TWI730055B - Laminated film - Google Patents

Abstract

The present invention is a laminated film comprising a substrate layer and a hard shell layer. The hard shell layer is formed using a hard shell agent containing the following components (A), component (B), and component (C), and the hard shell layer is measured using an atomic force microscope For the Young's coefficient of the surface, the area with Young's coefficient of 1~5GPa is a continuous structure, and the area with Young's coefficient of 6-10GPa 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 present invention provides a laminated film of a hard shell layer with high hardness, scratch resistance and good bending resistance.

Description

Laminated film

The present invention relates to a laminated film of a hard shell layer with high hardness, scratch resistance and good bending resistance.

In recent years, various displays and other display devices are equipped with touch screens, which are mostly used as data input devices.

When using this touch screen, a pen or finger is usually used to touch the surface of the touch screen. 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 the resin film constituting the touch screen.

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

【Prior Technical Literature】 【Patent Literature】

Patent Document 1: International Patent No. 2010/103944

As can be seen from the above, Patent Document 1 describes that its clear coating has good flexibility, hardness, scratch resistance, abrasion resistance, and the like.

However, in order to form this clear coating, the resin composition must be sufficiently cured, but depending on the curing conditions, it is impossible to form a clear coating with desired characteristics.

In view of this, the object of the present invention is to provide a hard-shell laminated film with high hardness, scratch resistance, and good bending resistance.

In order to solve the above-mentioned problems, the inventors have extensively studied hard shell agents. As a result, it was found that the use of a hard shell agent containing organic silicon compounds with reactive functional groups and hydrolyzable groups, polythiol compounds, and inorganic fillers with reactive functional groups can effectively form high hardness and good properties. Scratch-resistant hard shell layer. In addition, adding an inorganic filler to the hard shell layer will reduce the bending resistance of the hard shell layer. However, by controlling the dispersion state of the inorganic filler in the hard shell layer, the decrease in the bending resistance can be suppressed.

Based on this finding, the present invention has been completed.

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

(1) A laminated film comprising a base layer and a hard shell layer. The hard shell layer is formed using a hard shell agent containing the following components (A), (B), and (C), using an atomic force microscope Measure the Young's coefficient on the surface of the hard shell layer. The area with Young's coefficient of 1~5GPa is a continuous structure, and the area with Young's coefficient of 6-10GPa 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 present invention provides high hardness, scratch resistance and good bending resistance Good hard-shell laminated film.

Figure 1 is the Young's coefficient mapping image of the laminated film (1) obtained in Example 1.

Figure 2 is the Young's coefficient mapping image of the laminated film (2) obtained in Comparative Example 1.

Figure 3 is the Young's coefficient mapping image of the laminated film (3) obtained in Comparative Example 2.

Figure 4 is the Young's coefficient mapping image of the laminated film (4) obtained in Comparative Example 3.

Figure 5 is the Young's coefficient mapping image of the laminated film (5) obtained in Comparative Example 4.

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

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

The synthetic resin film can be selected from, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene/vinyl acetate copolymer, ethylene/vinyl alcohol copolymer, polyethylene terephthalate, poly Butylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, polycarbonate And other films.

In the present invention, a primer layer is provided on at least one surface of the above-mentioned base material layer. The primer layer is a substance that has good adhesion to the hard shell layer provided thereon and good adhesion to the substrate layer, and its type is not particularly limited. The primer layer may use a conventional primer layer such as an acrylic primer layer, a polyester primer layer, a polyurethane primer layer, a silicone primer layer, and a rubber primer layer.

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

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

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

The hard shell agent (α) contains as 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 that can react with the sulfhydryl group of the component (B) to form a chemical bond.

This reactive functional group can be selected from groups containing carbon-carbon unsaturated bonds such as vinyl, allyl, styryl, (meth)acryloxy, etc.; epoxy groups; isocyanates; mercapto groups, etc. Among them, a group having a carbon-carbon unsaturated bond is preferred, and a vinyl group is more preferred.

