JP6914244B2 - Hard coating agent and laminated film - Google Patents

Description

The present invention is a hard coat agent capable of efficiently forming a hard coat layer having high hardness and excellent bending resistance, scratch resistance, antifouling property and slipperiness, and a hard coat agent formed by using this hard coat agent. The present invention relates to a laminated film having a hard coat layer.

In recent years, display devices such as various displays are provided with a touch panel and are often 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 the contact with the pen or the finger is repeated.
For this reason, conventionally, a hard coat layer has been provided on the resin film constituting the touch panel.

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

International Publication No. 2010/103944 Pamphlet

As described above, Patent Document 1 describes that the transparent coating film is excellent in flexibility, hardness, scratch resistance, abrasion 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.
Further, since the transparent film described in Patent Document 1 is inferior in antifouling property, there is a problem that the aesthetic appearance is deteriorated with time, and because it is inferior in slipperiness, the work efficiency at the time of manufacturing or using the laminated film is lowered. There was a problem.

The present invention has been made in view of the above circumstances, and is a hard coat capable of efficiently forming a hard coat layer having high hardness and excellent bending resistance, scratch resistance, stain resistance and slipperiness. It is an object of the present invention to provide an agent and a laminated film having a hard coat layer formed by using the hard coat agent.

The present inventors have diligently studied a hard coating agent in order to solve the above problems. As a result, a hard coat agent containing an organic silicon compound having a reactive functional group and a hydrolyzable group, a polythiol compound, an inorganic filler having a reactive functional group, and a polymer having a reactive functional group and a polysiloxane side chain. It has been found that a hard coat layer having high hardness and excellent scratch resistance, antifouling property and slipperiness can be efficiently formed by using the above, and the present invention has been completed.

Thus, according to the present invention, the following hard coating agents (1) to (4) and the following laminated film (5) are provided.

(1) A hard coating agent containing the following components (A), (B), (C), and (D).
Component (A): Organic silicon compound having a reactive functional group and a hydrolyzable group (B) Component: Polythiol compound (C) Component: Inorganic filler having a reactive functional group (D) Component: Reactive functional group and poly The hard coat agent according to (1), wherein the content of the polymer (2) component (B) having a siloxane side chain is 50 to 120% by mass with respect to the component (A).
(3) The hard coating agent according to (1) or (2), wherein the content of the component (C) is 30 to 120% by mass with respect to the component (A).
(4) The hard coating agent according to any one of (1) to (3), wherein the content of the component (D) is 1 to 5% by mass with respect to the component (A).
(5) A laminated film having a base material layer and a hard coat layer, wherein the hard coat layer is formed by using the hard coat agent according to any one of (1) to (4). the film.

According to the present invention, a hard coat agent having high hardness and capable of efficiently forming a hard coat layer having excellent bending resistance, scratch resistance, antifouling property and slipperiness, and this hard coat agent are used. A laminated film having a hard coat layer formed in the above is provided.

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

1) Hard coating agent The hard coating agent of the present invention contains the following components (A), (B), (C), and (D).
Component (A): Organosilicon compound having a reactive functional group and a hydrolyzable group (B) Component: Polythiol compound (C) Component: Inorganic filler having a reactive functional group (D) Component: Reactive functional group and poly Polymer with siloxane side chain

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

The reactive functional group in the organosilicon compound (A) refers to a group capable of reacting with the mercapto group of the component (B) to form a chemical bond.
Examples of this 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; 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) refers to a group capable of forming a siloxane bond (Si—O—Si bond) by a hydrolysis reaction.
The hydrolyzable group includes an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an n-propoxy group, preferably 1 to 5; an alkoxy group having 6 to 15 carbon atoms such as a phenoxy group, preferably 6 to 10 carbon atoms. Aryloxy group; an acyloxy group having 1 to 10 carbon atoms such as a formyloxy group, an acetoxy group and a propionyloxy group; preferably an acyloxy group having 1 to 5 carbon atoms; a halogen atom such as a chlorine atom and a bromine atom; and the like. Among these, an alkoxy group having 1 to 10 carbon atoms or an acyloxy group having 1 to 10 carbon atoms is preferable, and an acyloxy group having 1 to 10 carbon atoms is more preferable.

