JPWO2017150422A1 - Hard coating agent and laminated film - Google Patents

Abstract

The present invention is a laminated film having a hard coat agent containing the following component (A), component (B), and component (C), and a hard coat layer formed using the hard coat agent.
(A) component: organosilicon compound having reactive functional group and hydrolyzable group (B) component: polythiol compound (C) component: inorganic filler having reactive functional group According to the present invention, the hardness is high, and There are provided a hard coat agent capable of efficiently forming a hard coat layer excellent in scratch resistance and flex resistance, and a laminated film having a hard coat layer formed using this hard coat agent.

Description

  The present invention relates to a hard coat agent that can efficiently form a hard coat layer having high hardness and excellent scratch resistance and flex resistance, and a laminated film having a hard coat layer formed using this hard coat agent About.

In recent years, display devices such as various displays have a touch panel and are increasingly used as data input devices.
When using such a touch panel, a pen or a finger is usually brought into contact with the surface of the touch panel. Therefore, the surface of the touch panel is required not to be damaged even if contact with a pen or a finger is repeated.
For this reason, conventionally, providing the hard-coat layer in the resin film which comprises a touchscreen has been performed.

  For example, Patent Document 1 describes a resin composition for forming a transparent coating layer containing an organosilicon compound having a reactive functional group and a polythiol compound, and a method for forming a transparent coating using this resin composition. Has been. This document also describes that a transparent film formed using the resin composition is excellent in flexibility, hardness, scratch resistance, and wear resistance.

International Publication No. 2010/103944 Pamphlet

As described above, Patent Document 1 describes that the transparent film is excellent in flexibility, hardness, scratch resistance, wear resistance, and the like.
However, in order to form such a transparent film, it is necessary to sufficiently cure the resin composition, and depending on the curing conditions, it may not be possible to form a transparent film having the desired performance.

  The present invention has been made in view of the above circumstances, and uses a hard coat agent capable of efficiently forming a hard coat layer having high hardness and excellent scratch resistance and flex resistance, and the hard coat agent. It aims at providing the laminated film which has the hard-coat layer formed in this way.

  In order to solve the above-mentioned problems, the present inventors diligently studied hard coat agents. As a result, by using a hard coat agent containing an organic silicon compound having a reactive functional group and a hydrolyzable group, a polythiol compound, and an inorganic filler having a reactive functional group, the hardness is high and the scratch resistance is high. The present inventors have found that a hard coat layer having excellent resistance can be efficiently formed, and have completed the present invention.

  Thus, according to the present invention, the following hard coating agents (1) to (3) and the laminated film (4) are provided.

(1) A hard coat agent containing the following component (A), component (B), and component (C).
(A) Component: Organosilicon compound having reactive functional group and hydrolyzable group (B) Component: Polythiol compound (C) Component: Inorganic filler having reactive functional group (2) Content of component (B) Is a hard-coat agent as described in (1) which is 50-120 mass% with respect to (A) component.
(3) The hard-coat agent as described in (1) or (2) whose content of the said (C) component is 30-130 mass% with respect to (A) component.
(4) A laminated film having a base material layer and a hard coat layer,
A laminated film in which the hard coat layer is formed using the hard coat agent according to any one of (1) to (3).

  ADVANTAGE OF THE INVENTION According to this invention, the hard-coat agent which can form efficiently the hard-coat layer which is high in hardness, and is excellent in abrasion resistance and bending resistance, and the hard-coat layer formed using this hard-coat agent A laminated film having is provided.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a hard coat agent and 2) a laminated film.

1) Hard coat agent The hard coat agent of this invention contains the following (A) component, (B) component, and (C) component.
(A) Component: Organosilicon compound having reactive functional group and hydrolyzable group (B) Component: Polythiol compound (C) Component: Inorganic filler having reactive functional group

  The hard coat agent of the present invention contains an organosilicon compound having a reactive functional group and a hydrolyzable group (hereinafter sometimes referred to as “organosilicon compound (A)”) as the component (A).

The reactive functional group in the organosilicon compound (A) refers to a group that can react with the mercapto group of the component (B) to form a chemical bond.
Examples of the reactive functional group include a group having a carbon-carbon unsaturated bond such as a vinyl group, an allyl group, a styryl group, and a (meth) acryloyloxy group; an epoxy group; an isocyanate group; a mercapto group; 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) refers to a group that can form a siloxane bond (Si—O—Si bond) by hydrolysis reaction.
Examples of the hydrolyzable group include alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group and n-propoxy group, preferably 1 to 5 carbon atoms; 6 to 15 carbon atoms such as phenoxy group, preferably 6 to 10 carbon atoms. An acyloxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms such as a formyloxy group, an acetoxy group and a propionyloxy group; a halogen atom such as a chlorine atom and a bromine atom; Among these, a C1-C10 alkoxy group or a C1-C10 acyloxy group is preferable, and a C1-C10 acyloxy group is more preferable.

