JP2020100020A - Substrate with cured resin layer, decorative sheet, decorative plate, window for vehicle, and method for producing substrate with cured resin layer - Google Patents

Abstract

To provide a substrate with a cured resin layer having excellent scratch resistance, abrasion resistance, and weather resistance.SOLUTION: There is provided a substrate 100 with a cured resin layer, which comprises a substrate 1 and a cured resin layer 3 formed on at least one surface of the substrate. The cured resin layer is obtained by drying and curing a coating liquid containing the following (A) to (C) and has 2.0 or more of ratio Y/X between X (at%) of carbon atom content rate and Y (at%) of silicon atom content rate in a region of 10 nm in the depth direction measured using X-ray photoelectron spectroscopy from the surface of the cured resin layer and 1.5 or less of Y/X in a region of 1500 nm in the depth direction. (A) is a methylsiloxane resin comprising a combination of methylsiloxane structural units having at least one functionality of bifunctionality, trifunctionality and tetrafunctionality. (B) is alumina nanoparticles having a carbon-carbon double bond in the modifying group structure. (C) is an alkoxysilane having a carbon-carbon double bond in the modifying group structure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin-cured layer-coated substrate, a decorative sheet, a decorative plate, a vehicle window, and a method for manufacturing a resin-cured layer-coated substrate.

Interior and exterior members such as walls and floors of houses and buildings, surface materials such as furniture and home appliances, automobiles, and windows and glazing are made of particles board, thermoformed resin, etc. It is generally performed to bond a sheet or a surface protective film or a hard coat film for the purpose of improving durability, scratch resistance, chemical resistance, etc. of a substrate (for example, Patent Document 1). 2).
Furthermore, in recent years, in windows of automobiles, railroads, etc., windows and doors of buildings, furniture, etc., glass has been replaced with resin in order to reduce weight and the degree of freedom in shape, and it corresponds to floor materials for commercial facilities and public transportation. Therefore, stronger scratch resistance and abrasion resistance are required, and a method of depositing an inorganic film such as glass on the surface by a method such as CVD or excimer light modification is used (for example, Patent Document 3, 4).

Japanese Patent No. 5521886 International publication 2017/090679 gazette Japanese Patent No. 5940409 Japanese Patent No. 4536824

However, the method of depositing these inorganic films provides relatively strong scratch resistance and abrasion resistance, but is not sufficient as the hardness of the thin film, and further hardness comparable to that of bulk glass is required. There is. In addition, the strong internal stress of the inorganic film and insufficient adhesion with the underlying lower layer in contact with the inorganic film combine to cause fine cracks or peeling in a high-humidity heat environment or long-term use. It was a challenge.
The present invention has been made to solve these drawbacks, and has a substrate with a resin cured layer having scratch resistance, abrasion resistance, and weather resistance, a decorative sheet, a decorative sheet, a vehicle window, and a resin cured layer. It is an object to provide a method for manufacturing a substrate.

In order to solve the above problems, a substrate with a resin cured layer of an embodiment according to the present invention includes a substrate and a resin cured layer formed on at least one surface of the substrate, and the resin cured layer is as follows: The coating liquid containing (A) to (C) is dried and cured, and the carbon atom content rate X in the region of 10 nm in the depth direction measured from the surface of the resin cured layer using X-ray photoelectron spectroscopy. The ratio Y/X of (at %) to the silicon atom content Y (at %) is 2.0 or more, and the Y/X in the region of 1500 nm in the depth direction is 1.5 or less. (A) is a methylsiloxane resin composed of a combination of at least any one of bifunctional to tetrafunctional methylsiloxane structural units, and (B) is an alumina nanoparticle having a carbon-carbon double bond in the modifying group structure. The particles (C) are alkoxysilanes having a carbon-carbon double bond in the modifying group structure.

In addition, a method for producing a substrate with a resin cured layer according to an embodiment of the present invention is to apply a coating liquid containing the following (A) to (C) to at least one surface of the substrate, dry it, and cure it. The method includes a step of forming a resin cured layer, a step of installing a photomask on the resin cured layer, and a step of subjecting the surface of the resin cured layer to Xe ₂ excimer light irradiation treatment through the photomask. The base material has a transmittance of light having a wavelength of 172 nm of 60% or more, the photomask has a light-shielding pattern formed thereon, and the width of the light-shielding portion of the light-shielding pattern is 3 μm or more and 20 μm or less, and the light-shielding pattern is repeated. The pitch is 23 μm or more and 300 μm or less. (A) is a methylsiloxane resin composed of a combination of at least any one of bifunctional to tetrafunctional methylsiloxane structural units, and (B) is an alumina nanoparticle having a carbon-carbon double bond in the modifying group structure. Particles (C) are alkoxysilanes having a carbon-carbon double bond in the modifying group structure.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the board|substrate with a resin hardening layer which has a scratch resistance, abrasion resistance, and weather resistance, a decorative sheet, a decorative board, a window for vehicles, and a board|substrate with a resin hardening layer can be provided.

It is a top view showing a substrate with a resin hardening layer concerning the present invention. FIG. 2 is a sectional view taken along the line II-II in FIG. 1. It is a figure explaining the method of mapping Martens hardness at the time of forming a grid pattern on the surface of the resin hardening layer which constitutes the substrate with a resin hardening layer of the present invention. It is a figure which shows the grid-shaped photo pattern formed in the surface of the resin hardened layer in the Example which illustrates this invention concretely. FIG. 5 is a cross-sectional view taken along the line VV of FIG. 4. It is a figure which shows the circular photo pattern formed in the surface of the resin cured layer in the Example which illustrates this invention concretely. It is a figure which shows the hexagonal photo pattern formed in the surface of the resin cured layer in the Example which illustrates this invention concretely. It is sectional drawing which shows the decorative sheet or decorative plate which concerns on this invention. It is a sectional view showing a window for vehicles concerning the present invention.

