JP2019098655A - Substrate with resin hardened layer and manufacturing method therefor - Google Patents

Abstract

To provide a substrate with a resin hardened layer having sufficient abrasion resistance even with a material easy to be scratched such as a polycarbonate resin, and a manufacturing method therefor.SOLUTION: A substrate 100 with a resin hardened layer has a substrate 1 and a resin hardened layer 2 arranged on one surface of the substrate 1. Martens hardness when load of 0.5 mN is added from a normal direction to a surface of the resin hardened layer 2 is 150 N/mmto 800 N/mmand percentage content of a carbon atom X (at%) and percentage content of a silicon atom Y (at%) when an energy dispersion type X ray spectrometry is conducted on the surface of the resin hardened layer 2 under a condition of accelerating voltage of 20 kV have a relationship of the formula (1). Y/X≥2.0 (1).SELECTED DRAWING: Figure 1

Description

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

Polycarbonate resins have been widely applied and used as window materials and structural materials for various buildings and automobiles because they are excellent in transparency, light in weight and high in impact resistance.
However, there is a disadvantage that the glass is significantly inferior to the glass in terms of abrasion resistance, weather resistance and chemical resistance. Therefore, there has been proposed a method (for example, Patent Document 1) of forming a hard coat layer having a function of covering these performances on a polycarbonate.
As such a hard coat layer, a method is used in which an underlying hard coat layer containing a hydrolytic condensate of an organosilicon compound as a main component and a silicon oxide layer formed by PE-CVD on the upper layer are laminated. There is.

Patent No. 5944069

However, when the hard coat layer is to be formed by the above method, the productivity is low because the film forming speed is slow, or it is necessary to introduce both the wet coating apparatus and the dry coating apparatus. There is a drawback in 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 abrasion resistance even in a fragile material such as polycarbonate resin. It is.
Furthermore, another object of the present invention is to provide a method of manufacturing a substrate with a resin cured layer which can suppress the deterioration of productivity and the increase of manufacturing cost due to the introduction of equipment.

In order to solve the above problems, a 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 0.5mN direction normal to the surface of the cured resin layer is at 150 N / mm ² or more 800 N / mm ² or less and an acceleration voltage 20kV the surface of the cured resin layer The content ratio of carbon atoms X (at%) and the content ratio of silicon atoms Y (at%) in the case of performing energy dispersive X-ray spectrometry under the condition of (1) are the relationship of Formula (1).
Y / X ≧ 2.0 (1)

In the substrate with a resin cured layer according to an aspect of the present invention, the substrate may have an organic resin as a main component.
In the substrate with the resin cured layer according to an aspect of the present invention, the resin cured layer may be a cured layer containing an ultraviolet curable resin or a thermosetting resin.
In the substrate with the 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 the 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.

In the method for producing a substrate with a resin cured layer according to an aspect of the present invention, a step of forming a resin cured layer on at least one surface of the substrate, a step of subjecting the resin cured layer to Xe ₂ excimer light irradiation treatment, And the resin cured layer after the light irradiation treatment satisfies the following requirements (a) and (b).
(A) Martens hardness of 150 N / mm ² or more 800 N / mm ² or less when a load of 0.5mN direction normal to the surface of the cured resin layer.
(B) The content X (at%) of carbon atoms and the content Y (at%) of silicon atoms in the case of performing energy dispersive X-ray spectrometry under the conditions of an accelerating voltage of 20 kV on the surface of the resin cured layer It is the relationship of (1).
Y / X ≧ 2.0 (1)

  According to the substrate with a resin cured layer of an aspect of the present invention, a substrate with a resin cured layer having sufficient abrasion resistance can be provided. In addition, according to the method for producing a substrate with a resin cured layer according to an aspect of the present invention, dry coating such as a CVD method is not used when forming the resin cured layer, so the production cost is deteriorated due to the deterioration of productivity It is possible to provide a method for producing a substrate with a resin cured layer that can suppress the increase of

It is sectional drawing which shows an example of the laminated structure of the board | substrate with a resin cured layer of a certain aspect of this invention. It is sectional drawing which shows an example of the laminated structure of the film laminated body used for manufacture of the board | 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 planar dimension, the ratio of the thickness of each layer, and the like may be different from actual ones. Further, the embodiments shown below exemplify the configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the materials, shapes, structures and the like of the components are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

