second composition when the film is cured, thereby improving the hardness of the film. Table 1 shows specific examples of silane coupling agents.

[Cluster Forming Agent]
The cluster forming agent is preferably contained in an amount of 1 to 30 parts by mass with respect to a total of 100 parts by mass of the first particles and the second particles in the coating liquid. If the amount of the cluster-forming agent is less than 1 part by mass, the interaction between the cluster-forming agent and the first particles is insufficient, so primary clusters large enough to form unevenness cannot be obtained. Therefore, releasability is deteriorated. If it is more than 30 parts by mass, the stability of the coating liquid may deteriorate. Further, it is more preferably 5 to 25 parts by mass, and even more preferably 10 to 20 parts by mass.

Examples of the cluster forming agent include acrylic, acrylic silicone, silicone and fluorine surface control agents. By using at least one of these surface conditioners, the primary clusters and the second particles are likely to interact in a heteroaggregative manner during drying of the coating liquid, and secondary clusters are likely to be formed. Examples of acrylic surface conditioners include Disparlon (registered trademark) UVX-271, UVX-272, UVX-3750, UVX-35 and UVX-36 manufactured by Kusumoto Kasei Co., Ltd. Examples of acrylic silicone surface conditioners include Disparon NSH-8430HF, LHP-810, NSF-8363, UVX-2280 and UVX-2285 manufactured by Kusumoto Chemicals. Examples of silicone-based surface conditioners include LS-430, LS-220, LS-240, LS-260, LS-280 and LS-480 manufactured by Kusumoto Chemicals. Examples of fluorine-based surface conditioners include F-555 and F-558 manufactured by DIC Corporation, and Futergent (registered trademark) 208G and 212P manufactured by Neos Corporation.

[First composition, second composition]
The weight average molecular weight of the first composition is preferably 30,000 or less. If it is more than 30,000, the compatibility between the first composition and the particles in the coating liquid is low, which may reduce the stability of the coating liquid. 20000 or less is more preferable. The weight average molecular weight of the first composition is particularly preferably 4000-12000. Within this range, the first composition tends to be unevenly distributed on the surface of the film, making it easier to obtain a film with excellent releasability.

It is preferable that the first composition is contained in an amount of 1 to 20% by mass based on the solid content of the coating liquid. If it is less than 1% by mass, the releasability is lowered because the amount of elemental fluorine on the surface of the film is small. If it is more than 20% by mass, the first composition tends to transfer to transfer paper, products, etc. when the transfer paper, products, etc. are released from the film-coated substrate. The first composition is more preferably contained in an amount of 2 to 15% by mass, more preferably 3 to 10% by mass in the solid content of the coating liquid. When the content is in the range of 3 to 10% by mass, fluorine is homogeneously present on the surface of the film, resulting in excellent releasability. In addition, the adhesiveness of the film is also excellent.

Preferably, the first composition has two or more acryloyl or methacryloyl groups. Thereby, the first composition and the second composition are chemically bonded when the second composition has an acryloyl group or a methacryloyl group. Therefore, when the transfer paper, the product, or the like is released from the film-coated substrate, the first composition is less likely to transfer to the transfer paper, the product, or the like. As the first composition, Optool (registered trademark) DAC-HP manufactured by Daikin Industries, Megafac (registered trademark) RS series manufactured by DIC, Fluorosurf (registered trademark) series manufactured by Fluorotechnology, Shin-Etsu Chemical Co., Ltd. KY-1203 and the like can be mentioned.

The weight average molecular weight of the second composition is preferably 20,000 or less. If it is more than 20,000, the compatibility between the second composition and the particles in the coating liquid becomes poor, which may lower the stability of the coating liquid. 10,000 or less is more preferable, and 5,000 or less is even more preferable. When it is 5000 or less, the second composition is compatible with the first particles and the second particles in the coating liquid. On the other hand, in the film-forming process, since the hydrophobicity of the second composition is higher than that of the first particles and the second particles, it promotes the formation of secondary clusters. As a result, sufficient unevenness is formed on the surface of the film, so that excellent releasability is likely to be obtained.

It is preferable that the second composition is contained in an amount of 10 to 70% by mass in the solid content of the coating liquid. If it is less than 10% by mass, the amount of the second composition that binds to the base material will be small, which may reduce the adhesion. If it is more than 70% by mass, the amount of fluorine unevenly distributed on the surface of the film decreases. In addition, since the secondary clusters become smaller, the releasability may deteriorate. The content of the second composition is more preferably 15 to 50% by mass, more preferably 20 to 30% by mass.

The second composition preferably has acryloyl or methacryloyl groups. This improves hardness and adhesion. The number of acryloyl groups is preferably 2-15. 2 to 10 are more preferred. 8 to 10 are more preferred. A high number of acryloyl or methacryloyl groups improves hardness. Moreover, it is preferable that the second composition has a urethane bond. As the second composition, NK Oligo UA-33H manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 8402 and EBECRYL 3708 manufactured by Daicel Ornex Co., Ltd., Shiko (registered trademark) UV-7550B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. etc. can be mentioned. A film obtained using a coating liquid containing such a second composition is excellent in releasability, adhesion, hardness, and heat resistance.