Next, embodiments of the present invention will be described with reference to the drawings. In the following description of the drawings, the same or similar reference numerals are given to the same or similar parts. However, it should be noted that the drawings are schematic, and the relationship between the thickness and the plane dimension, the ratio of the thickness of each layer, and the like are different from the actual ones. Therefore, the specific thickness and dimensions should be determined in consideration of the following description. Further, it is needless to say that the drawings include parts in which dimensional relationships and ratios are different from each other.
Further, the embodiments described below exemplify an apparatus and a method for embodying the technical idea of the present invention, and the technical idea of the present invention is the material, shape, structure, and arrangement of components. Etc. are not specified below. Various changes can be added to the technical idea of the present invention within the technical scope defined by the claims described in the claims.

1 and 2 are cross-sectional views showing the structure of a substrate with a resin cured layer according to an embodiment of the present invention. The substrate 100 with a cured resin layer of the present embodiment includes a substrate 1, an intermediate layer 2 provided on at least one surface 1 a of the base material 1, and a cured resin layer 3 provided on the intermediate layer 2. ing.
The material of the substrate 1 is not particularly limited, and various materials such as resin, glass, paper, wood and metal can be used. Among these, when molding the base material by injection molding of a resin, a thermoplastic resin or a thermosetting resin (including a one-component or two-component curable resin) described later can be used. Examples of the thermoplastic resin material include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride, polystyrene, acrylonitrile-styrene copolymer, and styrene resins such as ABS resin (acrylonitrile-butadiene-styrene copolymer resin). Acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate and polyacrylonitrile, polyolefin resins such as polyethylene, polypropylene and polybutene, polyethylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polybutylene terephthalate And the like, polyester-based resins, polycarbonate resins, and the like. Examples of the thermosetting resin include one-component or two-component reaction-curable polyurethane resin and epoxy resin. These resins may be used alone or in combination of two or more.

In addition, various additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a flame retardant, a plasticizer, silica, alumina, calcium carbonate, and hydroxide may be added to the resin of the substrate 1 as necessary. Inorganic powder such as aluminum, wood powder, filler such as glass fiber, lubricant, mold release agent, antistatic agent, colorant and the like can be added. As the resin, a resin colored by adding a colorant may be used depending on the application. The thickness of the substrate 1 is not particularly limited and is selected according to the application of the substrate.

The intermediate layer 2 provided on the one surface 1a of the base material 1 is a member that improves the adhesion between the substrate 1 and the resin cured layer 3, and is a known heat-sealable adhesive, pressure-sensitive adhesive, or ultraviolet curable resin, A thermosetting resin can be used. For example, as the adhesive layer, vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl chloride vinyl acetate resin, acrylic resin, butyral resin, epoxy resin, polyester resin, polyurethane resin, acrylic adhesive, rubber adhesive, silicone adhesive Examples thereof include adhesives and urethane-based adhesives. Further, a weather resistance improver may be added in order to impart an ultraviolet shielding function.

The ultraviolet curable resin as the intermediate layer 2 is a resin that is cured by ultraviolet rays (UV), and includes, for example, acryl (meth)acrylate having an acryloyl group in the molecule, polycarbonate (meth)acrylate, urethane (meth)acrylate, epoxy ( Mixtures of monomers, oligomers, polymers, etc., such as (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, polybutadiene (meth)acrylates, silicone (meth)acrylates are used.

The UV-curable resin as the intermediate layer 2 is preferably added with an appropriate amount of a known photopolymerization initiator in order to smoothly cure the resin with UV irradiation. Examples of such a photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones and the like. Further, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as the photosensitizer.
The resin cured layer 3 provided on the intermediate layer 2 is a resin that is cured by heat, and examples thereof include a one-component or two-component reaction-curable polyurethane resin, an epoxy resin, a methylated melamine resin, and a silicone resin. To be These resins may be used alone or in a mixed composition of several kinds, or may be used in combination with the above-mentioned ultraviolet curable resin.

In the present embodiment, the intermediate layer 2 may contain inorganic fine particles having an average particle diameter of 10 nm or more and 100 nm or less in order to improve the adhesion between the base material 1 and the resin cured layer 3 and increase the Martens hardness. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide, antimony-doped tin oxide, complex oxides such as phosphorus-doped tin oxide, calcium carbonate, and the like. Talc, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like can also be used. You may use these inorganic fine particles in mixture of 2 or more types. Among the inorganic fine particles contained in the intermediate layer, it is preferable to use silicon oxide or aluminum oxide.

The inorganic fine particles preferably have an average particle diameter of 10 nm or more in order to increase the Martens hardness or contribute to the adhesion, and by maintaining the average particle diameter of 100 nm or less, the transparency of the resin cured layer can be maintained. it can. More preferably, the average particle size of the inorganic fine particles is 10 nm or more and 50 nm or less. The amount of the inorganic fine particles added varies depending on the type and particle size of the particles, but is 20 to 500 parts by weight, and more preferably 50 to 300 parts by weight, based on 100 parts by weight of the ultraviolet curable resin.
Further, the intermediate layer 2 may be added with a curing agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a lubricant or the like in order to improve various physical properties. In particular, in order to impart weather resistance, by adding an ultraviolet absorber or a light stabilizer, it becomes possible to effectively suppress discoloration or deterioration of the resin due to exposure to ultraviolet rays or wind and rain. The thickness of the intermediate layer is preferably in the range of 0.2 μm to 10 μm.

