JP7027851B2 - Substrate with resin hardened layer and its manufacturing method - Google Patents

Description

The present invention relates to a substrate with a resin cured layer having excellent wear resistance, and a method for manufacturing the same.

Polycarbonate resin has excellent transparency, light weight, and high impact resistance, and has been widely applied and developed as window materials and structural materials for various buildings and automobiles.
However, it has the drawback of being significantly inferior to glass in terms of wear resistance, weather resistance, and chemical resistance. Therefore, a method of forming a hard coat layer having a function of covering these performances on polycarbonate (for example, Patent Document 1) has been proposed.
As such a hard coat layer, a method of laminating a base hard coat layer containing a hydrolyzed condensate of an organic silicon compound as a main component and a silicon oxide layer formed by a PE-CVD method on the base hard coat layer is used. There is.

Japanese Patent No. 5944069

However, when the hard coat layer is to be formed by the above method, the productivity is poor due to the slow film forming speed, or it is necessary to introduce both a wet coating device and a dry coating device. In that respect, there is a drawback that the manufacturing cost is high.
The present invention has been made to solve these drawbacks, and an object thereof is to provide a substrate with a resin cured layer having sufficient wear resistance even for a fragile material such as a polycarbonate resin. There is something in it.
Further, another object of the present invention is to provide a method for manufacturing a substrate with a resin cured layer, which can suppress deterioration of productivity and increase in manufacturing cost due to introduction of equipment.

In order to solve the above problems, the substrate with a resin cured layer according to an aspect of the present invention has a substrate and a resin cured layer on at least one surface of the substrate.
The Martens hardness when a load of 0.5 mN is applied to the surface of the resin cured layer from the normal direction is 150 N / mm ² or more and 800 N / mm ² or less, and the surface of the resin cured layer has an acceleration voltage of 20 kV. The relationship between the carbon atom content X (at%) and the silicon atom content Y (at%) when energy-dispersed X-ray spectroscopy is performed under the conditions of (1).
Y / X ≧ 2.0 ・ ・ ・ (1)

Further, in the substrate with a resin cured layer according to a certain aspect of the present invention, the substrate may contain an organic resin as a main component.
Further, in the substrate with a resin curing layer according to an aspect of the present invention, the resin curing layer may be a cured layer containing an ultraviolet curable resin or a thermosetting resin.
Further, in the substrate with a resin cured layer according to an aspect of the present invention, the resin cured layer may contain fine particles containing silicon oxide as a main component.
Further, in the substrate with a resin cured layer according to an aspect of the present invention, the film thickness of the resin cured layer may be 3 μm or more and 20 μm or less.

Further, the method for manufacturing a substrate with a resin-cured layer according to an aspect of the present invention includes a step of forming a resin-cured layer on at least one surface of the substrate and a step of applying Xe ₂ excima light irradiation treatment to the resin-cured layer. The cured resin layer after the light irradiation treatment satisfies the following requirements (a) and (b).
(A) The Martens hardness when a load of 0.5 mN is applied to the surface of the cured resin layer from the normal direction is 150 N / mm ² or more and 800 N / mm ² or less.
(B) The carbon atom content X (at%) and the silicon atom content Y (at%) when the surface of the resin cured layer is subjected to energy dispersion type X-ray spectroscopy under the condition of an acceleration voltage of 20 kV are expressed by the formulas. It is the relationship of (1).
Y / X ≧ 2.0 ・ ・ ・ (1)

According to a substrate with a resin cured layer according to an aspect of the present invention, it is possible to provide a substrate with a resin cured layer having sufficient wear resistance. Further, according to the method for manufacturing a substrate with a cured resin layer according to an aspect of the present invention, since a dry coating method such as a CVD method is not used when forming the cured resin layer, the productivity is deteriorated and the manufacturing cost due to the introduction of equipment is reduced. It is possible to provide a method for manufacturing a substrate with a resin cured layer, which can suppress the increase in the amount of the resin.

