TW201803944A - Laminated film - Google Patents

Abstract

The laminated film according to the present invention has a base layer and a hard coat layer, and is characterized in that the hard coat layer is formed using a hard coat agent containing components (A), (B), and (C), namely, (A) an organic silicon compound having a reactive functional group and a hydrolyzable group, (B) a polythiol compound, and (C) an inorganic filler having a reactive functional group, and that the measurement of the Young's modulus of the surface of the hard coat layer using an atomic-force microscope shows that regions where the Young's modulus is 1-5 GPa constitute a continuous structure, and regions where the Young's modulus is 6-10 GPa are isolated and distributed. The laminated film according to the present invention has a hard coat layer which has high hardness and excellent scratch resistance and flex resistance.

Description

Laminated film

The present invention relates to a laminated film of a hard shell layer having high hardness, abrasion resistance and excellent bending resistance.

In recent years, display devices such as various displays have touch screens, and are mostly used as data input devices.

When using this touch screen, the surface of the touch screen is usually touched with a pen or finger. However, it is hoped that the surface of the touch screen will not be damaged even after repeated contact with a pen or finger.

Therefore, previously, a hard shell layer was provided on a resin film constituting a touch screen.

For example, Patent Document 1 discloses a resin composition for a transparent coating containing an organic silicon compound and a polythiol compound having a reactive functional group, or a transparent coating formed using the resin composition. In addition, this document describes that the transparent coating layer formed using the resin composition has good flexibility, hardness, abrasion resistance, and abrasion resistance.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Patent Publication No. 2010/103944

From the above, it is known that Patent Document 1 describes that the transparent coating has good flexibility, hardness, abrasion resistance, abrasion resistance, and the like.

However, in order to form this transparent coating layer, the resin composition must be sufficiently hardened, but depending on the conditions of hardening, a transparent coating layer having desired characteristics cannot be formed.

In view of this, an object of the present invention is to provide a laminated film of a hard shell layer having high hardness, good abrasion resistance, and good bending resistance.

In order to solve the above problems, the present inventors have extensively studied hard shell agents. As a result, it was found that the use of a hard shell agent containing an organosilicon compound having a reactive functional group and a hydrolyzable group, a polythiol compound, and an inorganic filler having a reactive functional group can effectively form a high-hard, good Scratch-resistant hard shell. In addition, when an inorganic filler is added to the hard shell layer, the bending resistance of the hard shell layer is reduced. However, by controlling the dispersion state of the inorganic filler in the hard shell layer, a decrease in the bending resistance can be suppressed.

The present invention has been completed based on this finding.

Therefore, this invention provides the laminated film of following (1).

(1) A laminated film comprising a laminated film of a substrate layer and a hard shell layer. The hard shell layer is formed using a hard shell agent containing the following component (A), component (B), and component (C), and an atomic force microscope is used. The Young's coefficient on the surface of the hard shell layer was measured. The area with a Young's coefficient of 1 to 5 GPa was a continuous structure, and the area with a Young's coefficient of 6 to 10 GPa was independently dispersed.

Component (A): an organosilicon compound having a reactive functional group and a hydrolyzable group; component (B): a polythiol compound; component (C): an inorganic filler having a reactive functional group.

The present invention provides high hardness, scratch resistance, and good flex resistance. Good hard shell laminated film.

FIG. 1 is a Young's coefficient map image of the laminated film (1) obtained in Example 1. FIG.

FIG. 2 is a Young's coefficient map image of the laminated film (2) obtained in Comparative Example 1. FIG.

FIG. 3 is a Young's coefficient map image of the laminated film (3) obtained in Comparative Example 2. FIG.

FIG. 4 is a Young's coefficient map image of the laminated film (4) obtained in Comparative Example 3. FIG.

FIG. 5 is a Young's coefficient map image of the laminated film (5) obtained in Comparative Example 4. FIG.

The laminated film of the present invention is a laminated film including a substrate layer and a hard shell layer. This hard shell layer is formed using a hard shell agent containing the following component (A), component (B), and component (C), and measured using an atomic force microscope. The Young's coefficient on the surface of the hard shell layer, the area with a Young's coefficient of 1 to 5 GPa is a continuous structure, and the area with a Young's coefficient of 6 to 10 GPa is independently dispersed.