The surface tension ST _A of the first composition is 22 mN/m or less, the surface tension ST _B of the second composition is 28 mN/m or more and 32 mN/m or less, and the surface tension of the second composition and the first composition is preferably 7.5 mN/m or more. Within this range, the first composition tends to be unevenly distributed on the surface of the film. In addition, convection in the film that occurs when the coating solution is dried tends to form irregularities on the surface of the film starting from the secondary clusters. The surface tension of the first composition is more preferably 21 mN/m or less. The surface tension of the second composition is more preferably 29 mN/m or more and 31 mN/m or less. The difference between these is more preferably 8.0 or more. In addition, the lower limit of the surface tension of the first composition is preferably 10 mN/m or more.

[Acrylate monomer]
The coating liquid preferably contains an acrylate monomer having a weight average molecular weight of 100 to 1000 and 2 to 6 acryloyl groups. When the weight-average molecular weight is within this range, the viscosity of the coating liquid is lowered, so that the stability and handleability of the coating liquid are likely to be improved. In addition, since the acrylate monomer has a lower reaction rate than the second composition during curing, the reaction rate for curing the coating liquid is lowered. This increases the number of bonds between the film and the base material, thereby improving the adhesion. More preferably, it has 2-4 acrylate groups, even more preferably 2-3 acrylate groups.

It is preferable that the acrylate monomer is contained in the solid content of the coating liquid in an amount of 1 to 5% by mass. If it is less than 1% by mass, it is difficult to improve the stability and adhesion of the coating liquid. If it is more than 5% by mass, the compatibility between the second composition and the particles is too high, resulting in small secondary clusters. As a result, the unevenness formed on the surface of the film is reduced, and the desired releasability cannot be obtained. More preferably, the acrylate monomer is contained in an amount of 1-2% by weight. Specific examples of acrylate monomers are shown in Table 2.

[Organic solvent]
The organic solvent is preferably contained in the coating liquid in an amount of 50 to 90% by mass. If it is less than 50% by mass, the stability of the coating liquid may be lowered. On the other hand, when the amount is more than 90% by mass, the viscosity becomes low, so that it is difficult to apply uniformly when forming a film having a thickness of 5 μm or more. Therefore, film unevenness and poor appearance may occur. 60 to 85% by mass is more preferable, and 70 to 80% by mass is even more preferable.

The SP value of the organic solvent is preferably 11 or less. If it is greater than 11, the compatibility between the first composition and the organic solvent will be insufficient, so that convection in the film will make it difficult for the first composition to move to the surface of the film when the coating liquid is dried. As a result, the first composition is less likely to be unevenly distributed on the surface of the film, and sufficient releasability of the film cannot be obtained. The SP value can be obtained by the Fedors calculation method (RF Fedors, Polym. Eng. Sci., 14(2), 147-154 (1974)). Note that the SP value is more preferably 10.5 or less.

Furthermore, the coating liquid preferably contains a plurality of organic solvents having different SP values and boiling points. The SP value of the first organic solvent having the highest boiling point among the plurality of kinds of organic solvents is preferably 11 (cal/cm ³ ) ^1/2 or less. According to the coating liquid containing such a first organic solvent, the compatibility between the first organic solvent and the first composition is improved during drying. As a result, when the first organic solvent finally evaporates, the first composition moves to the surface of the film together with the first organic solvent, so that the fluorine component is unevenly distributed on the surface of the film. The first organic solvent is preferably contained in the coating liquid in an amount of 100 parts by mass or more with respect to 100 parts by mass of the first composition. This makes it easier for the first composition to be unevenly distributed on the surface of the film. Moreover, it is more preferable to contain 500 mass parts or more. The second organic solvent having a boiling point different from that of the first organic solvent may have an SP value greater than 11 (cal/cm ³ ) ^1/2 .

Organic solvents with an SP value of 11 or less include methyl isobutyl ketone (SP value 8.3), methyl ethyl ketone (SP value 9.3), propylene glycol monomethyl ether (SP value 10.2) and diethyl ether (SP value 9.0). , acetone (SP value 9.1), methylcyclohexanone (SP value 10.0), and the like.

[Other ingredients]
Other components (photopolymerization initiator, leveling agent, etc.) are added to the coating liquid as necessary. A known photopolymerization initiator can be used without particular limitation. At this time, the photopolymerization initiator is preferably contained in the solid content of the coating liquid in an amount of 1 to 20% by mass. If it is less than 1% by mass, the curing reaction will be difficult to proceed, and the hardness will tend to decrease. If it is more than 20% by mass, the proportion of the second composition in the film will decrease, and the hardness and wear resistance of the film will tend to decrease. More preferably, the photopolymerization initiator content is 1 to 10% by mass.

A leveling agent may be added to the coating solution in order to adjust the wettability with the substrate, the leveling property of the surface of the film, and the like. The leveling agent is preferably contained in an amount of 0.05 to 5.0% by mass based on the solid content of the coating liquid. If the amount is less than 0.05% by mass, the leveling effect is difficult to develop, and film unevenness and poor appearance may occur. If the amount is more than 5.0% by mass, the leveling agent tends to exist in the film or at the interface between the film and the substrate, which tends to reduce the hardness, abrasion resistance and adhesion of the film. More preferably, the leveling agent is contained in an amount of 0.1 to 2.5% by mass. Examples of leveling agents include acrylic leveling agents, acrylic silicone leveling agents, silicone leveling agents, and fluorine leveling agents. However, the leveling agent is preferably of a type different from that used for the clustering agent. By using different types of the cluster-forming agent and the leveling agent, the respective effects of the cluster-forming agent and the leveling agent are sufficiently exhibited.