Next, the resin cured layer 3 provided on the intermediate layer 2 is obtained by applying, drying and curing a coating liquid satisfying the following requirements (A) to (C).
(A) A methylsiloxane resin comprising a combination of at least any one of bifunctional to tetrafunctional methylsiloxane structural units.
(B) Alumina nanoparticles having a carbon-carbon double bond in the modifying group structure.
(C) An alkoxysilane having a carbon-carbon double bond in the modifying group structure.

The methyl siloxane resin described under the requirement (A) is preferably a resin that cures a bifunctional, 2-3 functional, 2-4 functional, and further 3-4 functional alkoxysilane by heating. Further, those obtained by appropriately hydrolyzing and dehydrating and condensing these in a solution beforehand to appropriately oligomerize or polymerize are also preferably used. Examples of usable alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane Etc. Further, an alkoxysilane having a substituent whose terminal is an acroyl group or a metacroyl group is also preferably used. These resins may be used alone or as a mixed composition of several kinds, but it is more preferable that the unit structure having a methyl group is the main component. Examples of the olegomerized product include methyl silicone olegomers (Shin-Etsu Chemical Co., Ltd.; KR-500, KR-400).

The alumina nanoparticles having a carbon-carbon double bond in the modifying group structure described in the requirement of (B) have a median diameter D50 (particle diameter at which the relative particle amount is 50% when integrated in the particle size distribution) is 70 nm. It is preferably not more than 30 nm, more preferably not more than 30 nm. The surface of alumina nanoparticles is substituted with a hydrophobic or hydrophilic modifying group, and is uniformly dispersed in a solvent such as methyl ethyl ketone, ethyl acetate, butyl acetate, methyl ethyl isobutyl ketone, toluene, cyclohexanone, propylene glycol monomethyl ether, alcohol. Preferably. Further, a part of the modifying group has an acroyl group or a metacroyl group at the terminal, and when used together with a photoinitiator, it is irradiated with ultraviolet rays to promote a polymerization reaction and be fixed in the resin cured layer. The addition amount of the alumina nanoparticles having the carbon-carbon double bond in the modifying group structure described in the requirement of (B) is the same as that of the methylsiloxane resin described in the requirement of (A) in terms of solid content weight ratio. About 0.5 times to 2 times is preferable. If the amount is too small, the Martens hardness, which is a feature of the present invention, cannot be obtained, and if it is too large, the nanoparticles may be aggregated to impair the uniformity and flatness of the cured resin layer.

The alkoxysilane having a carbon-carbon double bond in the modifying group structure described in the requirement of (C) is an alkoxide of silicon or a siloxane having a silicon-oxygen bond, and at least one terminal thereof is an acroyl group or a metacroyl group. A compound having a modifying group as a group in its structure may be used as a monomer, or an oligomer which has undergone hydrolysis and dehydration condensation may be used. The alkoxide reacts with methyl siloxane resin and alumina nanoparticles, and the hydroxyl groups present on the surface of the substrate or the intermediate layer with carboxyl groups, etc., to enhance the cohesive force of the cured resin film and enhance the adhesion with the lower layer. be able to. Further, the acroyl group or the metacroyl group is used together with a photoinitiator and is irradiated with ultraviolet rays to promote a polymerization reaction to be fixed in the resin cured layer. The addition amount of the alkoxysilane having a carbon-carbon double bond in the modifying group structure described in the requirement of (C) is 3 with respect to the methylsiloxane resin described in the requirement of (A) in terms of solid content weight ratio. % To 20% is preferable. If it is too small, the cohesive force and adhesiveness of the cured resin layer are impaired, and if it is too large, the Martens hardness, which is a feature of the present invention, cannot be obtained.

It is preferable to add an appropriate amount of a known photopolymerization initiator to the coating liquid that gives the resin of the resin cured layer 3 in order to smoothly cure the resin with ultraviolet irradiation. Examples include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones and the like. Further, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as the photosensitizer. Further, in order to improve various physical properties, a curing agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a lubricant, etc. may be added. The film thickness of the resin cured layer is preferably 0.6 μm or more and 10 μm or less.

The intermediate layer 2 and the resin cured layer 3 of the substrate 100 with a resin cured layer are formed by applying a coating liquid prepared by dissolving or dispersing the respective precursors, monomers, additives, etc. in a solvent such as water, alcohol or an organic solvent. Coater, curtain flow coater, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, spin coater, micro gravure coater, etc. After coating on the substrate 1 by a known coating method, drying or curing by heating. By doing. If it is an ultraviolet curable resin, it is irradiated with ultraviolet light using a light source capable of irradiating light wavelengths that are sensitive to photopolymerization initiators and photoacid generators, and excimer lamps, high pressure mercury lamps, xenon lamps, metal halide lamps, etc. Can be used. In addition, in order to improve the adhesion to the lower layer when applying the coating liquid, corona treatment, low temperature plasma treatment, ion bombardment treatment, chemical treatment or the like may be performed as pretreatment.

Next, in the method for manufacturing the substrate 100 with a resin cured layer of the present embodiment, the surface of the resin cured layer 3 formed as described above is irradiated with Xe ₂ excimer light so that the surface is closer to the surface. The carbon component is decomposed and removed, and mineralization proceeds. As a result, the Xe ₂ excimer-irradiated region exhibits extremely high Martens hardness as a thin film, and is preferably at least 600 N/mm ² or more, more preferably 700 N/mm ² or more, further preferably 1,000 N/mm ^2. mm ² or more. Generally, Martens hardness of methylsiloxane resin was 80N / mm ² ~200N / mm ² approximately, by adding a metal oxide nanoparticles, we can achieve 200 N / mm ² or more, even higher at most 550 N / It is about mm ² . In the present embodiment, as a result of earnestly examining the material formulation and the Xe ₂ excimer irradiation treatment, it has been possible to achieve a very excellent surface hardness.