  Examples of the organosilicon compound (A) include compounds represented by the following formula (I).

In the formula (I), R ¹ represents a group having a reactive functional group, R ² represents a hydrolyzable group, and R ³ represents 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 the sum of x, y and z is 4.
When x, y, or z is 2 or more, the plurality of R ¹ , R ^2, or R ³ may be the same or different from each other.

Examples of R ¹ include a reactive functional group and a group having a reactive functional group. Specific examples thereof include a group having a vinyl group such as a vinyl group and a vinyloxymethyl group; a group having an allyl group such as an allyl group and an allyloxymethyl group; a group having a styryl group such as a styryl group and a styrylmethyl group. A group having a (meth) acryloyl group such as a (meth) acryloyl group or a 3- (meth) acryloyloxypropyl group; a group having an epoxy group such as an epoxy group, a glycidyl group or a 3-glycidyloxypropyl group; an isocyanate group; A group having an isocyanate group such as a 3-isocyanatopropyl group; a group having a mercapto group such as a mercapto group or a 3-mercaptopropyl group; Among these, a group having a carbon-carbon unsaturated bond is preferable, and a vinyl group is more preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group (the same applies hereinafter).
R ¹ preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.

Examples of R ² include the hydrolyzable group.
R ² preferably has 0 to 15 carbon atoms, more preferably 0 to 10 carbon atoms.

R ³ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; Preferably 6-15 aryl groups; etc. are mentioned.

As the organosilicon compound (A), vinyl group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, and vinyltribromosilane; allyltrimethoxysilane, allyltriethoxysilane, Allyl group-containing silane compounds such as allyltriacetoxysilane, allyltrichlorosilane, and allyltribromosilane; γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ-acrylic Γ-acryloxyalkyl group-containing silane compounds such as loxypropyltribromosilane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy Γ-methacryloxyalkyl group-containing silane compounds such as propyltrichlorosilane and γ-methacryloxypropyltribromosilane; α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyl Trimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxyethyltrichlorosilane, α-glycidoxyethyltribromosilane, β-glycidoxyethyltrichlorosilane, β-glycidoxyethyltribromo And epoxy group-containing silane compounds such as silane;
Among these, as the organosilicon compound (A), a vinyl group-containing silane compound is preferable, and vinyltriacetoxysilane is more preferable.
An organosilicon compound (A) can be used individually by 1 type or in combination of 2 or more types.

The hard coat agent of the present invention contains a polythiol compound as the component (B).
By using a hard coat agent containing a polythiol compound in addition to the organosilicon compound (A), a hard coat layer having excellent transparency, high pencil hardness, and excellent flex resistance can be formed.

The polythiol compound is a compound having two or more mercapto groups in the molecule.
Examples of polythiol compounds include compounds having 2 mercapto groups such as ethylene bis (mercaptoacetate) and ethylene bis (3-mercaptopropionate); trimethylol ethane tris (mercapto acetate), trimethylol ethane tris (3-mercaptopropio) Compound) such as pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropio) ), Dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), and the like. And the like are; compound.

Among these, as the polythiol compound, a compound having 3 mercapto groups or a compound having 4 or more mercapto groups is preferable, and trimethylolpropane tris (mercaptopropionate) is more preferable.
A polythiol compound can be used individually by 1 type or in combination of 2 or more types.

The content of the polythiol compound is not particularly limited. Content of a polythiol compound is 50-120 mass% normally with respect to (A) component, Preferably it is 60-100 mass%, More preferably, it is 60-90 mass%.
If a hard coat layer is formed using a hard coat agent with too little polythiol compound content, curling may occur in the laminated film. On the other hand, if a hard coat agent containing too much polythiol compound is used, it may be difficult to form a hard coat layer having high hardness.

The hard coat agent of the present invention refers to an inorganic filler having a reactive functional group as the component (C) (an inorganic filler having a reactive functional group introduced on the surface by a modification treatment. (Sometimes referred to as “inorganic filler (C)”).
By using a hard coat agent containing an inorganic filler (C) in addition to the organosilicon compound (A) and the polythiol compound, it has excellent transparency, high pencil hardness, flex resistance, scratch resistance, curling property. A hard coat layer excellent in all of the above can be formed.