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

In 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 of these 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 and a 3- (meth) acryloyloxypropyl group; a group having an epoxy group such as an epoxy group, a glycidyl group and a 3-glycidyloxypropyl group; an isocyanate group, Examples thereof include a group having an isocyanate group such as 3-isocyanatopropyl group; a group having a mercapto group such as a mercapto group and a 3-mercaptopropyl group; and the like. 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, more preferably 2 to 10.

The R ^2, the hydrolyzable group.
The number of carbon atoms of R ² is preferably 0 to 15, more preferably 0-10.

As R ^3, a methyl group, an ethyl group, n- propyl group, having 1 to 20 carbon atoms such as isopropyl group, preferably 1 to 15 alkyl group; a phenyl group, 1-6-20 carbon atoms, such as naphthyl group, Preferably, 6 to 15 aryl groups; and the like.

Examples of the organic silicon compound (A) include vinyl group-containing silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, and vinyltribromosilane; allyltrimethoxysilane, allyltriethoxysilane, and the like. Allyl group-containing silane compounds such as allyltriacetoxysilane, allyltrichlorosilane, and allyltribromosilane; γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ-acry Γ-Acryloxyalkyl group-containing silane compounds such as loxypropyltribromosilane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, γ-methacryloxypropyltribromo Γ-Methyloxyalkyl group-containing silane compounds such as silane; α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltri Epoxy group-containing silane compounds such as ethoxysilane, α-glycidoxyethyl trichlorosilane, α-glycidoxyethyl tribromosilane, β-glycidoxyethyl trichlorosilane, β-glycidoxyethyl tribromosilane; etc. Can be mentioned.
Among these, as the organosilicon compound (A), a vinyl group-containing silane compound is preferable, and vinyl triacetoxysilane is more preferable.
The organosilicon compound (A) can be used alone or in combination of two or more.

The hard coat agent of the present invention contains a polythiol compound as the component (B).
The polythiol compound refers to a compound having two or more mercapto groups in the molecule.

Examples of the polythiol compound include compounds having 2 mercapto groups such as ethylenebis (mercaptoacetate) and ethylenebis (3-mercaptopropionate); trimethylolethanetris (mercaptoacetate) and trimethylolethanetris (3-mercaptopropionate). Nate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) and other compounds with 3 mercapto groups; pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropioate) Nate), dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate) and other compounds with 4 or more mercapto groups; and the like.

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

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 the hard coat layer is formed by using a hard coat agent containing too little a polythiol compound, the laminated film may be curled. On the other hand, if a hard coat agent containing too much polythiol compound is used, the hard coat layer may have poor scratch resistance, or 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) (meaning an inorganic filler in which a reactive functional group is introduced into the surface by a modification treatment. Hereinafter, the component (C) is used. It may be referred to as "inorganic filler (C)"). By using a hard coat agent containing an inorganic filler (C), a hard coat layer having excellent scratch resistance can be formed.

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

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

Examples of the metal oxide include silica, titanium oxide, alumina, boehmite, chromium oxide, nickel oxide, copper oxide, titanium oxide, zirconium oxide, indium oxide, zinc oxide and the like.
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; and metal silicates such as aluminum silicate, calcium silicate and magnesium silicate; and the like.
Among these, as the inorganic component constituting the inorganic filler (C), a metal oxide is preferable, and silica is more preferable.

The shape of the inorganic filler (C) may be spherical, chain-shaped, needle-shaped, plate-shaped, flaky, rod-shaped, fibrous, or the like, but is preferably spherical. Here, the spherical shape means a substantially spherical shape including a polyhedral shape that can be approximated to a sphere, such as a spheroid, an oval shape, a flat sugar shape, and an eyebrows shape, in addition to a true sphere.

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

In the hard coating 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. The content of the inorganic filler (C) is usually 30 to 125% by mass, preferably 50 to 125% by mass, based on the component (A).
If the hard coat layer is formed by using a hard coat agent containing too little of the inorganic filler (C), the laminated film may be curled. On the other hand, if a hard coating agent containing too much inorganic filler (C) is used, the bending resistance of the laminated film may decrease.