Here, the Xe ₂ excimer light is ultraviolet light having a wavelength of 172 nm, and the surface structure of the resin cured layer 3 is changed by irradiating the resin surface of the resin cured layer 3 formed as described above with Xe ₂ excimer light. You can Specifically, it is possible to specifically break the bond between the silicon atom and the carbon atom or the bond between the carbon atom and the carbon atom existing on the surface of the cured resin layer 3. Simultaneously with the breaking of such a bond, it reacts with oxygen atoms existing inside the resin or in the atmosphere around it, so that silicon has a composition close to that of silicon oxide and carbon is gasified by oxidation.
As a result of the above reaction, the surface of the resin cured layer 3 irradiated with Xe ₂ excimer light is mineralized, and the Martens hardness becomes hard, and at the same time, excellent scratch resistance or abrasion resistance is exhibited.

Xe ₂ excimer light is generally enclosing a xenon (Xe ₂ ) gas in a synthetic quartz tube and applying high-frequency power between external electrodes. The gas becomes an excimer molecule state due to a dielectric barrier discharge. When returning to the ground state, it refers to a gas that emits excimer light specific to the gas species. In the present embodiment, it is most suitable to use Xe ₂ excimer light having a radiant light wavelength of 172 nm, which is highly versatile and capable of stable discharge with high productivity, but other excimer light or lamp having a 185 nm radiant wavelength is used. Can also For example, it is possible to use krypton (Kr ₂ ) excimer light having an emission wavelength of 146 nm. Since excimer light is strongly absorbed by oxygen gas, it is effective to replace the irradiation atmosphere with nitrogen gas and adjust the oxygen concentration to 10% or less, and more preferably 6% or less, to the surface of the object to be irradiated with excimer light. To reach.

Here, on the surface of the resin cured layer 3 of the substrate 100 with a resin cured layer of the present embodiment, there can be a site having a different Martens hardness produced by varying the degree of irradiation treatment with Xe ₂ excimer light. As a manufacturing method in which the surface of the resin cured layer 3 has different Martens hardness, a photomask is set on the resin cured layer 3 when the surface of the resin cured layer 3 is irradiated with excimer light. Then, the surface of the resin cured layer 3 is subjected to Xe ₂ excimer light irradiation treatment through the photomask. By irradiating in this manner, the excimer light that has passed through the light-transmitting portion of the photomask modifies the surface of the resin cured layer 3, and the excimer light that is blocked by the light-shielding portion of the photomask is reflected by the resin cured layer 3. The surface is not modified. The material of the photomask substrate preferably has a transmittance of light having a wavelength of 172 nm of 60% or more, more preferably 70% or more, in order to allow excimer light to pass, and synthetic quartz can be generally used. It is more preferable to use a special-grade synthetic quartz having a higher transmittance in the vacuum ultraviolet light region, and the transmittance at a wavelength of 172 nm in this case is 85% to 90% or more. Further, as long as the transmittance at a wavelength of 172 nm is 60% or more, this is not a limitation, and magnesium fluoride, synthetic sapphire or the like may be used.

The light-shielding portion of the photomask has only to shield excimer light of 172 nm, and a chromium film or a laminated film of chromium oxide is usually used for durability and resolution, but the invention is not limited to this. The light-shielding portion of the photomask is formed in a pattern, the line width of the light-shielding pattern is 3 μm or more and 20 μm or less, more preferably 10 μm or more and 20 μm or less, and the repeating pitch of the light-shielding pattern is 23 μm or more and 300 μm or less. , And more preferably 50 μm or more and 150 μm or less.
The shape of the light shielding pattern formed on the surface of the resin cured layer 3 is not particularly limited, and may be a lattice pattern, a circular pattern, or a hexagonal (honeycomb) pattern described later.
It is preferable that the light-shielding portion of the photomask does not exceed 50% of the area of the photomask overlaid on the cured resin layer 3. Here, if the light-transmitting portion of the photomask is less than 50%, the area where the surface of the cured resin layer 3 has a hard Martens hardness becomes small, and excellent scratch resistance or abrasion resistance cannot be obtained. More preferably, the area of the transparent portion of the photomask is 60% or more.
The region where the Martens hardness is hardened by the Xe ₂ excimer irradiation treatment on the surface of the resin cured layer 3 is defined as a region (R), and the area formed by the region (R) continuously is less than 0.09 mm ² . Further, a portion of the surface of the cured resin layer 3 which is shielded during the Xe ₂ excimer irradiation treatment and which separates the region (R) is defined as a region (S). Martens hardness measured by indentation depth 0.1μm is more present in the cured resin layer surface area of less than 0.09mm ² 600N / m ² or more at a region (R) is continuously, each region ( R) is separated into a region (S) having a Martens hardness of 200 N/m ² or more smaller than that of the region (R).

As a result of irradiating the surface of the resin cured layer 3 in a pattern as described above, the surface of the resin cured layer 3 of the present embodiment is a surface of a region (R) and a region (S) having different Martens hardness in a pattern. Have. Preferably region excimer light is irradiated (R) is Martens hardness 600N / mm ² or more through a photomask, more preferably 700 N / mm ² or more, more preferably 1,000 N / mm ² or more is there. The area (S) not exposed to the excimer light through the photomask preferably has a Martens hardness of 200 N/m ² or more, which is smaller than that of the area (R), more preferably 300 N/mm ² or more, and further preferably 400 N/m ^2. mm ² or more.