<Configuration of Substrate with Resin Hardened 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 with resin cured layer 100 of the present embodiment is a substrate with resin cured layer having the resin cured layer 2 on at least one surface of the substrate 1. The substrate 1 may have an organic resin as a main component. The main component referred to here is the main component as weight. Direction normal to the surface of the cured resin layer 2 Martens hardness when a load of 0.5mN is 150 N / mm ² or more 800 N / mm ² or less, and the surface of the accelerating voltage 20kV cured resin layer The content ratio of carbon atoms X (at%) and the content ratio of silicon atoms Y (at%) in the case of performing energy dispersive X-ray spectrometry under the conditions are the relationship of Formula (1).
Y / X ≧ 2.0 (1)
The substrate with resin cured layer 100 of the present embodiment satisfies the following specific range of hardness and chemical composition. By satisfying such physical property values, the substrate 1 can be provided with excellent wear resistance.

<Hardness>
Cured resin layer-provided substrate 100 of this embodiment is Martens hardness measured from the cured resin layer 2 side may be satisfied to 150 N / mm ² or more 800 N / mm ² or less, preferably 200 N / mm ² or more 600N / mm ² or less is mentioned. With such Martens hardness, the substrate 1 can be provided with excellent wear resistance.
The said Martens hardness pushes the indenter of a diamond into the sample surface with a load of maximum load 0.5mN, and the following formula (2) using the maximum load (A) and the surface area (B) of an indenter from the indentation depth at that time Calculate as follows.
Martens hardness = A / B (2)
In addition, the Martens hardness in this embodiment is a value measured according to the method of ISO14577. In order to make the substrate 10 with the resin cured layer of the present embodiment have the above-mentioned Martens hardness, the composition, thickness, etc. of the resin cured layer 2 may be appropriately adjusted.

<Chemical composition>
In the substrate with the resin cured layer 100 of the present embodiment, the ratio (silicon / carbon ratio) of the carbon atom content X (at%) to the silicon atom content Y (at%) measured from the resin cured layer 2 side is Although 2.0 or more may be satisfied, 2.5 or more is preferably mentioned.
By providing such a chemical composition, the substrate 1 can be provided with excellent abrasion resistance.
The said chemical composition is using content X (at%) of carbon atom at the time of performing energy dispersive X-ray spectroscopy measurement on conditions of acceleration voltage 20kV on the sample surface, and content Y (at%) of a silicon atom. Calculated according to the following equation (3).
Silicon / carbon ratio = Y / X (3)
In order to provide the above-described chemical composition to the resin cured layer-attached substrate 100 of the present embodiment, 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 a resin cured layer of the present embodiment will be described.
In the substrate 100 with the resin cured layer of the present embodiment, the material of the substrate 1 is not particularly limited, and various materials such as resin, glass, paper, wood, metal and the like can be used. Among these, when forming a base material by injection molding of resin, the thermoplastic resin or thermosetting resin (a 1-component or 2-component curable resin is included) mentioned later can be used. Examples of thermoplastic resin materials include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; styrene resins such as polystyrene, acrylonitrile-styrene 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 And polyester resins, such as polycarbonate resins.

The thermosetting resin may, for example, be a one-component or two-component reaction-curable polyurethane resin or an epoxy resin. These resins may be used alone or in combination of two or more. Among these, polycarbonate is excellent in impact resistance and transparency, and is preferably used.
In addition, various additives may be added to these resins as required, such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, calcium carbonate, aluminum hydroxide and the like. Inorganic powder, fillers such as wood powder and glass fibers, lubricants, mold release agents, antistatic agents, coloring agents and the like can be added.
In addition, you may use the resin which added and colored the coloring agent suitably according to the use, and injection resin. There is no restriction | limiting in particular about the thickness of the board | substrate 1, According to the use of the said board | substrate, it selects.

  Here, in order to improve 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 seal adhesive or pressure sensitive adhesive can be used. For example, as an adhesive layer, 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, silicone type Pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives and the like can be mentioned. Moreover, in order to provide an ultraviolet shielding function, a weather resistance improving agent may be added. 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. The types of UV curable resin or thermosetting resin used for the resin cured layer 2 include the above-described Martens hardness, and carbon atom content X (at%) and silicon atom content Y (at%). It may be appropriately set so as to satisfy the ratio, and is not particularly limited as long as these physical property values can be satisfied.