It is sectional drawing which shows an example of the laminated structure of the substrate with the resin hardened layer of a certain aspect of this invention. It is sectional drawing which shows an example of the laminated structure of the film laminate used for manufacturing the substrate with a resin cured layer of a certain aspect of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimensions, the ratio of the thickness of each layer, and the like may differ from the actual ones. Further, the embodiments shown below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention describes the materials, shapes, structures, etc. of the constituent parts as follows. It is not specific to things. The technical idea of the present invention may be modified in various ways within the technical scope specified by the claims described in the claims.

<Structure of substrate with resin cured layer>
FIG. 1 is a cross-sectional view showing a laminated structure in an embodiment of a substrate with a resin cured layer.
The substrate 100 with a resin curing layer of the present embodiment is a substrate with a resin curing layer having a resin curing layer 2 on at least one surface of the substrate 1. The substrate 1 may contain an organic resin as a main component. The main component here is the main component as weight. The Martens hardness when a load of 0.5 mN is applied to the surface of the resin cured layer 2 from the normal direction is 150 N / mm ² or more and 800 N / mm ² or less, and the surface of the resin cured layer has an acceleration voltage of 20 kV. The relationship between the carbon atom content X (at%) and the silicon atom content Y (at%) when energy dispersive X-ray spectroscopy is performed under the conditions is the relationship of the formula (1).
Y / X ≧ 2.0 ・ ・ ・ (1)
The substrate 100 with a resin cured layer of the present embodiment satisfies the hardness and chemical composition in a specific range shown below. By satisfying such physical property values, it becomes possible to provide the substrate 1 with excellent wear resistance.

<Hardness>
The substrate 100 with a resin cured layer of the present embodiment may satisfy the Martens hardness of 150 N / mm ² or more and 800 N / mm ² or less measured from the resin cured layer 2 side, but is preferably 200 N / mm ² or more and 600 N / mm. ² or less can be mentioned. By providing such a Martens hardness, it is possible to provide the substrate 1 with excellent wear resistance.
The Martens hardness is determined by the following formula (2) using the maximum load (A) and the surface area (B) of the indenter from the pressing depth at which the diamond indenter is pressed into the sample surface with a maximum load of 0.5 mN. Calculate as follows.
Martens hardness = A / B ... (2)
The Martens hardness in this embodiment is a value measured according to the method described in ISO14577. In order to equip the substrate 10 with the resin cured layer of the present embodiment with the above-mentioned Martens hardness, the composition, thickness and the like of the resin cured layer 2 may be appropriately adjusted.

<Chemical composition>
In the substrate 100 with the resin cured layer of the present embodiment, the ratio (silicon / carbon ratio) of the carbon atom content X (at%) and the silicon atom content Y (at%) measured from the resin cured layer 2 side is It suffices to satisfy 2.0 or more, but 2.5 or more is preferable.
By providing such a chemical composition, the substrate 1 can be provided with excellent wear resistance.
The chemical composition uses the carbon atom content X (at%) and the silicon atom content Y (at%) when energy dispersive X-ray spectroscopy is performed on the sample surface under the condition of an acceleration voltage of 20 kV. Calculate according to the following formula (3).
Silicon / carbon ratio = Y / X ... (3)
In order to provide the substrate 100 with the resin cured layer of the present embodiment with the above chemical composition, the composition, thickness and the like of the resin cured layer 2 may be appropriately adjusted, and specific conditions thereof will be described later.

Hereinafter, the composition, thickness, and the like of each layer constituting the substrate with the resin cured layer of the present embodiment will be described.
In the substrate 100 with a resin curing layer of the present embodiment, 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 the base material is molded by injection molding of the 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-based polymers such as polyvinyl chloride and polyvinylidene chloride; styrene-based resins such as polystyrene, acrylonitrile-styrene-based copolymer, and 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. Such as polyester resin; polycarbonate resin and the like can be mentioned.