The region (R) and the region (S) provided on the surface of the resin cured layer 3 are overlapped with a photomask and irradiated with excimer light, and then the photomask is removed and then the excimer light is applied to the entire surface of the resin cured layer 3 again. Irradiation may be performed, and as a result, a predetermined Martens hardness may be obtained.

In order to confirm the regions (R) and the regions (S) having different Martens hardness, the 300 μm square regions in the surface direction of the resin cured layer 3 are vertically and horizontally pushed at intervals of 1 μm and the Martens hardness is 0.1 μm. It can be confirmed by measuring the hardness and mapping the Martens hardness when, for example, a grid pattern is formed on the surface of the resin cured layer 3 in FIG. In FIG. 3, reference numeral H1 is the width of the light shielding portion, and reference numeral H2 is the width of the transparent portion.

The Martens hardness is expressed by the following formula (1) using the maximum load (a) and the surface area (b) of the indenter from the indentation depth at that time when the diamond indenter is pressed into the sample surface with the maximum load (a). Calculate to.
Martens hardness = a/b (1)
The Martens hardness is a value measured according to the method described in ISO14577. In the present embodiment, the indentation depth is measured in the nano-range with a depth of 0.1 μm, and one measurement is considered to represent the hardness of a region having a diameter of approximately 1 μm.
In the present embodiment, the region (R) and the region (S) having different Martens hardnesses are made to coexist on the surface of the resin cured layer 3, so that it is possible to achieve both excellent scratch resistance and wear resistance and excellent toughness. And

The resin-cured layer-provided substrate 100 of the present embodiment has a ratio Y/of the carbon atom content rate X (at %) and the silicon atom content rate Y (at %) in the region of 10 nm in the depth direction measured from the resin cured layer 3 side. X is 2.0 or more, and Y/X in the region of 1500 nm in the depth direction is 1.5 or less. By providing such a chemical composition, the substrate 100 with a cured resin layer of the present embodiment can have excellent hardness, scratch resistance, and abrasion resistance.
The above chemical composition uses the carbon atom content rate X (at %) and the silicon atom content rate Y (at %) when energy dispersive X-ray spectroscopy is performed on the sample surface under the condition of an acceleration voltage of 20 kV. It is calculated according to the following equation (2).
Silicon/carbon ratio=Y/X (2)

[Example 1]
A substrate 1 having a thickness of 100 μm and a biaxially stretched polyester film (Toyobo Co., Ltd.; A4100) was coated with a coating solution having the following formulation mixed as an intermediate layer 2 by a gravure method, dried at 60° C., and a high pressure mercury lamp was used. A film having a thickness of 6 μm was formed by irradiating with ultraviolet rays of 600 mJ/cm ² .
Next, the intermediate layer 2 is formed by applying a coating liquid containing the following formulation on one surface of the substrate 1.
50 parts by weight of pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd.; A-TMMT),
50 parts by weight of tris(2-acryloxyethyl) isocyanurate (Shin-Nakamura Chemical Co.; A-9300-1CL),
Acrylic group-containing alkoxysilane (Shin-Etsu Chemical; KR-513) 10 parts by weight,
100 parts by weight of colloidal silica (Nissan Chemical Industry; MIBK-AC-2140Z),
Photopolymerization initiator (BASF Japan; IRGACURE 184) 4 parts by weight,
UV absorber (BASF Japan; TINUVIN400) 6 parts by weight,
3 parts by weight of hindered amine light stabilizer (BASF Japan; TINUVIN 292),
Methyl isobutyl ketone 40 parts by weight

Further, a coating solution obtained by mixing the following formulations as a resin cured layer 3 was applied onto the intermediate layer 2 by a gravure method, dried at 80° C., cured at room temperature for 12 hours, and further exposed to ultraviolet rays of 600 mJ/at a high pressure mercury lamp. It was formed with a film thickness of 2 μm by irradiation with cm 2.
80 parts by weight of methyl silicone oligomer (Shin-Etsu Chemical; KR-500),
20 parts by weight of methyl silicone oligomer (Shin-Etsu Chemical; KR-400),
Acrylic group-containing alkoxysilane (Shin-Etsu Chemical Co., Ltd.; KBM-503) 10 parts by weight Nano-alumina slurry (CIK Nanotech; particle size 30 nm, MIBK dispersion) 100 parts by weight,
3 parts by weight of curing catalyst (Shin-Etsu Chemical; D-20),
Photopolymerization initiator (BASF Japan; IRGACURE 184) 4 parts by weight,
Methyl isobutyl ketone 100 parts by weight

Subsequently, nitrogen gas was flowed around the substrate 1 obtained above to make a nitrogen atmosphere having an oxygen concentration of 1% or less, and then Xe ₂ excimer light was irradiated from above the resin cured layer. The irradiation amount of excimer light on the surface of the resin cured layer was such that it was 6000 mJ/cm ² when measured with an ultraviolet integrating illuminometer UIT-150-A/VUV-S172 manufactured by Ushio Inc. As described above, the substrate 100 with a cured resin layer was produced.
Subsequently, when the Martens hardness was measured with a pushing force of 0.5 N/mm ² using a nano indenter, it was 820 N/mm ² .

[Example 2]
In the same manner as in Example 1, the resin cured layer 3 was formed on the substrate 1 with the intermediate layer 2 interposed therebetween. Then, as shown in FIGS. 4 and 5, a photomask made of synthetic quartz having a chrome light-shielding portion in a lattice pattern is used, the photomask is installed with a gap of 100 μm, and nitrogen gas is flowed to generate nitrogen having an oxygen concentration of 1% or less. After setting the atmosphere, Xe ₂ excimer light was irradiated from above the photomask.
At this time, the width H1 of the light-shielding portion was 20 μm, the width H2 of the light-transmitting portion was 130 μm, and the pattern pitch was 150 μm. The same pattern pitch was used in the vertical and horizontal directions in the surface of the resin cured layer 3. The irradiation amount of the excimer light on the surface of the resin cured layer 3 was such that it was 6000 mJ/cm ² when measured by a UV integration illuminometer UIT-150-A/VUV-S172 manufactured by Ushio Inc. As described above, the substrate 100 with a resin cured layer was formed.
Further, when the Martens hardness was measured at a pitch of 1 μm using a nano indenter so that the indentation depth was 0.1 μm, the region (R) was 810 N/mm ² , and the region (S) was 540 N/mm ^2. Met.