Component (A): an organosilicon compound having a reactive functional group and a hydrolyzable group; component (B): a polythiol compound; component (C): an inorganic filler having a reactive functional group.

The base material layer constituting the laminated film of the present invention is used to support a hard shell layer.

The type of the base material layer is not particularly limited. For example, a synthetic resin film is used as the base material layer.

The synthetic resin film can be selected from, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, polyethylene terephthalate, polymer Butyl terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polystyrene, cellulose acetate, cellophane, polycarbonate, etc. Of the film.

In the present invention, a primer layer is provided on at least one side of the substrate layer. The primer layer is a substance having good adhesion to the hard shell layer provided above it and good adhesion to the base material layer, and the kind thereof is not particularly limited. As the primer layer, conventional primer layers such as an acrylic primer layer, a polyester primer layer, a polyurethane primer layer, a silicone primer layer, and a rubber primer layer can be used.

The thickness of the substrate layer (synthetic resin film) is not particularly limited, and can be determined according to the use of the laminated film.

The thickness of the substrate layer is usually 10 to 500 μm, and preferably 20 to 200 μm.

The hard shell layer constituting the laminated film of the present invention is formed by using a hard shell agent (hereinafter, referred to as "hard shell agent (α)") containing the following component (A), component (B), and component (C).

The hard shell agent (α) contains, as a component (A), an organosilicon compound having a reactive functional group and a hydrolyzable group (hereinafter referred to as "organosilicon compound (A)").

The reactive functional group in the organosilicon compound (A) is a group capable of reacting with a thiol group of the component (B) to form a chemical bond.

The reactive functional group may be selected from a group containing a carbon-carbon unsaturated bond such as a vinyl group, an allyl group, a styryl group, a (meth) acryl fluorenyl group, an epoxy group, an isocyanate, a mercapto group, and the like. Among these, a group having a carbon-carbon unsaturated bond is preferable, and a vinyl group is more preferable.

The hydrolyzable group in the organosilicon compound (A) is a group capable of forming a siloxane bond (Si-O-Si bond) by a hydrolysis reaction.

Hydrolyzable groups can be selected from alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and n-propoxy groups, and preferably 1 to 5 alkoxy groups; It is an aryloxy group having 6 to 10 carbon atoms, such as methyloxy, ethoxy, and propoxy, having a carbon number of 1 to 10. Preferred is 1 to 5 fluorenyloxy groups; halogen atoms such as chlorine atom and bromine atom. Among these, an alkoxy group having 1 to 10 carbon atoms or a fluorenyl group having 1 to 10 carbon atoms is preferred, and a fluorenyl group having 1 to 10 carbon atoms is more preferred.

The organosilicon compound (A) can be selected from the compounds represented by the following formula (I).

In the formula (I), R ¹ is a group having a reactive functional group, R ² is a hydrolyzable group, and R ³ is a non-hydrolyzable group having no reactive functional group.

x is 1, 2 or 3, y is 1, 2 or 3, z is 0, 1 or 2, and x, y, and z are 4 in total.

When x, y or z is 2 or more, a plurality of R ¹ , R ² or R ³ may be the same or different.

R ¹ is a group selected from a reactive functional group or a group having a reactive functional group. Specific examples thereof may be selected from groups having a vinyl group such as vinyl, vinyloxymethyl; groups having an allyl group such as allyl, allyloxymethyl; styryl, styrylmethyl Groups such as styryl; Groups with (meth) acrylfluorenyl such as (meth) acrylfluorenyl, 3- (meth) acrylfluorenyloxypropyl; epoxy, epoxypropyl Groups having an epoxy group, such as 1,3-glycidyloxypropyl; groups having an isocyanate group, such as isocyanate group and 3-isocyanatepropyl group; groups having a mercapto group, such as mercapto group and 3-mercaptopropyl group. Among these, a group having a carbon-carbon unsaturated bond is preferable, and a vinyl group is more preferable.

The carbon number of R ¹ is preferably 2 to 20, and more preferably 2 to 10.

R ² may be selected from the above-mentioned hydrolyzable group.

The carbon number of R ² is preferably from 0 to 15, more preferably from 0 to 10.

R ³ may be selected from methyl, ethyl, n-propyl, isopropyl and other alkyl groups having 1 to 20 carbon atoms, preferably 1 to 15 alkyl groups; phenyl; 1 to naphthyl and 6 to 20 carbon atoms , Preferably an aryl group of 6 to 15 and the like.