Examples of the thermosetting resin include a one-component or two-component reaction-curable polyurethane resin and an epoxy resin. These resins may be used alone or in combination of two or more. Among these, polycarbonate has excellent impact resistance and transparency, and is preferably used.
In addition, various additives such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, calcium carbonate, aluminum hydroxide, etc. may be added to these resins as required. Inorganic powder, wood powder, fillers such as glass fiber, lubricants, mold release agents, antistatic agents, colorants and the like can be added.
As the injection resin, a resin colored by adding a colorant may be used as appropriate depending on the intended use. The thickness of the substrate 1 is not particularly limited and is selected according to the application of the substrate.

Here, for the purpose of improving the adhesion between the substrate 1 and the resin cured layer 2, an adhesive layer may be provided at the interface, and a known heat-sealing adhesive or pressure-sensitive adhesive can be used. For example, the adhesive layer includes vinyl acetate resin, ethylene vinyl acetate copolymer resin, vinyl chloride resin, acrylic resin, butyral resin, epoxy resin, polyester resin, polyurethane resin, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, and silicon-based adhesive. Examples include adhesives and urethane adhesives. Further, a weather resistance improving agent may be added to impart the ultraviolet shielding function. The thickness of the adhesive layer is preferably in the range of 0.5 μm to 10 μm.

The resin cured layer 2 is a layer provided to impart mechanical strength such as abrasion resistance to the substrate 1, and is made of a cured product of a resin composition containing an ultraviolet curable resin or a thermosetting resin. Regarding the types of the ultraviolet curable resin or the thermosetting resin used for the resin curable layer 2, the above-mentioned Martens hardness and the carbon atom content X (at%) and the silicon atom content Y (at%) It may be appropriately set so that the ratio can be satisfied, and is not particularly limited as long as these physical property values can be satisfied.

In the present embodiment, the ultraviolet curable resin means a resin that is cured by ultraviolet rays (UV). A typical resin that undergoes a radical polymerization reaction is a resin having an acryloyl group in the molecule, and is an acrylic (meth) acrylate, a polycarbonate (meth) acrylate, a urethane (meth) acrylate, an epoxy (meth) acrylate, or a polyester (meth). Mixtures of monomers such as acrylates, polyether (meth) acrylates, polybutadiene (meth) acrylates, silicone (meth) acrylates, oligomers, polymers and the like are used.

The silicone (meth) acrylate can be obtained by modifying a silicone having a polysiloxane bond in the main chain with (meth) acrylic acid, and by containing this resin, silicon having a chemical composition of the formula (3) can be obtained. The content rate can be improved. These resins may be used in a single composition, in a mixed composition of several kinds, or in combination with a thermosetting resin described later.
It is preferable to add an appropriate amount of a known photopolymerization initiator in order to smoothly cure the resin with ultraviolet irradiation. Examples of such a photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones and the like.
Further, as a photosensitizer, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used.

In the present embodiment, the thermosetting resin means a resin that is cured by heat. Above all, in order to improve the silicon content of the chemical composition of the formula (3), it is preferable to use a silicone-based thermosetting resin, and silicon having 2 to 4 functionalities, more preferably 3 to 4 functionalities. Those in which the alkoxide is cured by heating are preferable.
Further, those obtained by appropriately hydrolyzing and dehydrating and condensing these in a solution in advance to be appropriately oligomerized or polymerized are also preferably used.

Examples of usable silicon alkoxides 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 And so on. These resins may be used in a single composition, in a mixed composition of several kinds, or in combination with the above-mentioned ultraviolet curable resin.
Here, when the resin cured layer 2 is laminated on the substrate 1 by transfer, it is preferably made of a resin that is in a tack-free state before transfer and can be crosslinked by irradiating the substrate 1 with ultraviolet rays. The reason for cross-linking after transfer is that when the film laminate 10 is used in injection molding or a thermal transfer method, if it is cross-linked in advance, cracks are likely to occur during stretching of the transfer, resulting in poor appearance.