  In the present embodiment, the ultraviolet curable resin refers to a resin that is cured by ultraviolet (UV) light. Representative resins that undergo radical polymerization reaction are resins having an acryloyl group in the molecule, and acrylic (meth) acrylate, polycarbonate (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) Mixtures of monomers, oligomers, polymers, etc., such as acrylates, polyether (meth) acrylates, polybutadiene (meth) acrylates, silicone (meth) acrylates, etc. 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 the silicon of the chemical composition of the formula (3) can be obtained by containing this resin. The content rate can be improved. These resins may be used alone or in combination of several kinds, or may be used in combination with a thermosetting resin described later.
In addition, it is preferable to add an appropriate amount of a known photopolymerization initiator in order to allow the curing of the resin to proceed smoothly with ultraviolet irradiation. Examples of such a photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones and the like.
In addition, n-butylamine, triethylamine, poly-n-butylphosphine and the like can be mixed and used as a photosensitizer.

In the present embodiment, a thermosetting resin refers to a resin that is cured by heat. Among them, 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 functionality, more preferably 3 to 4 functionality. Preferably, the alkoxide is cured by heating.
In addition, those obtained by appropriately performing hydrolysis and dehydration condensation beforehand in a solution and appropriately oligomerizing or polymerizing them are also preferably used.

Examples of silicon alkoxides that can be used include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4- (silane) Epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane Etc. These resins may be used alone or in combination of several types, or may be used in combination with the above-described UV curable resin.
Here, when laminating the resin cured layer 2 on the substrate 1 by transfer, it is preferable to use a resin which is tack free before transfer and which can be crosslinked by irradiation of ultraviolet rays after transfer to the substrate 1. The reason for crosslinking after transfer is that, when the film laminate 10 is used in injection molding or a heating transfer method, if it is crosslinked in advance, it is likely to be cracked at the time of extension of transfer, resulting in an appearance defect.

  In the present embodiment, the resin cured layer 2 preferably 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, and complex oxides such as antimony-doped tin oxide and phosphorus-doped tin oxide, and calcium carbonate Talc, clay, kaolin, calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like can also be used. These inorganic fine particles may be used as a mixture of two or more.

Among these, it is preferable to use silicon oxide. By containing silicon oxide, the silicon / carbon ratio of the chemical composition of Formula (3) can be improved. As the fine particles, silicon oxide may be used as the main component. The main component referred to 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 the 50% particle size (d50 median size) when the particle size distribution is represented by cumulative distribution. It is. For example, it can be measured by a commercially available apparatus called Nanotrac UPA-EX 150 manufactured by Microtrac, USA.

By adding the inorganic fine particles, the fine particles fill the voids in the cured resin layer, thereby increasing the hardness. In addition, when the average particle diameter of the inorganic fine particles is 10 nm or more, the production of the fine particles is facilitated, and when the average particle diameter is 100 nm or less, the light transmittance of the resin cured layer can be imparted. The average particle diameter of the inorganic fine particles is more preferably 10 nm or more and 50 nm or less.
The addition amount of the inorganic fine particles varies depending on the type of particles and the particle size, but is 20 to 500 parts by weight, more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin.

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

As the support film 3, for example, a base material 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 nylon film, a cellophane film, and an acrylic film can be used. The thickness of the support film 3 which can be used is 25 μm to 150 μm, preferably 38 μm to 50 μm.
The releasability from the resin cured layer 2 is most important for the release layer 4, and heat resistance, solvent resistance and stretchability are also required. Therefore, the release layer 4 is preferably a curing system, and for example, a cured product such as a melamine resin, a polyolefin resin, a urethane resin, and cellulose acetate can be used. As a curing crosslinking system, epoxy resin / amines, alkyd resin / acid catalyst, acrylic polyol resin / isocyanate compound, acrylic oligomer / photoinitiator can be used. The thickness of the release layer 4 is not particularly limited, but is preferably 0.1 μm to 3 μm.

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

The manufacturing method of the present embodiment includes the step of forming the resin cured layer 2 on at least one surface of the substrate 1 and the step of subjecting the resin cured layer 2 to Xe ₂ excimer light irradiation treatment.
Then, in the step of performing Xe ₂ excimer light irradiation treatment on the resin cured layer 2, cured resin layer 2 after the light irradiation treatment is Xe ₂ excimer light irradiation treatment so as to satisfy the following requirements (a) and (b).
(A) Martens hardness of 150 N / mm ² or more 800 N / mm ² or less when a load of 0.5mN direction normal to the surface of the cured resin layer 2.
(B) The content X (at%) of carbon atoms and the content Y (at%) of silicon atoms when energy dispersive X-ray spectrometry is performed under the conditions of an accelerating voltage of 20 kV on the surface of the resin cured layer 2 It is the relationship of Formula (1).
Y / X ≧ 2.0 (1)