The organosilicon compound (A) can be selected from vinyltrimethoxysilyl, vinyltriethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltribromosilane, etc. Silane compounds; allyl trimethoxysilane, allyl triethoxysilane, allyl triethoxysilane, allyl trichlorosilane, allyl tribromosilane, etc. Silane compounds; γ-propenyloxypropyltrimethoxysilane, γ-propenyloxypropyltriethoxysilane, γ-propenyloxypropyltrichlorosilane, γ-propenyloxypropyltribromosilane Silane compounds containing γ-acrylic acid oxypropyl; γ-methacrylic acid oxytrimethoxysilane, γ-methacrylic acid oxypropyltriethoxysilane, γ-methacrylic acid oxypropyltrisiloxane Silyl compounds containing γ-methacrylic acid alkyl groups, such as chlorohydrogen silicon, γ-methacryloxypropyltribromosilane; α-epoxypropylethyltrimethoxysilane, α-epoxypropylethyl Triethoxysilane, β-epoxypropyltrimethoxysilane, β-epoxypropyltriethoxysilane, α-epoxypropylethyltrichlorosilane, α-cyclo Cyclopropylethyl tribromo Silane, β- trichloro-ethyl glycidyl Silane, β- epoxy silane-cyclopropylethyl tribromo other epoxy group-containing silane-compound.

Among these, the organosilicon compound (A) is preferably a vinyl-containing silane compound, and more preferably vinyltriethoxysilane.

The organosilicon compound (A) may be used alone or in combination of two or more.

The hard shell agent (α) contains a polythiol compound as a component (B).

In addition to the above-mentioned organosilicon compounds, the use of a hard shell agent containing a polythiol compound can form a hard shell layer with good transparency, high pencil hardness, and good resistance to bending.

The polythiol compound is a compound having two or more mercapto groups in the molecule.

The polythiol compound can be selected from compounds having a mercapto group number 2 such as ethylbis (mercaptoacetic acid) and ethylbis (3-mercaptopropionic acid); trimethylolethane tri (mercaptoacetic acid), trimethylol Compounds with a thiol number of 3, such as ethanetri ((3-mercaptopropionic acid), trimethylolpropane tri (mercaptoacetic acid), and trimethylolpropane tri (3-mercaptopropionic acid); pentaerythritol tetra (mercaptoacetic acid) Compounds having a mercapto group number of 4 or more such as pentaerythritol tetrakis (3-mercaptopropionic acid), dipentaerythritol hexa (mercaptoacetic acid), and dipentaerythritol hexa (3-mercaptopropionic acid).

Among these, the polythiol compound is preferably a compound having 3 mercapto groups or a compound having 4 or more mercapto groups, and more preferably trimethylolpropane tris (mercaptopropionic acid).

The polythiol compound may be used singly or in combination of two or more kinds.

The content of the polythiol compound is not particularly limited. The content of the polythiol compound is usually 50 to 120% by mass, preferably 60 to 100% by mass, and more preferably 60 to 90% by mass with respect to the component (A).

When a hard shell layer is formed by using a hard shell agent with too little polythiol compound content, the laminated film may curl. In addition, it may be difficult to form a hard shell layer with high hardness by using a hard shell agent in which the polythiol compound is excessive.

The hard shell agent (α) contains an inorganic filler having a reactive functional group as a component (C) (an inorganic filler having a reactive functional group introduced on the surface after modification treatment, and the component (C) is hereinafter referred to as "inorganic filler物 (C) ″).

In addition to the above-mentioned organosilicon compound and polythiol compound, the use of a hard-shell agent containing an inorganic filler (C) can form a hard-shell layer having excellent transparency, high pencil hardness, and excellent resistance to bending.

The reactive functional group of the inorganic filler (C) is The mercapto group (B) forms a chemically bonded group. This reactive functional group can be selected from the same substance as the organosilicon compound (A). Among them, a group having a carbon-carbon unsaturated bond is preferable, and a (meth) acrylic fluorenyloxy group is more preferable.

The inorganic component (the component of the inorganic filler before the modification treatment) constituting the inorganic filler (C) can be selected from metal oxides, metal hydroxides, and metal salts.