<Method for producing coating liquid>
The manufacturing process of the coating liquid includes a first step of preparing first particles surface-treated with a surfactant, a second step of preparing second particles surface-treated with a silane coupling agent, and a first composition and a third step of mixing the second composition, the first particles, the second particles and the clustering agent.

In the first step, it is preferable to stir the mixture after mixing the first inorganic oxide particles and the surfactant. It is preferable to heat the mixture during stirring. By heating, the surfactant is sufficiently adsorbed on the surfaces of the first inorganic oxide particles, so that the first particles are less likely to aggregate in the coating liquid. Also, the reaction time is shortened. The heating temperature is preferably 40-60° C., and the heating time is preferably 10-30 hours. Through the first step, the first particles are stably dispersed in the coating liquid.

In the second step, it is preferable to stir the mixture after mixing the second inorganic oxide particles, the silane coupling agent, water and the dehydration catalyst. It is preferable to heat the mixture during stirring. Heating accelerates the hydrolytic condensation reaction between the second inorganic oxide particles and the silane coupling agent, shortening the reaction time. The heating temperature is preferably 40-60° C., and the heating time is preferably 3-30 hours. It is preferable to replace the solvent after stirring the mixture. By this second step, the silane coupling agent is sufficiently bonded to the second inorganic oxide particles, so that the second particles are stably dispersed in the coating liquid.

In the third step, it is preferable to mix the first composition and the second composition after preparing the cluster precursor by mixing the first particles, the second particles and the cluster forming agent. Furthermore, it is preferable to prepare the cluster precursor by mixing the first particles and the cluster forming agent, and then mixing the second particles. This makes it easier for the secondary particles to interact with the primary clusters in a hetero-aggregating manner when the coating liquid is dried, thereby facilitating the formation of secondary clusters. Therefore, the unevenness of the surface of the film is increased. The heating temperature is preferably 20 to 60° C., and the heating time is preferably 1 to 30 hours.

[Base material with film]
A film-coated substrate can be obtained by applying the coating liquid onto the substrate, drying it, and then curing it. By curing the film obtained by drying the coating liquid, the first composition and the second composition contained in the coating liquid are cured to become a fluororesin and a cured resin, respectively. Drying means heating the coated base material to 50 to 150° C. to volatilize and remove the solvent. After drying the coating liquid, the film is cured by irradiating the film with ultraviolet rays. Irradiation with ultraviolet rays is preferably performed in a nitrogen atmosphere.

The film-coated substrate has irregularities formed on the surface of the film, starting from the secondary clusters, due to convection in the film during drying of the coating liquid. Thereby, high releasability can be obtained. At this time, it is preferable that the secondary clusters in the film are formed from first particles having a particle size smaller than 300 nm and second particles having a particle size smaller than that of the first particles. The secondary cluster size is 500-7000 nm. If the thickness is less than 500 nm, the unevenness formed on the surface of the film will be small. Therefore, the releasability is deteriorated. If it is larger than 7000 nm, the adhesion may deteriorate. At this time, first particles and second particles that are not clustered may exist in the film. It may also contain primary clusters, secondary clusters and particles of 500 nm or less. More preferably, the secondary cluster size is 750 to 5000 nm.

The average surface roughness (R _a ) of the film is 150-1000 nm, and the maximum height difference (R _max ) is 1500-5000 nm. The average roughness and the maximum height difference can be adjusted by adjusting the average particle size of the first particles and the second particles, the amount of the first particles and the second particles added, the amount of the cluster forming agent added, and the like. More preferably, the average roughness is 200-800 nm, and even more preferably 300-600 nm. The maximum height difference is more preferably 2500 to 5000 nm, even more preferably 3000 to 4500 nm.

It is preferable that the film of the film-attached base material contains a fluororesin and a curable resin, and the fluororesin is unevenly distributed on the surface side of the film. The degree of uneven distribution of the fluororesin can be estimated by measuring the ratio of fluorine atoms using X-ray photoelectron spectroscopy. The degree of uneven distribution of fluorine atoms in the film can be determined from the ratio of the fluorine atom ratio (X _o [%]) on the film surface to the fluorine atom ratio (X ₇₀₀ [%]) at a depth of 700 nm from the film surface. I understand. When this ratio (X _o /X ₇₀₀ ) is 3.0 to 8.0 and X ₀ is 30 to 40, the film has excellent releasability. This ratio is more preferably 4.0 to 6.0. The ratio of fluorine atoms is the number of fluorine atoms with respect to the total number of atoms of carbon, oxygen, silicon and fluorine. The atomic proportions of carbon, oxygen, silicon and fluorine can be determined by measuring the peaks of C1s, O1s, Si2p and F1s respectively by X-ray photoelectron spectroscopy. KRATOS ULTRA2 manufactured by Shimadzu Corporation was used as an X-ray photoelectron spectroscopic analyzer. The spectrum measurement conditions are X-Ray: 300 W, Pass Energy: Wide 160 eV, Narrow 80 eV, analysis diameter: 110 μm, Charge Neutralizer: On. Ion gun uses Ar Gass Cluster Ion, acceleration voltage: 5 kV, cluster size: 3000, paste size: 1.0 × 1.0 mm, etching rate: 25.0 mm / min (PLGA: polylacto, polylactic acid, glycol acid copolymers). The analysis was performed with a binding energy calibration of 285.0 eV for C1s(C—H). The energy intensity of the C1s peak is observed at 284-286 eV. O1s is observed at 532-534 eV, Si2p at 103-104 eV, and F1s at 687-689 eV. Ar etching was performed for 28 minutes in the measurement at a depth of 700 nm from the surface of the film. Further, the ratio (X _o /X ₁₀₀ ) between X _o [%] and the ratio X ₁₀₀ [%] of fluorine atoms at a depth of 100 nm from the surface of the film is in the range of 1.0 to 4.0. preferable. More preferably, it is in the range of 1.5 to 2.5. Within this range, the film has excellent releasability. Furthermore, (X _o /X ₁₀₀ ) is preferably less than (X _o /X ₇₀₀ ).