Specifically, after laminating on a substrate 1 a film laminate 10 in which at least a release layer 4 and a cured resin layer 2 are laminated in this order on a support film 3, the support film 3 and the release layer 4 are The substrate 100 with the resin cured layer of the present invention can be manufactured by a method of peeling and irradiating the ultraviolet rays to cure the resin cured layer 2.
Further, in the method for producing a substrate with a resin cured layer of the present embodiment, the resin cured layer 2 formed as described above may be subjected to irradiation treatment with Xe ₂ excimer light.
Here, 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 Xe ₂ excimer light. it can. Specifically, it is possible to specifically cut the bond of the silicon atom and the carbon atom or the bond of the carbon atom and the carbon atom present on the surface of the hardened layer. By performing such treatment, the silicon / carbon ratio of the chemical composition of the formula (3) can be improved.

Example 1
An acrylic melamine resin (Hitachi Chemical Polymer Co., Ltd .; Tesfine) is formed by dry method to a dry thickness of 0.2 μm on a 50 μm thick biaxially stretched polyester film (Mitsubishi Resin Co., Ltd .; G440E50) which is the support film 3 The release layer 4 was obtained. Here, "Dry 0.2 μm thick" means that it becomes 0.2 μm thick after drying. Similarly to this, "Dry 厚」 m thickness "described below means that it becomes μ μm thickness after drying.

Subsequently, on the release layer 4,
Acrylic acrylate (DIC; RC 29-120) 20 parts by weight Silicone acrylate (Shin-Etsu Chemical KR-513) 80 parts by weight Colloidal silica (Nissan Chemical Industries; MEK-ST-ZL) 150 parts by weight Photopolymerization initiator (BASF Japan; Irgacure 184) A UV curable resin composition obtained by stirring and mixing 4 parts by weight of methyl isobutyl ketone and 50 parts by weight of methyl isobutyl ketone was coated by a gravure method at a dry thickness of 10 μm to form a resin cured layer 2.

Next, an ink prepared by dissolving salt and vinyl acetate resin (Nisshin Chemical Industry Co., Ltd .; Solvaine A) as an adhesive layer in toluene and methyl ethyl ketone is applied by dry method to a thickness of 1 μm on the cured resin layer 2 by a gravure method. I got
Furthermore, the film laminate 10 was set in a mold of an injection molding machine, and injection molding was performed using a polycarbonate resin as the substrate 1. The resulting molded product is in a state in which the support film 3 and the release layer 4 are removed, and the cured resin surface of the molded product is irradiated with ultraviolet light with an exposure amount of 1000 mJ / cm ² with a high pressure mercury lamp of 120 W / cm to completely cure I did. Thereafter, the cured resin layer was irradiated with 5000 mJ / cm ² of Xe ₂ excimer light to obtain a substrate 100 with a cured resin layer.

(Example 2)
A substrate with a resin cured layer of Example 2 was obtained by the same procedure as Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
Acrylic acrylate (DIC; RC 29-120) 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 of methyl isobutyl ketone 50 parts by weight

(Example 3)
A substrate with a resin cured layer of Example 3 was obtained by the same procedure as Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
Acrylic acrylate (DIC; RC 29-120) 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 of methyl isobutyl ketone 50 parts by weight

(Example 4)
A substrate with a resin cured layer of Example 4 was obtained by the same procedure as Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
Acrylic acrylate (DIC; RC 29-120) 80 parts by weight Silicone acrylate (Shin-Etsu Chemical KR-513) 20 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 of methyl isobutyl ketone 50 parts by weight

(Comparative example 1)
A substrate with a resin cured layer of Comparative Example 1 was obtained by the same procedure as in Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
Acrylic acrylate (DIC; RC 29-120) 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)
A substrate with a resin cured layer of Comparative Example 2 was obtained in the same manner as in Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
-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)
A substrate with a resin cured layer of Comparative Example 3 was obtained by the same procedure as in Example 1, except that the ultraviolet curable resin composition as the resin cured layer 2 used in Example 1 was changed as follows. The
Acrylic acrylate (DIC; RC 29-120) 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 Evaluation items and evaluation criteria of the substrate with a resin cured layer obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are shown below.