The hydrolyzable group in the organosilicon compound (A) is a group that can form a siloxane bond (Si-O-Si bond) by a hydrolysis reaction

The hydrolyzable group can be selected from methoxy, ethoxy, n-propoxy and other alkoxy groups with carbon numbers of 1 to 10, preferably 1 to 5; carbon numbers such as phenoxy group are 6 to 15, preferably It is an aryloxy group of 6~10; carbon number 1~10 such as formoxy, acetoxy, propoxy, etc. Preferably, they are 1 to 5 acyloxy groups; halogen atoms such as a chlorine atom and a bromine atom. Among these, an alkoxy group having 1 to 10 carbons or an acyloxy group having 1 to 10 carbons is preferable, and an acyloxy group having 1 to 10 carbons is more preferable.

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 selected from a reactive functional group or a group having a reactive functional group. Specific examples can be selected from groups having vinyl groups such as vinyl and ethyleneoxymethyl; groups having allyl groups such as allyl and allyloxymethyl; styryl and styrylmethyl Groups having a styryl group; groups having a (meth)acryloyl group such as (meth)acryloyl group, 3-(meth)acryloyloxypropyl group, etc.; epoxy group, glycidyl group , 3-glycidoxypropyl and other groups having epoxy groups; groups having isocyanate groups such as isocyanate groups and 3-isocyanate propyl groups; groups having mercapto groups such as mercapto groups and 3-mercaptopropyl groups. Among them, a group having a carbon-carbon unsaturated bond is preferred, and a vinyl group is more preferred.

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

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

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

R ³ can be selected from methyl, ethyl, n-propyl, isopropyl and other alkyl groups with carbon numbers 1-20, preferably 1-15; phenyl; 1-naphthyl, etc. carbon numbers 6-20 , Preferably 6-15 aryl groups and the like.

The organosilicon compound (A) can be selected from vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, vinyl tribromosilane, etc. containing vinyl groups Silane compounds; allyl trimethoxysilane, allyl triethoxy silane, allyl triethoxy silane, allyl trichlorosilane, allyl tribromosilane, and other allyl-containing silanes Compounds; γ-acryloxypropyl trimethoxysilane, γ-acryloxypropyl triethoxysilane, γ-acryloxypropyl trichlorosilane, γ-acryloxypropyl tribromosilane, etc. Silane compounds of γ-propylene oxyalkyl group; γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl trichloride Silane, γ-methacryloxypropyltribromosilane and other silane compounds containing γ-methacrylic acid alkyl groups; α-epoxypropylethyltrimethoxysilane, α-epoxypropylethyltri Ethoxysilane, β-epoxypropylethyltrimethoxysilane, β-epoxypropylethyltriethoxysilane, α-epoxypropylethyltrichlorosilane, α-epoxypropyl Ethyltribromosilane, β-epoxypropylethyltrichlorosilane, β-epoxypropylethyltribromosilane and other epoxy-containing silane compounds, etc.

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

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

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

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

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

Polythiol compounds can be selected from compounds with 2 mercapto groups such as ethylenebis(thioglycolic acid) and ethylenebis(3-mercaptopropionic acid); trimethylolethane tris(thioglycolic acid), trihydroxymethyl Methyl ethane tris (3-mercaptopropionic acid), trimethylolpropane tris (thioglycolic acid), trimethylolpropane tris (3-mercaptopropionic acid) and other compounds with mercapto groups of 3; neopentylerythritol tetra (Mercaptoacetic acid), Neopentyl erythritol tetra (3-mercaptopropionic acid), Dine pentaerythritol hexa (mercaptoacetic acid), Dine pentaerythritol hexa (3-mercaptopropionic acid) and other compounds with a mercapto group number of 4 or more .

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

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

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

If a hard shell agent with too little polythiol compound content is used to form a hard shell layer, curling of the laminated film may occur. In addition, it may be difficult to form a hard shell layer with high hardness by using an excessive amount of the hard shell agent of the polythiol compound.

The hard shelling agent (α) contains an inorganic filler with reactive functional groups as component (C) (inorganic filler in which reactive functional groups are introduced on the surface after modification, and component (C) is referred to as "inorganic filler" below.物(C)”).

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

The reactive functional group possessed by the inorganic filler (C) is The sulfhydryl group of (B) forms a chemically bonded group. The 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 preferred, and a (meth)acryloxy group is more preferred.

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

The metal oxide can be selected from silicon dioxide, titanium dioxide, alumina, diaspore, chromium oxide, nickel oxide, copper oxide, titanium dioxide, zirconium oxide, 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 them, the inorganic component constituting the inorganic filler (C) is preferably a metal oxide, more preferably silicon dioxide.