  The reactive functional group contained in the inorganic filler (C) refers to a group that can react with the mercapto group of the component (B) to form a chemical bond. Examples of the reactive functional group include the same functional groups as those shown as the reactive functional group of the organosilicon compound (A). Among these, a group having a carbon-carbon unsaturated bond is preferable, and a (meth) acryloyloxy group is more preferable.

  Examples of the inorganic component constituting the inorganic filler (C) (component of the inorganic filler before modification treatment) include metal oxides, metal hydroxides, and metal salts.

Examples of the metal oxide include silica, titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, and zinc oxide.
Examples of the metal hydroxide include aluminum hydroxide.
Examples of the metal salt include 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, as an inorganic component which comprises an inorganic filler (C), a metal oxide is preferable and a silica is more preferable.

  The shape of the inorganic filler (C) may be any of a spherical shape, a chain shape, a needle shape, a plate shape, a piece shape, a rod shape, a fiber shape, and the like, but a spherical shape is preferable. Here, the spherical shape means a substantially spherical shape including a polyhedron shape that can be approximated to a spherical shape, a spheroidal shape, an oval shape, a confetti shape, an eyebrow shape, and the like.

The magnitude | size of an inorganic filler (C) is not specifically limited. The average particle diameter of the inorganic filler (C) is usually 5 to 1000 nm, preferably 7 to 500 nm, more preferably 10 to 100 nm, and particularly preferably 10 to 30 nm.
When the average particle diameter of the inorganic filler (C) is within the above range, a hard coat layer having excellent transparency and scratch resistance can be efficiently formed.
The average particle diameter of the inorganic filler (C) can be calculated using the specific surface area obtained by the BET method.

  In the hard coat agent of the present invention, the inorganic filler (C) can be used alone or in combination of two or more.

The content of the inorganic filler (C) is not particularly limited. Content of an inorganic filler (C) is 30-130 mass% normally with respect to (A) component, Preferably it is 60-125 mass%.
In particular, when a hard coat agent having a content of the inorganic filler (C) of 90 to 125% by mass with respect to the component (A) is used, a hard coat layer having high hardness is easily formed.
Moreover, when the content of the inorganic filler (C) is 90 to 125% by mass with respect to the component (A), a hard coat layer having excellent scratch resistance can be easily formed.

  The hard coat agent of the present invention may contain other components in addition to the component (A), the component (B), and the component (C) as long as the effects of the present invention are not impaired. Examples of other components include a solvent and a photopolymerization initiator.

Since the hard coat agent containing a solvent is excellent in coatability, a thin hard coat layer can be efficiently formed by using a hard coat agent containing a solvent.
Solvents include aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as methylene chloride and ethylene chloride; methanol, ethanol, propanol, Alcohol solvents such as butanol and 1-methoxy-2-propanol; Ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone and isophorone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve such as ethyl cellosolve System solvents and the like.
A solvent can be used individually by 1 type or in combination of 2 or more types.

  When the hard coat agent of the present invention contains a solvent, the content of the solvent is preferably such that the solid content concentration of the hard coat agent of the present invention is 30 to 95% by mass or more, and is an amount that makes 35 to 90% by mass. Is more preferable, and an amount of 40 to 85% by mass is even more preferable.

By using a hard coating agent containing a photopolymerization initiator, the resulting coating film can be efficiently cured after coating the hard coating agent.
Examples of the photopolymerization initiator include 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-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzof Non, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, and the like.
A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  When the hard-coat agent of this invention contains a photoinitiator, content of a photoinitiator is 0.01-10 mass% normally with respect to the solid content whole quantity of a hard-coat agent, Preferably it is 0.00. 5 to 10% by mass.

The hard coat agent of this invention contains the said (A) component, (B) component, and (C) component. The reactive functional group contained in the component (A) or the component (C) can react with the mercapto group contained in the component (B), and can react with these reactive functional groups. It is.
As described above, since the hard coat agent of the present invention can use both a reaction involving a mercapto group and a reaction not involving a mercapto group, the use of the hard coat agent of the present invention provides high hardness and resistance. A hard coat layer having excellent scratch resistance can be formed.