The metal oxide can be selected from silicon dioxide, titanium dioxide, alumina, gibbsite, chromium oxide, nickel oxide, copper oxide, titanium dioxide, zirconia, indium oxide, zinc oxide and the like.

The metal hydroxide can be selected from aluminum hydroxide.

The metal salt can be selected from metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; metal silicates such as aluminum silicate, calcium silicate, and magnesium silicate.

Among these, the inorganic component constituting the inorganic filler (C) is preferably a metal oxide, and more preferably silicon dioxide.

Although the shape constituting the inorganic filler (C) may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a sheet shape, a rod shape, and a fibrous shape, it is preferably a spherical shape. In the present invention, the so-called spherical shape includes a polyhedral spherical shape similar to a sphere, such as a rotating ellipse, a circle, a gold candy shape, and a cocoon shape, in addition to a true spherical shape.

The size of the inorganic filler (C) is not particularly limited. The average particle diameter of the inorganic filler (C) is usually 5 to 1000 nm, preferably 10 to 500 nm, and more preferably 20 to 100 nm.

When the average particle diameter of the inorganic filler (C) is within the above range, a hard shell layer having good transparency and excellent scratch resistance can be effectively formed.

The average particle diameter of the inorganic filler (C) can be calculated using the specific surface area obtained by the BET method.

The inorganic filler (C) in the hard shell agent of the present invention may be used singly or in combination of two or more kinds.

The content of the inorganic filler (C) is not particularly limited. The content of the inorganic filler (C) with respect to the component (A) is usually 30 to 130% by mass, preferably 60 to 125% by mass, and more preferably 90 to 125% by mass.

A hard shell agent having an inorganic filler (C) content of 90 to 125% by mass relative to the component (A) is used to easily form a hard shell layer with high hardness.

A hard-shelling agent having an inorganic filler (C) content of 90 to 125% by mass relative to the component (A) can easily form a hard-shelling layer having good scratch resistance.

The hard shell agent (α) may contain components other than the component (A), the component (B), and the component (C) within a range that does not prevent the effects of the present invention. Other ingredients may be solvents or photopolymerization initiators.

Solvent-containing hard shell agents are easy to apply and apply. Using hard shell agents containing solvents can effectively form a thin hard shell layer.

The solvent can be selected from aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; halogen hydrocarbons such as dichloromethane and dichloroethane Solvents; alcohol solvents such as methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol; acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, isophor Ketone solvents such as ketones, etc .; Ester solvents such as ethyl acetate and butyl acetate; Celluloid solvents such as ethylcellulose.

The solvent may be used singly or in combination of two or more kinds.

When the hard shell agent (α) contains a solvent, the content of the solvent is preferably 30 to 95% by mass or more, more preferably 35 to 90% by mass, and most preferably 40 to 85% by mass, based on the solid portion of the hard shell agent of the present invention.

By using a hard-shell agent containing a photopolymerization initiator, the obtained coating can be effectively hardened after the hard-shell agent is applied.

The photopolymerization initiator can be selected from, for example, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2 2,2-dimethoxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholine-propane-1-one, 4- (2-hydroxyethyl) benzene -2 (hydroxy-2propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone , 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-bis Methylthioxanthone, 2,4-diethylthioxanthone, benzophenone dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate and the like.

The photopolymerization initiator may be used singly or in combination of two or more kinds.

When the hard shell agent (α) contains a photopolymerization initiator, the content of the photopolymerization initiator relative to the total amount of the solid portion of the hard shell agent is usually 0.01 to 10% by mass, and preferably 0.5 to 10% by mass.

The thickness of the hard shell layer constituting the laminated body film of the present invention is usually 0.1 to 50 μm, and preferably 0.5 to 20 μm.

The hard shell layer constituting the laminated body film of the present invention is measured with a Young's coefficient on the surface using an atomic force microscope. The area of the Young's coefficient of 1 to 5 GPa is a continuous structure, and the area of the Young's coefficient of 6 to 10 GPa is independent.

"The area constituting the Young's coefficient of 1 to 5 GPa is a continuous structure." The area of the Young's coefficient of 1 to 5 GPa forms a continuous large part (that is, the same part as the sea in the island structure).

"The area with a Young's coefficient of 6 to 10 GPa is independently dispersed." The area with a Young's coefficient of 6 to 10 GPa is dispersed throughout (that is, the same part of the island structure as the island structure is formed).