Although the shape constituting the inorganic filler (C) may be any of spherical, chain, needle, plate, sheet, rod, fibrous, etc., it is preferably spherical. In the present invention, the so-called spherical shape includes, in addition to the true spherical shape, a polyhedral-like spherical shape similar to a spherical body, such as a revolving ellipse, an oval shape, a sugar shape, a cocoon shape, and the like.

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

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

The average particle size 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 can be used alone or in combination of two or more.

The content of the inorganic filler (C) is not particularly limited. The content of the inorganic filler (C) relative 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.

Using a hard shell agent whose content of the inorganic filler (C) is 90 to 125% by mass relative to the component (A) makes it easy to form a hard shell layer with high hardness.

Using a hard shell agent with an inorganic filler (C) content of 90 to 125% by mass relative to the component (A), it is easy to form a hard shell layer with 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 components may be solvents or photopolymerization initiators.

Solvent-containing hard shell agents are easy to coat and apply. Using solvent-containing hard shell agents 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 hydrocarbon solvents such as dichloromethane and dichloroethane; methanol, ethanol, Alcohol solvents such as propanol, butanol, 1-methoxy-2-propanol; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, isophorone, etc. ; Ester solvents such as ethyl acetate and butyl acetate; celluloid solvents such as ethyl cellulose.

The solvent may be used alone 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 of the solid content concentration of the hard shell agent (α), more preferably 35 to 90% by mass, and most preferably 40 to 85 mass% %.

The use of a hard shell agent containing a photopolymerization initiator can effectively harden the obtained coating after the hard shell agent is applied.

The photopolymerization initiator can be selected from, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2 ,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one , 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylsulfide)phenyl]-2-morpholine-propane-1-one, 4-(2-hydroxyethoxy)benzene 2-(hydroxy-2-propyl) ketone, benzophenone, p-phenyl benzophenone, 4,4'-diethylamino benzophenone, dichloro benzophenone, 2- Methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amine anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2 ,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, etc. .

The photopolymerization initiator may be used alone 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 solid content of the hard shell agent is usually 0.01-10% by mass, preferably 0.5-10% by mass.

The thickness of the hard shell layer constituting the laminate film of the present invention is usually 0.1-50 μm, preferably 0.5-20 μm.

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

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

"The area with Young's coefficient of 6-10 GPa is dispersed independently" means that the area with Young's coefficient of 6-10 GPa is dispersed in the whole (that is, the same part of the island structure is formed in the island structure).

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

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

The regions with Young's coefficient of 6-10 GPa are each one by one, preferably nano-level. For example, when drawing an inscribed square or rectangle in this area, the side length is preferably 10-100 nm, preferably 40-60 nm.

As explained below, the amount of component (A), component (B), and component (C) in the hard shell agent (α) can be adjusted 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 reacts with these reactive functional groups with each other.

If it is mainly the reaction between the reactive groups of the component (C), a part of the component (C) will agglomerate and cannot form a hard shell layer with the desired structure.

However, the amount of component (B) that can sufficiently react the mercapto group of component (B) with the reactive functional group of component (A) or component (C) can improve the dispersibility of 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 unlikely to cause shrinkage of the hard shell layer. In addition, if more than necessary reactive functional groups react with each other, it will cause local hardening. Chemical shrinkage, lower optical properties, and curl.

In this regard, in order to carry out the reaction between the above-mentioned reactive functional groups, it is usually necessary to irradiate active energy beams such as ultraviolet rays or electron beams, and heat. fast. However, if necessary, the stages of irradiating active energy beams such as ultraviolet rays or electron beams and heating can be analyzed and studied to effectively form a hard shell layer with desired characteristics.

Therefore, corresponding to the amount of the reactive functional group contained in the component (A) or the component (C), use an appropriate amount of the component (B) to sufficiently react the reactive functional group with the mercapto group to form a structure having the above-mentioned structure, optical properties, Good bending resistance, hard shell layer that is not prone to curling.

The laminated film of the present invention is, for example, coated with a hardening agent (α) directly or through another layer on the synthetic resin forming the base layer, and the obtained coating layer is hardened to produce the laminated film.