In addition, when the reactive functional groups are reacted with each other, it is usually necessary to irradiate or heat active energy rays such as ultraviolet rays or electron beams, so that the reactive functional group and the mercapto group The reaction proceeds faster than the reaction between reactive functional groups. The reaction between the reactive functional group and the mercapto group is an addition reaction, and even if this reaction occurs, the hard coat layer is unlikely to shrink.
On the other hand, if the reaction between the reactive functional groups occurs more than necessary, local curing shrinkage occurs, which may reduce optical properties and curl properties.
Accordingly, by appropriately adjusting the amount of the component (B) and using a hard coat agent in which there is not too much unreacted reactive functional group after the reaction between the reactive functional group and the mercapto group, optical characteristics are obtained. In addition, a hard coat layer having excellent curling properties and flex resistance can be formed.

2) Laminated film The laminated film of the present invention is a laminated film having a base layer and a hard coat layer, wherein the hard coat layer is formed using the hard coat agent of the present invention. And

The base material layer which comprises the laminated | multilayer film of this invention is used in order to hold | maintain a hard-coat layer.
The kind of base material layer is not specifically limited. For example, a synthetic resin film can be used as the base material layer.
Examples of the synthetic resin film include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polymethacrylic acid. Examples of the film include methyl, polymethyl acrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, and polycarbonate.

  In the present invention, a primer layer may be provided on at least one surface of the base material layer. The primer layer is not particularly limited as long as it has good adhesion to the hard coat layer provided thereon and adhesion to the base material layer. As the primer layer, conventionally known 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 a primer layer is 0.01-20 micrometers normally, Preferably, it is 0.1-15 micrometers.

The thickness of a base material layer (synthetic resin film) is not specifically limited, It can determine suitably according to the use etc. of a laminated film.
The thickness of a base material layer is 10-500 micrometers normally, Preferably it is 20-200 micrometers.

The hard coat layer constituting the laminated film of the present invention is formed using the hard coat agent of the present invention.
The thickness of the hard coat layer is usually 0.1 to 50 μm, preferably 0.5 to 20 μm.

  The hard coat layer can be formed by applying the hard coat agent of the present invention on the synthetic resin film (or primer layer) for the base material layer and curing the obtained coating film.

  There is no restriction | limiting in particular as a method of coating a hard-coat agent on a synthetic resin film (or primer layer), A well-known method is employable. For example, roll coating method, curtain flow coating method, Mayer bar coating method, reverse coating method, gravure coating method, gravure reverse coating method, air knife coating method, kiss coating method, blade coating method, smooth coating method, roll knife coating method, etc. Is mentioned.

The method for curing the coating film is not particularly limited. For example, the coating film can be cured by irradiating the coating film with active energy rays such as ultraviolet rays and electron beams.
Ultraviolet irradiation can be performed by a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, or the like. The dose of ultraviolet rays, illuminance 50~1000mW / cm ^2, about the amount of light 50~1000mJ / cm ² is preferred. On the other hand, the electron beam irradiation can be performed by an electron beam accelerator or the like. The irradiation amount of the electron beam is preferably about 10 to 1000 krad.

When forming a hard-coat layer, you may perform a drying process before hardening of a coating film or after hardening of a coating film as needed.
Drying process conditions are not particularly limited. The drying temperature is, for example, 40 to 150 ° C., preferably 60 to 140 ° C., and the drying time is, for example, 30 seconds to 1 hour, preferably 1 to 30 minutes.

The hard coat layer is formed using the hard coat agent of the present invention, and has high hardness and excellent scratch resistance.
The hard coat layer constituting the laminated film of the present invention usually exhibits a hardness of F or higher and preferably H or higher when a pencil scratch hardness test is performed according to the method described in the examples.
When the hard coat layer constituting the laminated film of the present invention is evaluated for scratch resistance according to the method described in the examples, scratches are usually not observed.

The laminated film of the present invention is preferably excellent in transparency. 89% or more is preferable and 90% or more is more preferable when the laminated film of this invention measures a total light transmittance. Although there is no upper limit in particular, it is usually 95% or less.
The laminated film of the present invention preferably has excellent bending resistance. When the laminated film of the present invention is subjected to a mandrel bending test according to JIS K5600-5-1, it is preferably 4 mmΦ or less, more preferably 2 mmΦ or less.
The laminated film of the present invention is preferably one having little warpage. When the curl property of the laminated film of the present invention is evaluated according to the method described in Examples, it is usually 110 mm or less, preferably 50 mm or less. Although there is no lower limit in particular, it is usually 3.5 mm or more.

  These laminated films excellent in optical properties, flex resistance, and curling properties are adjusted as described above by adjusting the amounts of the (A) component, (B) component, and (C) component, and the (A) component and (C) It can manufacture by not causing reaction of the reactive functional groups which a component has more than necessary.

  The laminated film of the present invention has a hard coat layer having high hardness and excellent scratch resistance and flex resistance, and is suitably used as a touch panel manufacturing material.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.