[Example 3]
In the same manner as in Example 1, the resin cured layer 3 was formed on the substrate 1 with the intermediate layer 2 interposed therebetween. Then, as shown in FIG. 6, a synthetic quartz photomask having a chrome light shielding portion having a circular pattern is used, and Xe ₂ excimer light is irradiated from above the photomask to prepare a substrate 100 with a resin cured layer. did. At this time, the width H1 of the light-shielding portion was 15 μm, the width H2 of the light-transmitting portion was 205 μm, and the pattern pitch was 220 μm, and the same pattern pitch was used in the vertical and horizontal directions within the surface of the resin cured layer.

[Example 4]
In the same manner as in Example 1, the resin cured layer 3 was formed on the substrate 1 with the intermediate layer 2 interposed therebetween. Then, as shown in FIG. 7, a synthetic quartz photomask having a hexagonal (honeycomb-shaped) pattern of chrome light-shielding portions was used, and Xe ₂ excimer light was radiated from above the photomask to form a resin-cured layer. The substrate 100 was produced. At this time, the width H1 of the light-shielding portion was 10 μm, the width H2 of the light-transmitting portion was 110 μm, and the pattern pitch was 120 μm.

[Example 5]
A substrate 100 with a cured resin layer was produced in the same manner as in Example 1 except that the cured resin layer 3 was changed. The cured resin layer 3 is formed by applying a coating solution containing the following formulation by a gravure method, drying it at 80° C., curing it at 150° C. for 1 hour, and further irradiating it with ultraviolet rays of 600 mJ/cm ² with a high pressure mercury lamp. It was formed with a thickness of 2 μm.
Methyl silicone oligomer (Shin-Etsu Chemical; KR-500) 80 parts by weight Methyl silicone oligomer (Shin-Etsu Chemical; KR-400) 20 parts by weight Acrylic group-containing alkoxysilane (Shin-Etsu Chemical; KBM-503) 10 parts by weight Nano-alumina slurry (CIK Nanotech; particle size 30 nm, MIBK dispersion) 200 parts by weight Curing catalyst (Shin-Etsu Chemical; D-20) 3 parts by weight Photopolymerization initiator (BASF Japan; IRGACURE184) 6 parts by weight Methyl isobutyl ketone 100 parts by weight

Subsequently, nitrogen gas was flowed around the substrate obtained above to make a nitrogen atmosphere having an oxygen concentration of 1% or less, and then Xe2 excimer light was irradiated from above the resin cured layer 3. The irradiation amount of the excimer light on the surface of the resin cured layer 3 was such that it was 6,000 mJ/cm ² when measured with an ultraviolet integrating illuminometer UIT-150-A/VUV-S172 manufactured by Ushio Inc. As described above, the substrate 100 with a cured resin layer was produced.
When the Martens hardness was measured using a nano indenter at a pushing load of 0.5 N/mm ² , it was 1010 N/mm ² .

[Example 6]
In the same manner as in Example 5, the resin cured layer 3 was formed on the substrate 1 with the intermediate layer 2 interposed therebetween. Then, on the cured resin layer 3, a photomask made of synthetic quartz having a chrome light shielding portion having a lattice pattern shown in FIG. 4 was used, the photomask was placed with a gap of 100 μm, and nitrogen gas was flowed to obtain an oxygen concentration of 1 % Nitrogen or less, and then Xe ₂ excimer light was irradiated from above the photomask.
At this time, the width H1 of the light-shielding portion was 20 μm, the width H2 of the light-transmitting portion was 130 μm, and the pattern pitch was 150 μm. The same pattern pitch was used in the vertical and horizontal directions in the surface of the resin cured layer 3. The irradiation amount of the excimer light on the surface of the resin cured layer 3 was such that it was 6000 mJ/cm ² when measured by a UV integration illuminometer UIT-150-A/VUV-S172 manufactured by Ushio Inc. As described above, the substrate 100 with a cured resin layer was produced.
When the Martens hardness was measured using a nano indenter at a pitch of 1 μm so that the indentation depth was 0.1 μm, the region (R) was 1010 N/mm ² , and the region (S) was 620 N/mm ^2. It was

[Comparative Example 1]
A substrate 100 with a resin cured layer was produced in the same manner as in Example 1 except that the irradiation amount of Xe ² excimer light on the resin cured layer 3 was 2000 mJ/cm ² .
[Comparative example 2]
A resin cured layer-coated substrate 100 was produced in the same manner as in Example 2 except that the irradiation amount of Xe ² excimer light on the resin cured layer 3 was set to 2000 mJ/cm ² .
[Comparative Example 3]
A substrate 100 with a resin cured layer was produced in the same manner as in Example 5 except that the irradiation amount of Xe ₂ excimer light on the resin cured layer 3 was 2000 mJ/cm ² .
[Comparative Example 4]
A substrate 100 with a resin cured layer was produced in the same manner as in Example 6 except that the irradiation amount of Xe ² excimer light on the resin cured layer 3 was 2000 mJ/cm ² .
The evaluation items and evaluation criteria of the resin cured layer-provided substrate 100 produced in Examples 1 to 6 and Comparative Examples 1 to 4 are shown below.