In the present embodiment, it is preferable that the resin cured layer 2 contains inorganic fine particles having an average particle diameter of 10 nm or more and 100 nm or less. Examples of the inorganic fine particles include oxides such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide and antimony pentoxide, composite oxides such as antimony-doped tin oxide and phosphorus-doped tin oxide, and calcium carbonate. , Talk, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like can also be used. Two or more kinds of these inorganic fine particles may be mixed and used.

Among these, it is preferable to use silicon oxide. By containing silicon oxide, the silicon / carbon ratio of the chemical composition of the formula (3) can be improved. Silicon oxide may be the main component of the fine particles. The main component here is the main component as weight.
The average particle size of the inorganic fine particles in the present invention is the average particle size of the fine particles measured by the dynamic light scattering method, and is 50% particle size (d50 median size) when the particle size distribution is expressed as a cumulative distribution. Is. For example, it can be measured by a commercially available device called Nanotrac UPA-EX150 manufactured by Microtrac, USA.

By adding the inorganic fine particles, the fine particles fill the voids in the cured resin layer, so that the hardness is increased. Further, by setting the average particle size of the inorganic fine particles to 10 nm or more, the production of the fine particles becomes easy, and by setting the average particle size to 100 nm or less, the light transmittance of the resin cured layer can be imparted. 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, more preferably 50 to 300 parts by weight, based on 100 parts by weight of the ultraviolet curable resin.

Further, in order to improve various physical properties, a curing agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a lubricant and the like may be added. In particular, by adding an ultraviolet absorber or a light stabilizer in order to impart weather resistance, it is possible to effectively suppress discoloration and deterioration of the resin due to exposure to ultraviolet rays and wind and rain.
The thickness of the cured resin layer 2 may be appropriately set within a range in which the above-mentioned hardness and chemical composition can be satisfied according to the composition of the cured resin layer 2, but is usually 3 to 20 μm, preferably 5 to 15 μm. Can be mentioned. By satisfying such a thickness, it becomes possible to more effectively provide excellent wear resistance while satisfying the above-mentioned hardness and chemical composition.

As the support film 3, for example, a substrate such as a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a triacetyl cellulose film, a polycarbonate film, a nylon film, a cellophane film, or an acrylic film can be used. The thickness of the support film 3 that can be used is 25 μm to 150 μm, preferably 38 μm to 50 μm.
The release layer 4 is most important to be peelable from the resin cured layer 2, and is also required to have heat resistance, solvent resistance and stretchability. Therefore, the release layer 4 is preferably a curable system, and for example, a cured product such as a melamine resin, a polyolefin resin, a urethane resin, or cellulose acetate can be used. As the curing cross-linking system, epoxy resins / amines, alkyd resins / acid catalysts, acrylic polyol resins / isocyanate compounds, and acrylic oligomers / photoinitiators can be used. The thickness of the release layer 4 is not particularly limited, but is preferably 0.1 μm to 3 μm.

<Manufacturing method of substrate with resin cured layer>
The method for manufacturing the substrate with the resin cured layer of the present embodiment is not particularly limited, but for example, a film laminate in which each layer other than the substrate is laminated in advance is prepared, and each layer is used on the substrate using the film laminate. There is a method of laminating.
FIG. 2 is a cross-sectional view showing an example of a laminated structure of a film laminate used in the method for manufacturing a substrate with a resin cured layer according to an aspect of the present invention.
The film laminate 10 of the present embodiment is a film laminate having a release layer 4 and a resin curing layer 2 in this order on at least one surface of the support film 3.

The manufacturing method of the present embodiment includes a step of forming the resin cured layer 2 on at least one surface of the substrate 1 and a step of applying Xe ₂ excimer light irradiation treatment to the resin cured layer 2.
Then, in the step of applying the Xe ₂ excimer light irradiation treatment to the resin cured layer 2, the resin cured layer 2 after the light irradiation treatment was subjected to the Xe ₂ excimer light irradiation treatment so as to satisfy the following requirements (a) and (b).
(A) The Martens hardness when a load of 0.5 mN is applied to the surface of the resin cured layer 2 from the normal direction is 150 N / mm ² or more and 800 N / mm ² or less.
(B) The carbon atom content X (at%) and the silicon atom content Y (at%) when the surface of the resin cured layer 2 is subjected to energy dispersion type X-ray spectroscopy measurement under the condition of an acceleration voltage of 20 kV. It is the relationship of the equation (1).
Y / X ≧ 2.0 ・ ・ ・ (1)