Examples of the present invention will be specifically described below. Table 3 shows an overview of the preparation conditions of the coating liquid and the ζ potential of the particles.

[Example 1]
100 g of a methanol dispersion of silica particles (manufactured by Nikki Shokubai Kasei Co., Ltd.: ELCOM (registered trademark) V-8901, average particle diameter 120 nm, solid content concentration 20.5% by mass) and 1.03 g of a surfactant (C-1802). Mixed. After stirring at 50° C. for 20 hours, a methanol dispersion of first particles having a solid content concentration of 21.31% by mass was obtained.

100 g of a methanol dispersion of silica alumina particles (manufactured by Nikki Shokubai Kasei Co., Ltd.: OSCAL (registered trademark) 1132, average particle diameter 12 nm, solid content concentration 40.5% by mass), and γ-methacryloxypropyl as a silane coupling agent 6.08 g of trimethoxysilane (KBM-503), 8.8 g of ultrapure water, and 0.4 g of 5% aqueous ammonia were mixed. After stirring at 50° C. for 6 hours, the solvent was replaced with MIBK using a rotary evaporator to obtain an MIBK dispersion of second particles having a solid content concentration of 45.44% by mass.

The dispersion of the first particles and the dispersion of the second particles were diluted with water to a solid content of 0.5% by mass to prepare samples, and the ζ potential was measured with Zetasizer Nano Series Nano-ZS manufactured by Malvern. bottom. Table 3 shows the results.

9.76 g of the methanol dispersion of the first particles, 29.63 g of the MIBK dispersion of the second particles, and 20.00 g of the cluster forming agent (manufactured by Kusumoto Kasei Co., Ltd.: Disparon LHP-810, solid content concentration 10.0% by mass) were mixed. A cluster precursor was prepared by doing so.

59.39 g of this cluster precursor, 10.00 g of the first composition (RS-90), 8.00 g of the second composition (UA-33H), 17.42 g of the organic solvent (MIBK 12.50 g, PGME 4.92 g ), a leveling agent (manufactured by Kusumoto Kasei Co., Ltd.: Disparon NSH-8430HF, solid content concentration 10.0% by mass) 4.72 g, and a photopolymerization initiator (manufactured by IGM: Omnirad (registered trademark) 184) 0.48 g. By mixing, a coating liquid having a solid content concentration of 27.85% by mass was prepared. In the following examples and comparative examples, Disparon NSH-8430HF was used as a leveling agent, and Omnirad 184 was used as a photopolymerization initiator.

The coating liquid was applied to a 188 μm-thick PET film with an easy-adhesion layer (manufactured by Toyobo Co., Ltd.: A4300) by a bar coater method (#24). After drying at 80° C. for 120 seconds, a film-coated substrate was obtained by irradiating ultraviolet rays of 300 mJ/cm ² in an N ₂ atmosphere. The average film thickness was measured with a digital gauge (manufactured by Ono Sokki Co., Ltd.: ST-0230). The film thickness was 10 μm in all examples and comparative examples.

The film properties of the film-coated substrate, such as releasability, adhesion, R _a , R _max , and cluster size, were measured and evaluated by the following methods. Moreover, the storage stability of the coating liquid was evaluated by the following method. Table 4 shows the results. Also, the ratio of fluorine atoms in the film was measured by the method described above. Table 5 shows the results. Film-coated substrates were similarly prepared for Examples and Comparative Examples described later, and measured and evaluated.

[Evaluation of releasability]
A cellophane tape with a width of 18 mm (manufactured by Nichiban Co., Ltd.) was attached to the film of the film-coated substrate with a length of 20 mm, and the tape was peeled off with a finger, and the ease of peeling was evaluated according to the following evaluation criteria.

Evaluation criteria:
Peel off without resistance: ◎
There is a little resistance, but it can be easily peeled off: ○
There is resistance, but it can be peeled off: △
There is resistance, and if you pull it up strongly, it will come off : ×

[Evaluation of adhesion]
On the film on the film-coated substrate, 11 parallel scratches were made with a knife at intervals of 1 mm in length and width to form 100 squares. After adhering cellophane tape to these squares, the cellophane tape was peeled off. The number of squares remaining without peeling of the film was counted and evaluated according to the following evaluation criteria.