The hard shell layer constituting the Young's coefficient region of 1 to 5 GPa is a continuous structure, which can effectively reduce the stress during bending and has good bending resistance. In addition, on the other hand, when the area with a Young's coefficient of 6 to 10 GPa is independently dispersed, this hard shell layer has sufficient hardness for contact with a millimeter-level substance such as a pencil.

The Young's coefficient on the surface of the hard shell layer can be measured according to the method described in the examples.

The areas with Young's coefficients of 6 to 10 GPa are one by one, preferably nanometer grade. For example, when a square or rectangle is drawn in this area, the side length is preferably 10 to 100 nm, and more preferably 40 to 60 nm.

As described below, the amount of the component (A), the component (B), and the component (C) in the hard shell agent (α) can be used to effectively form a hard shell layer having these structures.

First, the reactive functional group contained in the component (A) or the component (C) constituting the hard shell agent (α) is capable of reacting with the mercapto group of the component (B) and reacting with these reactive functional groups in the same manner.

If the reaction of the reaction group of the component (C) is mainly carried out, a part of the component (C) will agglomerate, and a hard shell layer having a desired structure cannot be formed.

However, the amount of the component (B) capable of sufficiently reacting the thiol group of the component (B) with the reactive functional group of the component (A) or the component (C) can improve the dispersibility of the component (C).

In addition, the reaction between these reactive functional groups and the mercapto group is an addition reaction, and even if this reaction occurs, it is not easy to cause the hard shell layer to shrink. In addition, if more than the necessary reactive functional groups of the same type occur, local hardening can occur. Shrinks, degrades optical characteristics, and produces curl.

On the other hand, in order to perform the same kind of reaction of the reactive functional group, it is usually necessary to irradiate an active energy beam such as ultraviolet rays or an electron beam and heat, and the reaction rate of the reactive functional group and the mercapto group is faster than that of the reactive functional group of the same type. However, if necessary, the active energy beam such as ultraviolet rays or electron beams can be analyzed and studied in order to effectively form a hard shell layer with desired characteristics.

Therefore, according to the amount of the reactive functional group contained in the component (A) or the component (C), using an appropriate amount of the component (B), the reactive functional group and the mercapto group are sufficiently reacted to form the above-mentioned structure, and the optical characteristics, Hard shell with good resistance to curling and less prone to curling.

The laminated film of the present invention, for example, coats the hard shell agent (α) directly or through other layers on the synthetic resin forming the substrate layer, and hardens the obtained coating to produce a laminated film.

The method for applying the hard shell agent to the synthetic resin is not particularly limited, and a conventional method can be used. For example, roll coating, curtain flow coating, Mylar bar coating, reverse coating, gravure coating, reverse gravure coating, pneumatic blade coating, contact coating, blade coating, smoothing Coating, roller blade coating, etc.

The method for hardening the coating is not particularly limited. For example, the coating may be hardened by irradiating the coating with an active energy beam such as ultraviolet rays or electron beams.

The ultraviolet irradiation can be performed by a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. The irradiation amount of ultraviolet rays is preferably 50 to 1000 mW / cm ² and the irradiation amount is 50 to 1000 mJ / cm ² . In addition, the electron beam can be irradiated with an electron beam accelerator. The irradiation amount of the electron beam is preferably 10 to 1000 krad.

When forming the hard shell layer, it can be before or after the coating is hardened. Perform the required drying treatment.

The conditions for the drying treatment are not particularly limited. The drying temperature may be, for example, 40 to 150 ° C, preferably 60 to 140 ° C, and the drying time may be, for example, 30 seconds to 1 hour, preferably 1 to 30 minutes.

The hard shell layer can be formed using the hard shell agent of the present invention, has high hardness, and is excellent in abrasion resistance.

The hard shell layer constituting the laminated film of the present invention can be evaluated for hardness by a pencil method according to the method of the examples, and usually shows a hardness of F or more, preferably H or more.

When the hard-shell layer constituting the laminated film of the present invention is evaluated for abrasion resistance according to the method of the examples, damage is generally not observed.