<Steel wool scratch resistance test>
After the steel wool (Bonster #0000) was reciprocated 20 times on the surface of the resin cured layer 3 under a load of 300 g/cm 2, the scratch was visually evaluated. In the evaluation, no scratches were excellent: ⊚, and thin scratches were good: ◯.

<Pencil hardness test>
A pencil hardness test according to JIS-K5600-5-4 was performed on the surface of the resin cured layer 3. The pencil hardness of F or higher was regarded as acceptable.

<Taber wear test>
A Taber abrasion test was performed on the surface of the resin cured layer 3 using CS-10F as an abrasion wheel according to the method specified in JIS R 3212. The conditions of the Taber abrasion test are 1000 rotations of the wear wheel, 60 rpm of the wear wheel rotation speed, and 500 gf load load of the wear wheel. Before and after the Taber abrasion test, the haze was measured on the surface of the cured resin layer, and the average value was calculated. The haze measurement points are four points on the surface. The haze was measured using a haze meter NDH-7000SP manufactured by Nippon Denshoku Industries Co., Ltd. according to the method specified in JIS K7136. Then, the haze change (ΔHz) before and after the Taber abrasion test was obtained by subtracting the haze before the Taber abrasion test from the haze after the Taber abrasion test. When ΔHz was 2.0% or less, it was evaluated as excellent: ◎, when ΔHz was 3.0% or less, it was evaluated as good: ◯, and when ΔHz was 5.0% or more and less than 6.0, it was evaluated as somewhat poor: Δ.

<Weather resistance test>
Irradiance 60W/m2 (300-400nm) by a xenon weatherometer for a substrate with a resin cured layer, tank temperature: 40°C, tank humidity: 50%, black panel temperature: 60°C, test cycle: light irradiation 102 minutes /Light irradiation + water spraying and left for 2000 hours in an environment of 18 minutes. After taking out, the surface of the cured resin layer was observed under a microscope to determine the presence or absence of cracks in the cured resin layer. Appropriate for no cracks: ◯.
Table 1 shows the evaluation results of each example and each comparative example.

In Examples 1 to 6, the surface of the resin cured layer 3 was made inorganic by setting the Xe ₂ excimer light irradiation amount to the resin cured layer 3 to 6000 mJ/cm ^2, and the depth measured from the resin cured layer 3 side. The ratio Y/X of the carbon atom content rate X (at %) to the silicon atom content rate Y (at %) in the region of 10 nm in the direction is 2.0 or more, and the Y/X in the region of 1500 nm in the depth direction is 1. Since it is 5 or less, the steel wool scratch resistance and taper wear resistance are good or excellent (the evaluation of the steel wool scratch resistance test and the taper wear test is ◯ or ⊚).
On the other hand, in Comparative Examples 1 to 4 in which the amount of Xe ₂ excimer light irradiation to the resin cured layer 3 was 2000 mJ/cm ² , the ratio Y/X in the region of 10 nm in the depth direction was less than 2.0. Poor scratch resistance and taper wear resistance.

Here, the resin cured layer 3 that constitutes the substrate 100 with a resin cured layer of Examples 1 to 4 has the above-described requirement (A) (at least one of the bifunctional, trifunctional, and tetrafunctional functions). 100 parts by weight of a coating liquid (methyl silicone oligomer) satisfying a methyl siloxane resin composed of a combination of methyl siloxane structural units), and the requirement (B) (alumina nanoparticles having a carbon-carbon double bond in the modifying group structure). The coating liquid (acrylic group-containing alkoxysilane) satisfying the above conditions contains 10 parts by weight. That is, the ratio (B/A) of the addition amount of the acrylic group-containing alkoxysilane and the addition amount of the methyl silicone oligomer is set to about 0.1 times. As in Examples 1 to 4, when the ratio (B/A) of the addition amount of the acrylic group-containing alkoxysilane and the addition amount of the methyl silicone oligomer of the resin cured layer 3 is less than 0.5 times, it is high. The value of Martens hardness cannot be obtained.

In contrast to Examples 1 to 4 as described above, the resin cured layer 3 constituting the substrate 100 with a resin cured layer of Examples 5 and 6 has a coating liquid (methyl silicone oligomer) satisfying the requirement (A). The coating liquid (acrylic group-containing alkoxysilane) containing 100 parts by weight and satisfying the requirement of (B) contains 200 parts by weight, and the ratio of the addition amount of the acrylic group-containing alkoxysilane and the addition amount of the methyl silicone oligomer (B/ A) is set to about 2.0 times. As described above, in Examples 5 and 6 in which the ratio (B/A) of the addition amount of the acrylic group-containing alkoxysilane and the addition amount of the methyl silicone oligomer of the resin cured layer 3 was 2.0 times, the high Martens hardness was obtained. Therefore, excellent evaluation can be obtained in both the steel wool scratch resistance test and the taper wear test (the steel wool scratch resistance test and the taper wear test are evaluated as ◎).

Further, in Example 6, the resin hardened layer 3 was provided with a chrome light shielding portion in a grid pattern and irradiated with Xe ₂ excimer light from above the resin hardened layer, whereby the surface of the resin hardened layer 3 had different Martens hardness. A region (R) and a region (S) are formed, the region (R) has a high Martens hardness of 1000 N/mm ² or more, and a small Martens hardness of about 400 N/mm ^{2 with} respect to this region (R) The region (S) can be formed, and even if an impact is applied to the surface of the resin cured layer 3, cracks are not easily generated, and excellent toughness can be obtained.
Therefore, the resin-cured layer-provided substrate 100 of Example 6 in which excellent toughness is obtained on the surface of the resin-cured layer 3 is excellent in scratch resistance and abrasion resistance, and has little weather-resistant surface deterioration even when left outdoors. Excellent (weatherability test evaluation is ◯).