Evaluation criteria:
Number of remaining squares: 100: ◎
Number of remaining squares 90 to 99: ○
Number of remaining squares 85 to 89: △
Number of remaining squares 84 or less: ×

[Measurement of average roughness (R _a ) and maximum in-plane height difference (R _max )]
Using an atomic force microscope (AFM), the average roughness (R _a ) of 50 μm square and the maximum in-plane height difference (Rmax) were measured.

[Cluster size]
The film-coated base material was embedded in a resin, the cross section of the film was cut with a microtome, and the cut surface was measured with a scanning electron microscope (SEM) to measure the size of clusters present in the film.

[Storage stability of coating solution]
After putting the paint in a 100 mL light-shielding plastic container, it was stored in a refrigerator (0 to 10° C.) for one month. After that, the light-shielding plastic container was shaken by hand 10 times. After coating this paint on a PET film, the film was evaluated according to the following evaluation criteria.

Evaluation criteria:
The paint disperses easily, and the releasability and adhesion properties are the same as in the initial stage. :◎
The dispersibility of the paint decreases, but the releasability and adhesion properties are the same as in the initial stage. :○
The dispersibility of the paint is reduced, and the releasability and adhesion are also reduced compared to the initial stage : △
The paint does not disperse completely, and the releasability and adhesion are greatly reduced from the initial stage : ×

[Example 2]
A methanol dispersion of the first particles (solid concentration: 23.65% by mass) was prepared in the same manner as in Example 1, except that 4.12 g of surfactant (C-1802) was mixed.

Thereafter, instead of 8.00 g of the second composition, 7.20 g of the second composition and 0.80 g of the acrylate monomer (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DCP-LC3) were used. A coating liquid having a solid content concentration of 27.72% by mass was prepared in the same manner as in Example 1.

[Example 3]
After adding 1025 g of ion-exchanged water to 1000 g of an aqueous dispersion of silica particles (manufactured by Nikki Shokubai Kasei Co., Ltd.: Cataloid (registered trademark) SI-50, average particle diameter 25 nm, solid content concentration 40.5% by mass), cation exchange 135 g of resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added and stirred for 1 hour. After separating the cation exchange resin, 135 g of anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added and stirred for 1 hour. 135 g of the cation exchange resin (SK-1BH) was added again and stirred for 1 hour to prepare a silica particle dispersion having a solid concentration of 20% by mass.

The solvent of this dispersion was replaced with methanol through an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 20.5% by weight. After 100 g of this methanol dispersion and 2.06 g of surfactant (C-1802) were mixed, the mixture was stirred at 50° C. for 20 hours to obtain a methanol dispersion of first particles having a solid concentration of 22.1% by mass. .

A cluster precursor was prepared in the same manner as in Example 1, except that the methanol dispersion of the first particles was used. Thereafter, in the same manner as in Example 2, a coating liquid having a solid concentration of 27.59% by mass was prepared.

[Example 4]
A MIBK dispersion of second particles having a solid content concentration of 60.75% by mass was obtained in the same manner as in Example 1, except that 20.25 g of a silane coupling agent (KBM-503) was used.

A cluster precursor was prepared in the same manner as in Example 1, except that the MIBK dispersion of the second particles was used. Thereafter, in the same manner as in Example 2, a coating liquid having a solid concentration of 32.05% by mass was prepared.

[Example 5]
After adding 1025 g of ion-exchanged water to 1000 g of an aqueous dispersion of silica alumina particles (manufactured by Nikki Shokubai Kasei Co., Ltd.: Cataloid SI-80, average particle diameter 80 nm, solid content concentration 40.5% by mass), a cation exchange resin (SK -1BH) was added and stirred for 1 hour. After separating the cation exchange resin, 135 g of anion exchange resin (SANUPC) was added and stirred for 1 hour. 135 g of the cation exchange resin (SK-1BH) was added again and stirred for 1 hour to prepare a silica particle dispersion having a solid concentration of 20% by mass.

The solvent of this dispersion was replaced with methanol through an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 20.5% by weight.

100 g of this methanol dispersion, 6.08 g of γ-methacryloxypropyltrimethoxysilane (KBM-503) as a silane coupling agent, 8.8 g of ultrapure water, and 0.4 g of 5% aqueous ammonia were mixed. After that, the mixture was stirred at 50°C for 6 hours. Thereafter, the solvent was replaced with MIBK using a rotary evaporator to obtain an MIBK dispersion containing second particles having a solid content concentration of 45.44% by mass.

By mixing 29.63 g of the MIBK dispersion containing the second particles, 9.76 g of the methanol dispersion containing the first particles prepared in Example 1, and 20.00 g of the cluster forming agent (LHP-810), a cluster precursor was obtained. body was prepared.

A coating liquid having a solid content concentration of 27.49% by mass was prepared in the same manner as in Example 2 except that this cluster precursor was used.

[Example 6]
4.88 g of the methanol dispersion of the first particles prepared in Example 1, 14.81 g of the MIBK dispersion of the second particles prepared in Example 1, and 20.00 g of the cluster forming agent (LHP-810) were mixed, A cluster precursor was prepared.

39.69 g of this cluster precursor, 10.00 g of the first composition (RS-90), 12.60 g of the second composition (UA-33H), 1.40 g of the acrylate monomer (A-DCP), an organic By mixing 30.75 g of solvent (22.10 g of MIBK, 8.65 g of PGME), 4.72 g of leveling agent, and 0.84 g of photopolymerization initiator, a coating liquid having a solid concentration of 26.08% by mass was prepared.