Specifically, after laminating a film laminate 10 in which at least the release layer 4 and the resin cured layer 2 are laminated in this order on the support film 3, the support film 3 and the release layer 4 are laminated. The substrate 100 with a resin-cured layer of the present invention can be manufactured by a method of peeling and curing the resin-cured layer 2 by irradiating with ultraviolet rays.
Further, in the method for manufacturing a substrate with a cured resin layer of the present embodiment, the cured resin layer 2 formed as described above may be irradiated with Xe ₂ excimer light.
Here, the Xe ₂ excimer light is ultraviolet light having a wavelength of 172 nm, and the surface structure of the cured layer can be changed by irradiating the surface of the resin cured layer 2 formed as described above with the Xe ₂ excimer light. can. Specifically, it is possible to specifically cleave the bond between the silicon atom and the carbon atom existing on the surface of the hardened layer or the bond between the carbon atom and the carbon atom. By performing such a treatment, the silicon / carbon ratio of the chemical composition of the formula (3) can be improved.

(Example 1)
Acrylic melamine resin (Hitachi Kasei Polymer Co., Ltd .; Tessfine) is formed on a biaxially stretched polyester film (Mitsubishi Plastics Co., Ltd .; G440E50) having a thickness of 50 μm, which is the support film 3, to a thickness of Dry 0.2 μm by the gravure method. A release layer 4 was obtained. Here, "Dry 0.2 μm thickness" means that the thickness becomes 0.2 μm after drying. Similarly, the "Dry XX μm thickness" described below means that the thickness becomes XX μm after drying.

Then, on the release layer 4,
・ Acrylic acrylate (DIC; RC29-120) 20 parts by weight ・ Silicone acrylate (Shinetsu Chemical Industry; KR-513) 80 parts by weight ・ Colloidal silica (Nissan Chemical Industry; MEK-ST-ZL) 150 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight and 50 parts by weight of methylisobutylketone were stirred and mixed, and the ultraviolet curable resin composition was applied by a gravure method to a thickness of 10 μm to form a resin cured layer 2.

Next, an ink obtained by dissolving vinyl acetate resin (Nisshin Kagaku Kogyo Co., Ltd .; Solvine A) in toluene and methyl ethyl ketone as an adhesive layer was applied onto the resin cured layer 2 by a gravure method to a thickness of Dry 1 μm, and the film laminate 10 was applied. Got
Further, the film laminate 10 was set in a mold of an injection molding machine, and injection molding was performed with a polycarbonate resin to be a substrate 1. The obtained molded product is in a state where the support film 3 and the release layer 4 are removed, and the resin cured layer surface of the molded product is completely cured by irradiating the surface of the cured resin layer with ultraviolet rays having an exposure amount of 1000 mJ / cm ² with a high-pressure mercury lamp of 120 W / cm. I let you. Then, the resin cured layer was irradiated with Xe ₂ excimer light of 5000 mJ / cm ² to obtain a substrate 100 with a resin cured layer.

(Example 2)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Example 2 was obtained by the same procedure as in Example 1. rice field.
・ Acrylic acrylate (DIC; RC29-120) 20 parts by weight ・ Silicone acrylate (Shin-Etsu Chemical; KR-513) 80 parts by weight ・ Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 50 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight, 50 parts by weight of methyl isobutyl ketone

(Example 3)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Example 3 was obtained by the same procedure as in Example 1. rice field.
・ Acrylic acrylate (DIC; RC29-120) 50 parts by weight ・ Silicone acrylate (Shin-Etsu Chemical; KR-513) 50 parts by weight ・ Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 300 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight, 50 parts by weight of methyl isobutyl ketone