In the hard coat agent of the present invention, as the component (D), a polymer having a reactive functional group and a polysiloxane side chain (hereinafter, the component (D) may be referred to as "polymer (D)"). contains. By using the hard coat agent containing the polymer (D), it is possible to form a hard coat layer having a high contact angle with water and excellent antifouling property.

The reactive functional group contained in the polymer (D) refers to a group capable of reacting with the mercapto group of the component (B) to form a chemical bond. Examples of this reactive functional group include those similar to those shown as the reactive functional group of the organosilicon compound (A). Of these, a group having a carbon-carbon unsaturated bond is preferable, and a (meth) acryloyloxy group is more preferable.

The polysiloxane side chain contained in the polymer (D) means a side chain having a repeating unit represented by the following formula (II).

In formula (II), R ⁴ and R ⁵ are independently hydrogen atoms, alkyl groups having substituents or substituents, cycloalkyl groups having substituents or substituents, alkenyl groups having substituents or substituents, respectively. Represents an aryl group that is unsubstituted or has a substituent.

Examples of the alkyl group of the alkyl group having no substituent or substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Examples thereof include alkyl groups having 1 to 10 carbon atoms such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.

Examples of the cycloalkyl group of the cycloalkyl group having no substituent or substituent include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

Examples of the alkenyl group of the alkenyl group having no substituent or substituent include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and the like having 2 to 2 carbon atoms. Included are 10 alkenyl groups.

Examples of the substituent of the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group. An aryl group having an unsubstituted or substituent such as a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group; and the like can be mentioned.

Examples of the aryl group of the aryl group having an unsubstituted or substituent include an aryl group having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

Examples of the substituent of the aryl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; and carbon atoms such as methoxy group and ethoxy group. 1 to 6 alkoxy groups; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc. An aryl group having a substituent; and the like can be mentioned.

Among these, as R ^4, R ^5, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, a hydrogen atom is particularly preferred.

The number of silicon atoms contained in one polysiloxane side chain is preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 40.

The main chain of the polymer (D) is not particularly limited. Examples of the polymer (D) include an acrylic polymer, a polyester polymer, a novolac polymer, and the like. Among these, as the polymer (D), an acrylic polymer is preferable.

An acrylic polymer having a reactive functional group and a polysiloxane side chain is reacted by, for example, copolymerizing an acrylic monomer and a polysiloxane macromer to obtain a copolymer, and then subjecting the copolymer to a modification treatment. It can be obtained by introducing a sex functional group.

As the acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylic (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl ( Acrylic monomer having no functional group for graft reaction such as meta) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate;

(Meta) acrylic acid, 2-hydroxyethyl (meth) acrylicate, 2-hydroxypropyl (meth) acrylicate, 4-hydroxybutyl (meth) acrylicate, N-methylolacrylamide, dimethylaminoethyl (meth) Acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxy Examples thereof include acrylic monomers having a functional group for a graft reaction such as methyl (meth) acrylamide, N-t-butyl acrylamide, N-octyl acrylamide, and glycidyl (meth) acrylate.
The "functional group for graft reaction" in the description of the acrylic monomer means a functional group that can be used for introducing the graft side chain, and is included in the components (A), (C), and (D). It is different from the "reactive functional group" of.

Examples of the polysiloxane macromer include one-terminal reactive organopolysiloxane having an acrylic group or a methacrylic group at one end, such as one-terminal methacrylic-modified dimethylpolysiloxane.

The copolymerization reaction of the acrylic monomer and the polysiloxane macromer can usually be carried out by a solution polymerization reaction using a polymerization initiator.
As the polymerization initiator, 2,2'-azobis [2- (2-imidazolin-2yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2' -Water-soluble azo polymerization initiator such as -azobis [2-methyl-N- (2-hydroxyethyl) propionamide]; Initiation of oil-soluble polymerization of benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, azobisisobutynitrile, etc. Agents: Polymer azo polymerization initiators such as polydimethylsiloxane unit-containing polymer azo polymerization initiators and polyethylene glycol unit-containing polymer azo polymerization initiators; and the like.

Solvents used for solution polymerization include alcohol solvents such as ethanol, isopropanol, butanol, and isobutanol; ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethyl benzene; methyl cellosolve, Glycol ethers such as butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl diethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate; octane, decane, etc. Aliphatic hydrocarbons; petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha; and the like can be mentioned.
The reaction temperature of the solution polymerization is preferably 50 to 150 ° C., and the reaction time is preferably 3 to 12 hours.