The laminated film of the present invention preferably has good transparency. When measuring the total light transmittance of the laminated film of the present invention, it is preferably 89% or more, and more preferably 90% or more. There is no special upper limit, usually 95% or less

The laminated film of the present invention preferably has good bending resistance. According to the JIS K5600-5-1 standard, the laminated film of the present invention is subjected to a mandrel bending test, preferably 4 mmΦ or less, and more preferably 2 mmΦ or less.

The laminated film of the present invention preferably has a small curvature. The laminated film of the present invention is used to evaluate the bendability according to the method of the embodiment, which is usually 75 mm or less, preferably 50 mm. The lower limit value is not particularly limited, and is usually 3.5 mm or more.

The laminated film of the present invention has a hard shell layer with high hardness and excellent scratch resistance and flex resistance, and is suitable as a manufacturing material of a touch panel.

[Example]

Hereinafter, examples are given to explain the present invention in detail. However, the following examples cannot be used to limit the present invention. Unless otherwise specified, parts and% in each example are based on quality.

The compounds used in the examples and comparative examples are shown below.

Organic silicon compound (vinyl triethoxysilane) solution (A1) (manufactured by Sakai Chemical Co., Ltd., trade name: SHC-001B, concentration 90%)

Polythiol compound (trimethylolpropane tris (3-mercaptopropionic acid)) solution (B1) (manufactured by Sakai Chemical Co., Ltd., trade name: SHC-001A, concentration 60%)

Dispersion liquid (C1) of inorganic filler (silica dioxide particles having acryloxy group) (manufactured by Nissan Chemical Industry Co., Ltd., trade name: AC-4130Y, concentration 30%, average particle size 40-50 nm)

[Example 1]

110 parts of an organosilicon compound solution (A1), 150 parts of a polythiol compound (B1), and 398 parts of an inorganic filler dispersion (C1) were mixed, and the obtained mixed solution was diluted with methyl ethyl ketone to prepare a solid 45% hard shell agent (1).

A polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: PET50A4100, thickness 50 μm) with a primer layer on one side was coated with a # 10 Meyer bar to harden the film thickness on the primer layer. The hard shell agent (1) was 5 μm, and the coating was hardened by irradiating ultraviolet rays (irradiation amount 500 mJ / cm ² ). Then, the hard-coat layer was dried at 120 ° C. for 20 minutes to form a hard shell layer to obtain a laminated film (1).

[Comparative Example 1]

110 parts of an organosilicon compound solution (A1) and 100 parts of a polythiol compound solution (B1) were mixed, and the obtained mixed solution was diluted with methyl ethyl ketone to prepare a hard shell agent (2) having a concentration of 50%.

A laminated film (2) was obtained in the same manner as in Example 1, except that the hard shell agent (2) was used instead of the hard shell agent (1) in Example 1.

[Comparative Example 2]

110 parts of an organosilicon compound solution (A1), 100 parts of a polythiol compound solution (B1), and 278 parts of an inorganic filler dispersion (C1) were mixed, and the obtained mixed solution was diluted with methyl ethyl ketone to prepare 50% hard shell agent (3).

A laminated film (3) was obtained in the same manner as in Example 1, except that the hard shell agent (3) was used instead of the hard shell agent (1) in Example 1.

[Comparative Example 3]

110 parts of an organosilicon compound solution (A1), 100 parts of a polythiol compound solution (B1), and 333 parts of an inorganic filler dispersion (C1) were mixed, and the obtained mixed solution was diluted with methyl ethyl ketone to prepare 50% hard shell agent (4).

A laminated film (4) was obtained in the same manner as in Example 1, except that the hard shell agent (4) was used instead of the hard shell agent (1) in Example 1.

[Comparative Example 4]

A mixture of organically modified silicon microparticles and a polyfunctional acrylate (made by JSR Corporation, trade name: OPSTAR-Z7530, 73% in concentration, containing a photopolymerization initiator, and an inorganic filler content of 60%) was diluted with propylene glycol methyl ether. A hard shell agent (5) was prepared at a concentration of 40%.

A polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: PET50A4100, thickness 50 μm) with a primer layer on one side was coated with a # 10 Meyer bar to harden the film thickness on the primer layer. The hard shell agent (5) was 5 μm, and was dried at 100 ° C. for 1 minute. Next, this coating was irradiated with ultraviolet rays (irradiation amount 500 mJ / cm ² ), the coating was hardened to form a hard shell layer, and a laminated film (5) was obtained.