(Example 4)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Example 4 was obtained by the same procedure as in Example 1. rice field.
・ Acrylic acrylate (DIC; RC29-120) 80 parts by weight ・ Silicone acrylate (Shin-Etsu Chemical; KR-513) 20 parts by weight ・ Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 150 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight, 50 parts by weight of methyl isobutyl ketone

(Comparative Example 1)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Comparative Example 1 was obtained by the same procedure as in Example 1. rice field.
・ Acrylic acrylate (DIC; RC29-120) 100 parts by weight ・ Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 150 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight ・ Methyl isobutyl ketone 50 parts by weight

(Comparative Example 2)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Comparative Example 2 was obtained by the same procedure as in Example 1. rice field.
-Silicone acrylate (Shin-Etsu Chemical; KR-513) 100 parts by weight-Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight-Methyl isobutyl ketone 50 parts by weight

(Comparative Example 3)
The ultraviolet curable resin composition as the resin curable layer 2 used in Example 1 was changed as follows, and the substrate 100 with the resin curable layer of Comparative Example 3 was obtained by the same procedure as in Example 1. rice field.
・ Acrylic acrylate (DIC; RC29-120) 100 parts by weight ・ Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 400 parts by weight ・ Photopolymerization initiator (BASF Japan; Irgacure 184) 4 parts by weight ・ Methyl isobutyl ketone 50 parts by weight The evaluation items and evaluation criteria of the substrate with the resin cured layer obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are shown below.

(hardness)
A diamond indenter is pushed into the surface of the resin hardened layer of the substrate with a resin hardened layer with a load of 0.5 mN from the normal direction, and the maximum load (A) and the surface area (B) of the indenter are calculated from the pushing depth at that time. Using the method described in ISO14577, the Martens hardness was calculated according to the following formula (2). The Martens hardness of 150 N / mm ² or more and 800 N / mm ² or less was regarded as "appropriate".
Martens hardness = A / B ... (2)

(Chemical composition)
Carbon atom content X (at%) and silicon atom content Y (at%) when energy-dispersed X-ray spectroscopy is performed on the surface of the resin-cured layer of the substrate with the resin-cured layer under the condition of an acceleration voltage of 20 kV. ) Was used to calculate the silicon / carbon ratio according to the following formula (3).
Silicon / carbon ratio = Y / X ... (3)

(Abrasion resistance)
A tabor wear test was performed using CS-10F for the wear wheel under the conditions of 1000 rotations, 60 rpm, and a load of 500 g. The haze was measured at four locations on the substrate with the resin cured layer before and after the Taber wear test according to the method described in JIS K7136 using a haze meter (NDH-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the average value was calculated. The haze difference (ΔHz) before and after the tabor wear test was obtained by subtracting the haze before the tabor wear test from the haze after the tabor wear test. The haze difference (ΔHz) of 2.0% or less was regarded as “appropriate”.
Table 1 shows the evaluation results of each Example and each Comparative Example.

When the hardness, chemical composition and wear resistance of the substrates with the resin cured layer obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated, the Martens hardness was 150 N / mm ² or more and 800 N / mm ² or less, and silicon. In Examples 1 to 4 having a / carbon ratio of 2.0 or more, wear resistance was good, and ΔHz was 2.0% or less in all cases.
On the other hand, in Comparative Example 1 in which the silicon / carbon ratio was as low as 1.5, the wear resistance was not improved and ΔHz was 4.5%. Further, in Comparative Example 2 in which the Martens hardness was as low as 130 N / mm ² , the wear resistance was not improved and ΔHz was 7.8%. Further, in Comparative Example 3 in which the Martens hardness was as high as 1040 N / mm ² , the wear resistance was not improved and ΔHz was 3.5%.

According to the substrate with a resin cured layer of the present embodiment, it is possible to provide a substrate with a resin cured layer having sufficient wear resistance even for a perishable material such as a polycarbonate resin.
Further, according to the method for manufacturing a substrate with a cured resin layer of the present embodiment, dry coating such as a CVD method is not used when forming a cured resin layer as a hard coat, so that productivity is deteriorated or equipment is introduced. It is possible to suppress an increase in manufacturing cost.
Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and is included in the present invention even if there are changes within a range that does not deviate from the gist of the present invention.