(hardness)
A diamond indenter is pressed with a load of 0.5 mN from the normal direction against the surface of the resin cured layer of the substrate with resin cured layer, and the maximum load (A) and surface area of the indenter (B) are calculated from the indentation depth at that time. The Martens hardness was calculated according to the method described in ISO 14577 using the following formula (2). Martens hardness was 150N / mm ² more than 800N / mm ² the following as "appropriate".
Martens hardness = A / B (2)

(Chemical composition)
Carbon atom content X (at%) and silicon atom content Y (at%) when energy dispersive X-ray spectrometry is performed on the surface of the resin cured layer of the substrate with resin cured layer under conditions of an acceleration voltage of 20 kV The silicon / carbon ratio was calculated according to the following equation (3) using
Silicon / carbon ratio = Y / X (3)

(Abrasion resistance)
A Taber abrasion test was conducted under the conditions of 1000 rotations, 60 rpm, and a load of 500 g using CS-10F for the abrasion wheel. The haze was measured according to the method described in JIS K7136 using a haze meter (NDH-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) at four locations on the substrate with the resin cured layer before and after the Taber abrasion test, and the average value was determined. The haze difference (Δ Hz) before and after the Taber abrasion test was determined by subtracting the haze before the Taber abrasion test from the haze after the Taber abrasion test. The haze difference (Δ Hz) was “proper” at 2.0% or less.
The evaluation results of each example and each comparative example are shown in Table 1.

Examples 1 to 4 and Comparative Examples 1 to 3 obtained in the cured resin layer-provided substrate of the hardness was evaluated for chemical composition and abrasion resistance, Martens hardness of 150 N / mm ² or more 800 N / mm ² or less, and silicon For Examples 1 to 4 in which the carbon / carbon ratio is 2.0 or more, the wear resistance was good, and all ΔHz were 2.0% or less.
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 the ΔHz was 4.5%. Further, in Comparative Example 2 in which the Martens hardness is as low as 130 N / mm ² , the wear resistance was not improved, and the ΔHz was 7.8%. Furthermore, in Comparative Example 3 in which the Martens hardness is as high as 1040 N / mm ² , the wear resistance was not improved, and the ΔHz was 3.5%.

According to the substrate with the resin cured layer of the present embodiment, it is possible to provide a substrate with a resin cured layer having sufficient abrasion resistance even with a scratch-resistant material such as polycarbonate resin.
In addition, according to the method for producing a substrate with a resin cured layer of the present embodiment, dry coating such as a CVD method is not used when forming a resin cured layer to be a hard coat, so that productivity is deteriorated or equipment is introduced. An increase in manufacturing cost can be suppressed.
As mentioned above, although the embodiment of the present invention has been described in detail, the present invention is not limited to the above embodiment in fact, and the present invention is included in the present invention even if there are changes within the scope 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 (7)

A substrate, and a resin cured layer on at least one surface of the substrate;
The Martens hardness when a load of 0.5mN direction normal to the surface of the cured resin layer is at 150 N / mm ² or more 800 N / mm ² or less and an acceleration voltage 20kV surface of the cured resin layer It is characterized in that the content ratio of carbon atoms X (at%) and the content ratio of silicon atoms Y (at%) in the case of performing energy dispersive X-ray spectrometry under the conditions of Substrate with resin cured layer.
Y / X ≧ 2.0 (1)   The substrate with a resin cured 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 said resin cured layer contains the microparticles | fine-particles which have silicon oxide as a main component, The board | substrate with a resin cured layer of any one of the Claims 1-3 characterized by the above-mentioned.   The film thickness of the said resin cured layer is 3 micrometers-20 micrometers, The board | substrate with a resin cured layer of any one of the Claims 1-4 characterized by the above-mentioned. The step of forming a cured resin layer on at least one surface of the substrate, and the step of subjecting the cured resin layer to Xe ₂ excimer light irradiation treatment, the cured resin layer after the light irradiation treatment includes the following (a) and (b) method for manufacturing a substrate with the resin cured layer, characterized in that the Xe ₂ excimer light irradiation treatment to meet the requirements of).
(A) Martens hardness of 150 N / mm ² or more 800 N / mm ² or less when a load of 0.5mN direction normal to the surface of the cured resin layer.
(B) The content X (at%) of carbon atoms and the content Y (at%) of silicon atoms in the case of performing energy dispersive X-ray spectrometry under the conditions of an accelerating voltage of 20 kV on the surface of the resin cured layer It is the relationship of (1).
Y / X ≧ 2.0 (1) The step of forming a cured resin layer on at least one surface of the substrate comprises:
After laminating a film laminate in which at least a release layer and a cured resin layer are laminated in this order on a support film, the support film and the release layer are peeled off. The manufacturing method of a substrate with a resin cured layer as described in 4.

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