The compounds used in Examples and Comparative Examples are shown below.
-Solution (A1) of organosilicon compound (vinyltriacetoxysilane) (manufactured by Sakai Chemical Co., Ltd., trade name: SHC-001B, concentration 90%)
-Solution (B1) of polythiol compound [trimethylolpropane tris (3-mercaptopropionate)] (manufactured by Sakai Chemical Co., Ltd., trade name: SHC-001A, concentration 60%)
Inorganic filler (silica nanofiller having acryloyloxy group) dispersion (C1) (manufactured by Nissan Chemical Industries, trade name: AC-4130Y, concentration 30%, average particle size 40-50 nm)
Inorganic filler (silica nanofiller having acryloyloxy group) dispersion (C2) (manufactured by Nissan Chemical Industries, trade name: AC-2140Z, concentration 40%, average particle size 10-15 nm)

[Example 1]
110 parts of the organosilicon compound solution (A1), 100 parts of the polythiol compound solution (B1) and 119 parts of the inorganic filler dispersion (C1) were mixed, and the resulting mixture was diluted with methyl ethyl ketone to obtain a solid content concentration of 45. % Hard coating agent (1) was prepared.
Apply a hard coat agent (1) to a polyethylene terephthalate film with a single-sided primer layer (manufactured by Toyobo Co., Ltd., trade name: PET50A4100, thickness 50 μm) using a Mayer bar # 10 so that the film thickness after curing is 5 μm. The coated film was cured by irradiating with ultraviolet rays (light quantity: 500 mJ / cm ² ). Next, the cured coating film was dried at 120 ^° C. for 20 minutes to form a hard coat layer to obtain a laminated film (1).

[Examples 2 to 9, Comparative Example 1]
In Example 1, in place of the hard coat agent (1), hard coat agents (2) to (10) having the compositions shown in Table 1 were prepared, and this was used to produce a laminated film. In the same manner as in Example 1, laminated films (2) to (10) were obtained.

  The laminated film obtained in Examples 1 to 9 and Comparative Example 1 was evaluated as follows. The results are shown in Table 1. In Table 1, “concentration” means “solid content concentration”.

[Thickness evaluation]
The thickness of the hard coat layer was measured according to JIS K 7130 (1999) using a thickness meter (trade name: MH-15, manufactured by Nikon Corporation).

[Total light transmittance]
Using a haze meter (Nippon Denshoku Co., Ltd., trade name: N-DH-2000), the total light transmittance of the laminated film was measured according to JIS K 7361-1 (1997).

[Pencil hardness]
Using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., trade name: No. 553-M) according to JIS K5600-5-4 (1999), a pencil with a load of 750 g and a scratching speed of 0.5 mm / sec. A scratch hardness test was conducted.

[Abrasion resistance evaluation]
The hard coat layer of the laminated film is rubbed 10 times in a 50 mm length range with a load of 250 g / cm ² using steel wool # 0000, and then visually checked for the presence or absence of scratches. Evaluated.
A: There is no scratch.
A: There are about 1 to 2 scratches.
X: There are innumerable scratches.

[Bend resistance evaluation]
In accordance with JIS K5600-5-1 (1999), a mandrel bending test was performed to evaluate the bending resistance of the laminated film.

[Curl evaluation]
The laminated film was cut into a 10 cm side square and used as a test piece. The test piece was placed on a horizontal table, and the floating (mm) at the four corners at this time was measured, and the total value was calculated.

From Table 1, the following can be understood.
The hard coat layers of the laminated films (1) to (9) obtained in Examples 1 to 9 are excellent in transparency, high in hardness, and excellent in scratch resistance and flex resistance.
In addition, the laminated films (5), (6), and (9) obtained in Examples 5, 6, and 9 have small warpage.
On the other hand, the laminated film (10) obtained in Comparative Example 1 has low hardness and inferior scratch resistance.

Claims (4)

The hard-coat agent containing the following (A) component, (B) component, and (C) component.
(A) Component: Organosilicon compound having reactive functional group and hydrolyzable group (B) Component: Polythiol compound (C) Component: Inorganic filler having reactive functional group   The hard-coat agent of Claim 1 whose content of the said (B) component is 50-120 mass% with respect to (A) component.   The hard-coat agent of Claim 1 or 2 whose content of the said (C) component is 30-130 mass% with respect to (A) component. A laminated film having a base layer and a hard coat layer,
A laminated film in which the hard coat layer is formed using the hard coat agent according to any one of claims 1 to 3.