1 Substrate 2 Resin cured layer 3 Support film 4 Release layer 10 Film laminate 100 Substrate with resin cured layer

Claims (12)

It has a substrate and a resin cured layer on at least one surface of the substrate.
The Martens hardness when a load of 0.5 mN is applied to the surface of the resin cured layer from the normal direction is 200 N / mm ² or more and 800 N / mm ² or less, and the surface of the resin cured layer is accelerated. It can be seen that the relationship between the carbon atom content X (at%) and the silicon atom content Y (at%) when energy-dispersed X-ray spectroscopy is performed under the condition of 20 kV is the relationship of the formula (1). A characteristic substrate with a cured resin layer.
Y / X ≧ 2.0 ・ ・ ・ (1) The substrate with a resin curing layer according to claim 1, wherein the substrate contains an organic resin as a main component. The substrate with a resin cured layer according to claim 1 or 2, wherein the resin cured layer is a cured layer containing an ultraviolet curable resin or a thermosetting resin. The substrate with a resin-cured layer according to any one of claims 1 to 3, wherein the resin-cured layer contains fine particles containing silicon oxide as a main component. The resin cured layer is characterized by containing fine particles containing silicon oxide as a main component within a range of 150 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the resin constituting the cured resin layer. The substrate with a resin cured layer according to any one of claims 1 to 3. The substrate with a resin-cured layer according to any one of claims 1 to 5 , wherein the film thickness of the resin-cured layer is 3 μm or more and 20 μm or less. The substrate with a resin-cured layer according to any one of claims 1 to 5, wherein the film thickness of the resin-cured layer is 10 μm or more and 20 μm or less. The Martens hardness when a load of 0.5 mN is applied to the surface of the resin cured layer from the normal direction is 380 N / mm. ² The substrate with a resin cured layer according to any one of claims 1 to 7, wherein the substrate is described above. When the surface of the cured resin layer is subjected to energy dispersive X-ray spectroscopy under the condition of an acceleration voltage of 20 kV, the carbon atom content X (at%) and the silicon atom content Y (at%) are given by the formula (at%). The substrate with a resin cured layer according to any one of claims 1 to 8, wherein the substrate has the relationship of 2).
Y / X ≧ 2.5 ・ ・ ・ (2) When the surface of the cured resin layer is subjected to energy dispersive X-ray spectroscopy under the condition of an acceleration voltage of 20 kV, the carbon atom content X (at%) and the silicon atom content Y (at%) are given by the formula (at%). The substrate with a resin cured layer according to any one of claims 1 to 8, which is related to 3).
Y / X ≧ 2.7 ... (3) A step of forming a resin cured layer on at least one surface of the substrate and a step of applying a Xe ₂ excima light irradiation treatment to the resin cured layer are included, and the resin cured layer after the light irradiation treatment is described in (a) and (b) below. ), A method for manufacturing a substrate with a resin cured layer, which is characterized by being subjected to Xe ₂ excimer light irradiation treatment so as to satisfy the requirements.
(A) The Martens hardness when a load of 0.5 mN is applied to the surface of the cured resin layer from the normal direction is 150 N / mm ² or more and 800 N / mm ² or less.
(B) The carbon atom content X (at%) and the silicon atom content Y (at%) when the surface of the resin cured layer is subjected to energy dispersion type X-ray spectroscopy under the condition of an acceleration voltage of 20 kV are expressed by the formulas. It is the relationship of (1).
Y / X ≧ 2.0 ・ ・ ・ (1) The step of forming the resin cured layer on at least one surface of the substrate is
11. The present invention is characterized in that a film laminate in which at least a release layer and a resin cured layer are laminated in this order on a support film is laminated on the substrate, and then the support film and the release layer are peeled off. The method for manufacturing a substrate with a resin cured layer according to the above.

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