The method of coating the hard shell agent on the synthetic resin is not particularly limited, and conventional methods can be used. Such as roller coating, curtain flow coating, Meeller rod coating, reverse coating, gravure coating, reverse gravure coating, pneumatic knife coating, contact coating, knife coating, smoothing Coating, roller blade coating, etc.

The method of hardening the coating is not particularly limited. For example, active energy beams such as ultraviolet rays and electron beams can be irradiated to the coating to harden the coating.

Ultraviolet radiation can be carried out by high-pressure mercury lamp, fusion H lamp, xenon lamp, etc. 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, electron beam accelerators can be used to irradiate electron beams. The irradiation amount of the electron beam is preferably 10 to 1000 krad.

When the hard shell layer is formed, it can be before or after the coating is hardened Carry out the required drying treatment.

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

The hard shell layer can be formed by using the hard shell agent of the present invention, which has high hardness and good scratch resistance.

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

When the hard shell layer constituting the laminated film of the present invention is evaluated for scratch resistance according to the method of the examples, no damage is usually observed.

The laminated film of the present invention preferably has good transparency. When the total light transmittance of the laminated film of the present invention is measured, it is preferably 89% or more, more preferably 90% or more. The upper limit is not particularly limited, usually 95% or less

The laminated film of the present invention preferably has good bending resistance. The laminated film of the present invention is subjected to a mandrel bending test in accordance with the JIS K5600-5-1 standard, and the mandrel bending test is 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 bendability of the laminated film of the present invention is evaluated according to the method of the examples, and it is usually 75 mm or less, preferably 50 mm. The lower limit is not particularly limited, but it is usually 3.5 mm or more.

The laminated film of the present invention has a hard shell layer with high hardness, good scratch resistance and good bending resistance, and is suitable as a manufacturing material for touch panels.

[Examples]

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

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

Organosilicon compound (vinyl triacetoxysilane) 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%)

Inorganic filler (silica nanoparticle with acryloxy group) dispersion (C1) (manufactured by Nissan Chemical Industry Co., Ltd., trade name: AC-4130Y, concentration 30%, average particle size 40-50nm)

[Example 1]

Mix 110 parts of organosilicon compound solution (A1), 150 parts of polythiol compound (B1), 398 parts of inorganic filler dispersion (C1), and dilute the obtained mixed solution with methyl ethyl ketone to prepare concentration 45% hard shell agent (1).

On a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., trade name: PET50A4100, thickness 50μm) with a primer layer on one side, a #10 Myler bar was used to coat the primer layer and the film thickness was cured The hard shell agent (1) of 5 μm is irradiated with ultraviolet rays (exposure amount 500mJ/cm ² ) to harden the coating. Next, 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 the organosilicon compound solution (A1) and 100 parts of the polythiol compound solution (B1) were mixed, and the obtained mixed solution was diluted with methyl ethyl ketone to prepare a hard shell agent (2) with a concentration of 50%.

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

[Comparative Example 2]

Mix 110 parts of organosilicon compound solution (A1), 100 parts of polythiol compound solution (B1), 278 parts of inorganic filler dispersion (C1), and dilute the obtained mixed solution with methyl ethyl ketone to prepare Hard shell agent with a concentration of 50% (3).

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

[Comparative Example 3]

Mix 110 parts of organosilicon compound solution (A1), 100 parts of polythiol compound solution (B1), 333 parts of inorganic filler dispersion (C1), and dilute the obtained mixed solution with methyl ethyl ketone to prepare Hard shell agent with a concentration of 50% (4).

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

[Comparative Example 4]

Dilute the mixture of organically modified silica microparticles and polyfunctional acrylate with propylene glycol monomethyl ether (made by JSR, trade name: OPSTAR-Z7530, concentration 73%, containing photopolymerization initiator, 60% inorganic filler content) ) To prepare a hard shell agent (5) with a concentration of 40%.

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

The laminated films (1) to (5) obtained in Example 1 and Comparative Examples 1 to 4 were subjected to the following evaluations. The results are shown in Table 1.

[Thickness Evaluation]

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

[Total light transmittance]

Using a turbidity meter (manufactured by Nippon Denshoku Co., Ltd., trade name: N-DH-2000), the total light transmittance of the laminated film was measured in accordance with the JIS K7361-1 (1997) standard.