[Example 7]
By mixing 25.61 g of the methanol dispersion of the first particles prepared in Example 1, 12.96 g of the MIBK dispersion of the second particles prepared in Example 1, and 20.00 g of the cluster forming agent (LHP-810), , to prepare cluster precursors.

58.57 g of this cluster precursor, 10.00 g of the first composition (RS-90), 5.40 g of the second composition (UA-33H), 0.60 g of the acrylate monomer (A-DCP), an organic By mixing 20.35 g of solvent (12.50 g of MIBK, 7.85 g of PGME), 4.72 g of leveling agent, and 0.36 g of photopolymerization initiator, a coating liquid having a solid concentration of 21.18% by mass was prepared.

[Example 8]
By mixing 9.76 g of the methanol dispersion of the first particles prepared in Example 1, 29.63 g of the MIBK dispersion of the second particles prepared in Example 1, and 2.00 g of the cluster forming agent (LHP-810), , to prepare cluster precursors.

41.39 g of this cluster precursor, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), 0.80 g of the acrylate monomer (A-DCP), an organic By mixing 35.42 g of solvent (25.20 g of MIBK, 10.22 g of PGME), 4.72 g of leveling agent, and 0.48 g of photopolymerization initiator, a coating liquid having a solid concentration of 25.69% by mass was prepared.

[Example 9]
59.39 g of the cluster precursor prepared in Example 1, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), and 0 acrylate monomer (A-DCP) .80 g, 17.42 g of organic solvent (MIBK 12.50 g, PGME 4.92 g), leveling agent 4.72 g, and photopolymerization initiator 0.48 g were mixed to form a coating with a solid content concentration of 27.85% by mass. A liquid was prepared.

[Example 10]
EBECRYL 3708 manufactured by Daicel Allnex Co., Ltd. was used in place of UA-33H of the second composition of Example 1. A coating liquid was prepared in the same manner as in Example 9 except for this.

[Example 11]
9.76 g of the methanol dispersion of the first particles prepared in Example 1, 29.63 g of the MIBK dispersion of the second particles prepared in Example 1, 10.00 g of the first composition (RS-90), Second composition (UA-33H) 7.20 g, acrylate monomer (A-DCP) 0.80 g, organic solvent 17.42 g (MIBK 12.50 g, PGME 4.92 g), cluster forming agent (LHP-810) 20.00 g, 4.72 g of a leveling agent, and 0.48 g of a photopolymerization initiator were mixed to prepare a coating liquid having a solid concentration of 27.49% by mass.

[Comparative Example 1]
A cluster precursor was prepared by mixing 34.57 g of the MIBK dispersion of the second particles prepared in Example 1 and 20.00 g of a cluster forming agent (LHP-810).

54.57 g of this cluster precursor, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), 0.80 g of the acrylate monomer (A-DCP), an organic By mixing 22.24 g of solvent (9.70 g of MIBK, 12.54 g of PGME), 4.72 g of leveling agent, and 0.48 g of photopolymerization initiator, a coating liquid having a solid concentration of 27.66% by mass was prepared.

[Comparative Example 2]
A cluster precursor was prepared by mixing 36.59 g of the methanol dispersion containing the first particles prepared in Example 1 and 20.00 g of a cluster forming agent (LHP-810).

56.59 g of this cluster precursor, 10.00 g of the first composition (RS-90), 6.75 g of the second composition (UA-33H), 0.75 g of the acrylate monomer (A-DCP), an organic By mixing 20.75 g of solvent (12.60 g of MIBK, 8.15 g of PGME), 4.72 g of leveling agent, and 0.45 g of photopolymerization initiator, a coating liquid having a solid concentration of 19.21% by mass was prepared.

Using this coating liquid, a film-coated substrate was produced in the same manner as in Example 1, except that the bar coater used in Example 1 was changed to #34.

[Comparative Example 3]
Silica particles (manufactured by Nikki Shokubai Kasei Co., Ltd.: SW1.4, average particle diameter 1400 nm, solid content concentration 100% by mass) dispersed in methanol at 20.50% by mass 100 g, surfactant (C-1802) 1 .03 g was mixed. After stirring at 50° C. for 20 hours, a methanol dispersion of first particles having a solid content concentration of 21.31% by mass was obtained.

A cluster precursor was prepared by mixing 36.59 g of the methanol dispersion of the first particles and 20.00 g of a cluster forming agent (LHP-810).

56.59 g of this cluster precursor, 10.00 g of the first composition (RS-90), 6.75 g of the second composition (UA-33H), 0.75 g of the acrylate monomer (A-DCP), an organic By mixing 20.75 g of solvent (12.60 g of MIBK, 8.15 g of PGME), 4.72 g of leveling agent, and 0.45 g of photopolymerization initiator, a coating liquid having a solid concentration of 19.21% by mass was prepared.

Using this coating liquid, a film-coated substrate was produced in the same manner as in Example 1, except that the bar coater was changed to #34.

[Comparative Example 4]
100 g of OSCAL1132, 6.18 g of surfactant (C-1802) and 97.56 g of methanol were mixed. After stirring at 50° C. for 20 hours, a methanol dispersion of first particles having a solid content concentration of 25.13% by mass was obtained.