(Modification)
8 is a cross-sectional view showing a configuration example of a decorative sheet according to a modified example of the embodiment of the present invention. The decorative sheet 20 of FIG. 8 includes a substrate 1, a printed layer 21 provided on one surface 1a of the substrate 1 with an adhesive layer, and an intermediate layer 2 provided on the printed layer 21 with an adhesive layer. And a cured resin layer 3 provided on the intermediate layer 2. In this decorative sheet 20, the intermediate layer 2 and the resin cured layer 3 are transparent, and the printed layer 21 can be visually observed from the resin cured layer 3 side. In this decorative sheet 20, the cured resin layer 3 can impart the scratch resistance, abrasion resistance, and weather resistance of the printed layer 21.

Further, the decorative sheet 20 shown in FIG. 8 may be read as a decorative plate. When the decorative board is used, the board 1 is a wood-based board 1. In the case of a decorative board, an upper resin may be provided between the printing layer 21 and the intermediate layer 2. The upper resin is composed of, for example, polyethylene (PE), polypropylene (PP) or polyethylene terephthalate (PET). The thickness of the upper resin is, for example, 50 μm or more and 125 μm or less. Thereby, the decorative board can be provided with scratch resistance, abrasion resistance and weather resistance.

Further, FIG. 9 is a cross-sectional view showing a configuration example of a vehicle window of a modified example according to the embodiment of the present invention. The vehicle window 30 of FIG. 9 includes a transparent plastic substrate 1A, a transparent intermediate layer 2 provided on the substrate 1A via an adhesive layer, and an intermediate layer 2A on the intermediate layer 2A via an adhesive layer. The resin cured layer 3A having transparency is provided. In this vehicle window 30, it is possible to visually observe from the resin cured layer 3A side to the inside of the substrate 1A. In this vehicle window 30, the resin cured layer 3A can give the substrate 1A scratch resistance, abrasion resistance and weather resistance.

1, 1A Substrate 1a One side of substrate 2, 2A Intermediate layer 3, 3A Resin cured layer 20 Decorative sheet 30 Vehicle window 100 Substrate with resin cured layer H1 Width H2 of light shielding part Width of transparent part

Claims (11)

Board,
A resin cured layer formed on at least one surface of the substrate,
The resin cured layer is obtained by drying and curing a coating liquid containing the following (A) to (C):
The ratio Y/X of the carbon atom content rate X (at %) and the silicon atom content rate Y (at %) in the region of 10 nm in the depth direction measured from the surface of the resin cured layer using X-ray photoelectron spectroscopy is A substrate with a cured resin layer, wherein Y/X in a region of 2.0 nm or more and 1500 nm in the depth direction is 1.5 or less.
(A) A methylsiloxane resin comprising a combination of at least any one of bifunctional to tetrafunctional methylsiloxane structural units.
(B) Alumina nanoparticles having a carbon-carbon double bond in the modifying group structure.
(C) An alkoxysilane having a carbon-carbon double bond in the modifying group structure. The substrate with a resin-cured layer according to claim 1, wherein the Martens hardness measured from the surface of the resin-cured layer with a pushing load of 0.5 mN is 600 N/m ² or more. More to the resin cured layer surface area of less than the area Martens hardness measured at a depth 0.1μm indentation from the surface of the cured resin layer is 600N / m ² or more (R) is continuously 0.09 mm ² The cured resin layer according to claim 1, wherein each region (R) exists and is separated into a region (S) having a Martens hardness of 200 N/m ² or more smaller than that of the region (R). Substrate with. The intermediate layer is provided between the substrate and the resin cured layer, and the intermediate layer is a mixture of an organic resin and a material containing silicon, and the intermediate layer is a mixture. Substrate with a cured resin layer. The resin-cured layer-attached substrate according to any one of claims 1 to 4, wherein the resin-cured layer has a thickness of 0.6 µm or more and 10 µm or less. The median diameter D50 of the alumina nanoparticles contained in the resin cured layer is 70 nm or less, and the resin cured layer-attached substrate according to any one of claims 1 to 5. A decorative sheet comprising the substrate with a resin cured layer according to claim 1. A decorative sheet comprising: the decorative sheet according to claim 7; and a base material having the decorative sheet bonded to at least one surface thereof. A vehicle window comprising the substrate with a resin-cured layer according to any one of claims 1 to 6. A step of applying a coating liquid containing the following (A) to (C) on at least one surface of the substrate, drying and curing to form a resin cured layer,
Installing a photomask on the resin cured layer,
A step of subjecting the surface of the resin cured layer to Xe ₂ excimer light irradiation through the photomask,
The base material of the photomask has a transmittance of light having a wavelength of 172 nm of 60% or more,
A light-shielding pattern is formed on the photomask,
The width of the light-shielding portion of the light-shielding pattern is 3 μm or more and 20 μm or less,
The method for producing a substrate with a resin cured layer, wherein the light-shielding pattern has a repeating pitch of 23 μm or more and 300 μm or less.
(A) A methylsiloxane resin comprising a combination of at least any one of bifunctional to tetrafunctional methylsiloxane structural units.
(B) Alumina nanoparticles having a carbon-carbon double bond in the modifying group structure.
(C) An alkoxysilane having a carbon-carbon double bond in the modifying group structure. The step of irradiating the surface of the resin cured layer with Xe ₂ excimer light through the photomask, and then irradiating with light having a wavelength of 400 nm or less with the photomask removed. Item 10. A method for manufacturing a substrate with a resin cured layer according to Item 10.

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