[Pencil Hardness]

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

[Scratch resistance evaluation]

Using a #0000 steel brush, ^{rubbing the hard shell layer of the laminated film over a length of 50 mm with a load of 250 g/cm 2} repeatedly 10 times, then visually confirm whether there is damage, and evaluate the scratch resistance based on the following criteria.

○: No scratches

×: There are scratches

[Assessment of Flexibility]

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

[Flexibility evaluation]

The laminated film was cut out to obtain a 10 cm square on one side, which was used as a test piece. Place this test piece on a water platform, measure the curl (mm) of the four corners at this time, and calculate the total value.

[Evaluation of Young's Coefficient]

Use the atomic force microscope (AFM) to measure the force curve, and use the following method to calculate the local Young's coefficient of the hard shell layer.

The AFM is the Multimode 8 AFM manufactured by Bruker AXS, the cantilever is the OMCL-AC160TS-C2 manufactured by Olympus [spring constant (nominal value 42N/m, thermal shake method measured value 32.7N/m), the tip radius of the probe is 15nm].

First, by measuring the force curve, pressing the cantilever into the hard shell layer, and then separating the cantilever from the hard shell layer, a graph showing the relationship between the curvature of the cantilever and the displacement of the piezoelectric scanner can be obtained. Then, it is transformed to obtain a graph (F-δ curve) showing the relationship between the load and the amount of deformation of the sample.

For the indentation process in the obtained F-δ curve, the DMT theory of Derjaguim, Muller, Toporov, etc. is used to perform curve fitting, thereby obtaining the local Young's coefficient E in the sample.

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

The measurement results are shown in Figures 1 to 5.

From Figures 1 to 5 and Table 1, we can see that The hard shell layer of the laminated film (1) obtained in Example 1 is as shown in Figure 1. The Young's coefficient 1 to 5 GPa area is a continuous structure, and the Young's coefficient 6 to 10 GPa area is independently dispersed. The laminated film (1) has good transparency, high hardness, and good scratch resistance and bending resistance.

The hard shell layer of the laminated film (2) obtained in Comparative Example 1 is as shown in Fig. 2, and the area with Young's coefficient of 1 to 5 GPa is enlarged to span the entirety. Although the laminated film (2) has good bending resistance, it has low hardness and poor scratch resistance.

The hard shell layers of the laminated films (3) and (4) obtained in Comparative Examples 2 and 3 are shown in Figures 3 and 4. The area with Young's coefficient of 6-10 GPa is not independent, and the area with Young's coefficient of 6-10 GPa is formed. Continuous construction. The hard-shell laminated films (3) and (4) with this structure, whether they contain the same or less inorganic filler content, have poor bending resistance.

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 scratch resistance, it has poor bending resistance.

Claims (3)

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 components (A), component (B), and component (C), wherein the hard shell agent contains The content of component (B) is 90.9 to 120% by mass relative to component (A), and the content of component (C) contained in the hard shell agent is 30 to 130% by mass relative to component (A). The content is measured using an atomic force microscope. The Young's coefficient on the surface of the hard shell layer. The area with Young's coefficient of 1 to 5 GPa is a continuous structure, and the area with Young's coefficient of 6 to 10 GPa is independently dispersed; component (A): with reactive functional groups and hydrolyzable groups An organosilicon compound, wherein the reactive functional group is selected from the group consisting of vinyl, allyl, styryl, (meth)acryloxy, epoxy, isocyanate and mercapto groups. The hydrolyzable group The group is selected from the group consisting of alkoxy, aryloxy, acyloxy and halogen atoms; component (B): polythiol compound; component (C): inorganic filler with reactive functional groups, wherein the The reactive functional group is selected from the group consisting of vinyl, allyl, styryl, (meth)acryloxy, epoxy, isocyanate and mercapto groups. The laminated film according to claim 1, wherein when a square or rectangle inscribed is drawn in the region with a Young's coefficient of 6-10 GPa, the side length is 10-100 nm. The laminated film as described in claim 1 or 2, in which, in accordance with JIS K5600-5-4 (1999), a pencil hardness test with a load of 750g and a moving speed of 0.5mm/sec, it shows a hardness of F or higher, and according to JIS According to the K5600-5-1 criterion, the mandrel bending test is carried out, and the value is less than 2mm Φ.

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