By mixing 9.76 g of the methanol dispersion containing the first particles, 29.63 g of the MIBK dispersion of the second particles prepared in Example 5, and 20.00 g of the cluster forming agent (LHP-810), a cluster precursor was obtained. was prepared.

59.39 g of this cluster precursor, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), 0.80 g of the acrylate monomer (A-DCP), an organic By mixing 17.42 g of solvent (MIBK 12.50 g, PGME 4.92 g), leveling agent 4.72 g, and photopolymerization initiator 0.48 g, a coating liquid having a solid concentration of 27.85% by mass was prepared.

[Comparative Example 5]
After adding 25 g of ion-exchanged water to 1000 g of an aqueous dispersion of silica (manufactured by Nikki Shokubai Kasei Co., Ltd.: SS-300, average particle size 300 nm, SiO _{concentration} 20.5% by weight), a cation exchange resin (SK-1BH) was added. 135 g was added and stirred for 1 hour. After separating the cation exchange resin, 135 g of anion exchange resin (SANUPC) was added and stirred for 1 hour. After adding 135 g of the cation exchange resin (SK-1BH) again, the mixture was stirred for 1 hour to prepare a silica particle dispersion having a SiO ₂ concentration of 20% by weight.

By replacing the solvent of this dispersion with methanol through an ultrafiltration membrane, a methanol dispersion having a solid concentration of 20.5% by weight was obtained.

After mixing 100 g of this methanol dispersion and 1.03 g of surfactant (C-1802), the mixture was stirred at 50° C. for 20 hours to obtain a methanol dispersion of first particles having a solid content concentration of 21.31% by mass. Obtained.

After adding 25 g of ion-exchanged water to 1000 g of an aqueous dispersion of silica (manufactured by Nikki Shokubai Kasei Co., Ltd.: SS-160, average particle size 160 nm, solid content concentration 20.5% by weight), a cation exchange resin (SK-1BH) was added. 135 g was added, stirred for 1 hour, and dealkalized. After separating the cation exchange resin, 135 g of anion exchange resin (SANUPC) was added and stirred for 1 hour. 135 g of the cation exchange resin (SK-1BH) was added again and stirred for 1 hour to prepare a silica particle dispersion having a solid concentration of 20% by weight.

By replacing the solvent of this dispersion with methanol through an ultrafiltration membrane, a methanol dispersion having a solid concentration of 20.5% by weight was obtained.

100 g of this methanol dispersion, 3.04 g of KBM-503 as a silane coupling agent, 8.8 g of ultrapure water, and 0.4 g of 5% aqueous ammonia were mixed and then stirred at 50° C. for 6 hours. After that, by replacing the solvent with MIBK using a rotary evaporator, an MIBK dispersion containing second particles having a solid content concentration of 45.44% by mass was obtained.

A cluster precursor was prepared by mixing 9.76 g of the methanol dispersion containing the first particles, 29.63 g of the MIBK dispersion containing the second particles, and 20.00 g of the cluster forming agent (LHP-810).

A coating liquid having a solid content concentration of 27.49% by mass was prepared in the same manner as in Example 1, except that this cluster precursor was used.

[Comparative Example 6]
Neugen (registered trademark) TDS-70 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration 100% by mass) 2.06 g was used as a surfactant in the same manner as in Example 1, solid content concentration 22.10 mass. % of the first particles in methanol was obtained.

A cluster precursor was prepared in the same manner as in Example 1 using the methanol dispersion of the first particles. Thereafter, in the same manner as in Example 2, a coating liquid having a solid concentration of 27.93% by mass was prepared.

[Comparative Example 7]
9.76 g of the MIBK dispersion of the first particles prepared in Example 1, 29.63 g of the MIBK dispersion of the second particles prepared in Example 1, 10.00 g of the first composition (RS-90), Second composition (UA-33H) 7.20 g, acrylate monomer (A-DCP) 0.80 g, organic solvent 37.42 g (MIBK 26.70 g, PGME 10.72 g), leveling agent 4.72 g, light A coating liquid having a solid concentration of 25.49% by mass was prepared by mixing 0.48 g of a polymerization initiator.

[Comparative Example 8]
59.39 g of the cluster precursor prepared in Example 1, the first composition having a weight average molecular weight of 154.1 (manufactured by Osaka Organic Chemical Industry Co., Ltd.: Viscoat 3F, solid content concentration 100% by mass) 1.00 g, Two compositions (UA-33H) 7.20 g, acrylate monomer (A-DCP) 0.80 g, organic solvent 26.42 g (MIBK 19.00 g, PGME 7.42 g), leveling agent 4.72 g, photopolymerization A coating liquid having a solid concentration of 27.49% by mass was prepared by mixing 0.48 g of an initiator.

[Comparative Example 9]
59.39 g of the cluster precursor prepared in Example 1, 10.00 g of the first composition (RS-90), and 8.00 g of an acrylate monomer (manufactured by Kyoeisha Chemical Co., Ltd.: Light Acrylate (registered trademark) DPE-6A) , 17.42 g of an organic solvent (MIBK 12.50 g, PGME 4.92 g), a leveling agent 4.72 g, and a photopolymerization initiator 0.48 g are mixed to prepare a coating liquid having a solid content concentration of 27.49% by mass. bottom.