The laminated films (1) to (5) obtained in Example 1 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Table 1.

[Thickness evaluation]

The thickness of the hard shell layer was measured using a thickness meter (manufactured by Nikon, trade name: MH-15) in accordance with JIS K7130 (1999).

[Full light transmittance]

The total light transmittance of the laminated film was measured using a turbidimeter (manufactured by Nippon Denshoku Corporation, trade name: N-DH-2000) in accordance with JIS K7361-1 (1997).

[Pencil hardness]

A pencil hardness tester (manufactured by Yasuda Seiki Co., Ltd., trade name: No. 553-M) was used to perform a pencil hardness test at a load of 750 g and a moving speed of 0.5 mm / sec in accordance with JIS K5600-5-4 (1999).

[Scratch resistance evaluation]

A # 0000 steel brush was used to repeatedly rub the hard shell layer of the laminated film 10 times in a range of 50 mm with a load of 250 g / cm ² , and then the presence or absence of damage was visually checked, and the abrasion resistance was evaluated according to the following criteria.

○: No abrasions

×: Scratched

[Evaluation of resistance to bending]

According to JIS K5600-5-1 (1999), a mandrel bending test was performed to evaluate the bending resistance of the laminated film.

[Bendability evaluation]

The laminated film was cut to obtain a square of 10 cm on one side as a test piece. This test piece was left standing on a water platform, and the curl (mm) of the four corners at this time was measured, and the total value was calculated.

[Young's coefficient evaluation]

The force curve was measured using an atomic force microscope (AFM), and the Young's coefficient on the surface of the hard shell surface was calculated by the following method.

AFM is Multimode 8 AFM manufactured by Bruker AXS, and the cantilever is OMCL-AC160TS-C2 [manufactured by Olympus] (spring constant (nominal value: 42N / m, measured by thermal rocking method: 32.7N / m)). 15nm].

First, by measuring the force curve, the cantilever is pressed into the hard shell layer, and then the cantilever is separated from the hard shell layer to obtain a relationship diagram (F-δ curve) showing the cantilever curvature and the displacement of the piezoelectric scanner. .

For the indentation process in the F-δ curve, Derjaguim, Muller, Toporov and DMT theory were used to perform curve fitting to obtain the local Young's coefficient E in the sample.

In this measurement, a force curve of 128 points × 128 points (16384 points) in the 1 μm × 1 μm plane of each sample was measured, and a Young's coefficient E was calculated.

The measurement results are shown in Figures 1 to 5.

As can be seen from Figures 1 to 5 and Table 1, As shown in FIG. 1, the hard shell layer of the laminated film (1) obtained in Example 1 has a continuous structure with a Young's coefficient of 1 to 5 GPa, and a region of Young's coefficient of 6 to 10 GPa is independently dispersed. The laminated film (1) has good transparency, high hardness, and excellent scratch resistance and flex resistance.

As shown in FIG. 2, the hard shell layer of the laminated film (2) obtained in Comparative Example 1 has a region with a Young's coefficient of 1 to 5 GPa that extends across the entirety. Although the laminated film (2) has good bending resistance, it has low hardness and poor abrasion resistance.

The hard shell layers of the laminated films (3) and (4) obtained in Comparative Examples 2 and 3 are shown in Figs. 3 and 4. The regions with a Young's coefficient of 6 to 10 GPa are not independent. Continuous construction. The laminated films (3) and (4) of the hard shell layer having this structure have poor bending resistance regardless of whether they contain the same or less inorganic filler content.

As shown in FIG. 5, the hard shell layer of the laminated film (5) obtained in Comparative Example 4 has a high Young's coefficient as a whole. Although the laminated film (5) has high hardness and good abrasion resistance, it has poor bending resistance.

Claims (1)

A laminated film comprising a substrate layer and a hard shell layer, wherein the hard shell layer is formed using a hard shell agent containing the following component (A), component (B), and component (C), and the hard shell layer is measured using an atomic force microscope The Young's coefficient on the surface. The area with a Young's coefficient of 1 to 5 GPa is a continuous structure, and the area with a Young's coefficient of 6 to 10 GPa is an independent dispersion. Component (A): an organosilicon compound having a reactive functional group and a hydrolyzable group. Component (B): a polythiol compound; Component (C): an inorganic filler having a reactive functional group.