[Comparative Example 10]
100 g of OSCAL 1132 and 12.15 g of surfactant (C-1802) were mixed. After stirring at 50° C. for 20 hours, a methanol dispersion of second particles having a solid content concentration of 49.95% by mass was obtained.

By mixing 29.63 g of the MIBK dispersion of the second particles, 9.76 g of the methanol dispersion containing the first particles prepared in Example 1, and 20.00 g of the cluster forming agent (LHP-810), a cluster precursor was obtained. was prepared.

59.39 g of the cluster precursor, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), 0.80 g of the acrylate monomer (A-DCP), and an organic solvent By mixing 17.42 g (MIBK 12.50 g, PGME 4.92 g), leveling agent 4.72 g, and photopolymerization initiator 0.48 g, a coating liquid having a solid concentration of 27.94% by mass was prepared.

[Comparative Example 11]
100 g of ELCOM V-8901, KBM-5036.08 g as a silane coupling agent, 8.8 g of ultrapure water, and 0.4 g of 5% aqueous ammonia were mixed. After stirring at 50° C. for 6 hours, the solvent was replaced with MIBK using a rotary evaporator to obtain an MIBK dispersion of first particles having a solid concentration of 23.0% by mass.

By mixing 9.76 g of the MIBK dispersion containing the first particles, 29.63 g of the MIBK dispersion of the second particles prepared in Example 1, and 20.00 g of the cluster forming agent (LHP-810), a cluster precursor was obtained. was prepared.
59.39 g of the cluster precursor, 10.00 g of the first composition (RS-90), 7.20 g of the second composition (UA-33H), 0.80 g of the acrylate monomer (A-DCP), and an organic solvent By mixing 17.42 g (MIBK 12.50 g, PGME 4.92 g), leveling agent 4.72 g, and photopolymerization initiator 0.48 g, a coating liquid having a solid content concentration of 27.65% by mass was prepared.

Claims (7)

a UV-curable first composition containing elemental fluorine;
a UV-curable second composition that does not contain elemental fluorine;
first particles, the surfaces of which are treated with at least one of cationic, nonionic and anionic surfactants;
a second particle, the surface of which is treated with a silane coupling agent having a functional group containing a double bond ;
a cluster-forming agent that is at least one of acrylic, acrylic silicone, silicone, and fluorine-based surface modifiers ;
A coating liquid for forming a film containing an organic solvent,
The weight average molecular weight of the first composition and the second composition is 1000 or more,
The first composition and the second composition contain a carbon skeleton,
The first composition has two or more acryloyl groups or methacryloyl groups,
the second composition has 2 to 15 acryloyl or methacryloyl groups;
Fluorine is bonded to some of the carbon atoms of the first composition,
the first particles have a particle diameter of 10 nm or more and less than 300 nm,
the particle diameter of the second particles is smaller than that of the first particles,
The second particles have a particle diameter of 9 to 100 nm,
When the first particles are dispersed in water, the ζ potential of the first particles is positive,
A coating liquid, wherein the ζ potential of the second particles is negative when the second particles are dispersed in water. 2. The coating liquid according to claim 1, wherein the difference between the .zeta.-potential of the first particles and the .zeta.-potential of the second particles is 20 to 60 mV. Containing 50 to 90% by weight of the organic solvent,
Containing 1 to 20% by weight of the first composition in solid content,
Containing 10 to 70% by weight of the second composition in solid content,
Containing 1 to 30% by weight of the first particles in the solid content,
The weight ratio of the first particles to the second particles contained in the coating liquid (weight of second particles/weight of first particles) is 1 to 10,
2. The coating liquid according to claim 1, wherein the cluster forming agent is contained in an amount of 1 to 30 parts by mass with respect to a total of 100 parts by mass of the first particles and the second particles in the coating liquid. The coating liquid according to any one of claims 1 to 3 , comprising an acrylate monomer having a weight average molecular weight of 100 to 1000 and having 2 to 6 acryloyl groups. A film-coated base material in which a film is formed on the surface of the base material,
The film contains clusters with an average particle size of 500 to 7000 nm,
The surface of the film has an average roughness (R _a ) of 150 to 1000 nm and a maximum height difference (R _max ) of 1500 to 5000,
The ratio (X 0 /X) of the ratio of fluorine atoms on the film surface (X ₀ [%] ) to the ratio of fluorine atoms ₍ X ₇₀₀ [%] ) at a depth of 700 nm from the film surface, measured by X-ray photoelectron spectroscopy. ₇₀₀ ) satisfies the following relational expression,
3.0<X _o /X ₇₀₀ <8.0
A substrate with a film, wherein X _o satisfies 30<X ₀ <40. The ratio of the fluorine atom ratio (X _o [%] ) on the film surface to the fluorine atom ratio (X ₁₀₀ [%] ) at a depth of 100 nm from the film surface, measured by the X-ray photoelectron spectroscopy ( X _o /X ₁₀₀ ) and the ratio of fluorine atoms (X ₇₀₀ ) at a depth of 700 nm from the film surface satisfy the following relational expression.
1.0<X _o /X ₁₀₀ <4.0
_Xo / _X100 < _Xo / _X700 A step of applying the coating liquid according to claim 1 onto a substrate;
a step of drying the coating liquid to form a film;
and a step of curing the film.