When the obtained copolymer is subjected to a modification treatment to introduce a reactive functional group, the functional group for graft reaction in the acrylic monomer can be used.
For example, when the copolymer contains a carboxyl group as a functional group for graft reaction, the reactive functional group can be introduced into the copolymer by reacting with the reactive functional group-containing monoglycidyl compound.
Similarly, when the copolymer contains a glycidyl group as a functional group for graft reaction, the reactive functional group can be introduced into the copolymer by reacting the reactive functional group-containing monocarboxyl compound. ..
For these reactions, known reaction conditions can be appropriately used.

In the hard coating agent of the present invention, the polymer (D) can be used alone or in combination of two or more.

The content of the polymer (D) is not particularly limited. The content of the polymer (D) is usually 1 to 5% by mass, preferably 3 to 5% by mass, based on the component (A).

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

Since the hard coat agent containing a solvent is excellent in coatability, a thin hard coat layer can be efficiently formed by using the hard coat agent containing a solvent.
Examples of the solvent 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 and propanol. Alcohol-based 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; cellosolves such as ethyl cellosolve System solvent; and the like.
The solvent may be used alone or in combination of two or more.

When the hard coat agent of the present invention contains a solvent, the content of the solvent is preferably an amount 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 of 35 to 90% by mass. Is more preferable, and an amount of 40 to 85% by mass is further preferable.

By using a hard coating agent containing a photopolymerization initiator, the obtained coating film can be efficiently cured after the hard coating agent is applied.
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, and 2,2-dimethoxy-2-phenylacetophenone. 2,2-Diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2- Methylanthraquinone, 2-ethylanthraquinone, 2-tershaly butyl anthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl Examples thereof include dimethyl ketal, acetphenone dimethyl ketal, p-dimethylaminobenzoic acid ester and the like.
The photopolymerization initiator may be used alone or in combination of two or more.

When the hard coat agent of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is usually 0.01 to 10% by mass, preferably 0.% by mass, based on the total solid content of the hard coat agent. It is 5 to 10% by mass.

The hard coat agent of the present invention contains the component (A), the component (B), the component (C), and the component (D). The reactive functional groups contained in the component (A), the component (C), and the component (D) can react with the mercapto group contained in the component (B), and these reactive functional groups are used with each other. But it can react.
As described above, since the hard coating agent of the present invention can utilize both the reaction involving the mercapto group and the reaction not involving the mercapto group, the hard coating agent of the present invention has high hardness and resistance. A hard coat layer having excellent scratch resistance can be formed.

Further, when the reactive functional groups are reacted with each other, it is usually necessary to irradiate or heat an active energy ray such as an ultraviolet ray or an electron beam, so that the reactive functional group and the mercapto group are combined. 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 may occur, which may reduce the optical properties and curlability.
Therefore, by appropriately adjusting the amount of the component (B) and using a hard coating agent in which the unreacted reactive functional group is not excessive after the reaction between the reactive functional group and the mercapto group, the optical characteristics are obtained. It is possible to form a hard coat layer having excellent curl property and bending resistance.

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

The base material layer constituting the laminated film of the present invention is used to hold the hard coat layer.
The type of the base material layer is not particularly limited. For example, a synthetic resin film can be used as a 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, and polymethacrylic acid. Examples thereof include films of methyl, methyl polyacrylate, polyethyl methacrylate, polystyrene, cellulose triacetate, cellophane, polycarbonate and the like.

In the present invention, a primer layer may be provided on at least one surface of the base material layer. The type of the primer layer is not particularly limited as long as it has good adhesion to the hard coat layer provided on the primer layer 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 the base material layer (synthetic resin film) is not particularly limited, and can be appropriately determined depending on the use of the laminated film and the like.
The thickness of the base material layer is usually 10 to 500 μm, preferably 20 to 200 μm.

The hard coat layer constituting the laminated film of the present invention is formed by 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 a synthetic resin film for a base material layer and curing the obtained coating film.

The method of applying the hard coating agent on the synthetic resin film is not particularly limited, and a known method can be adopted. 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. Can be 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, 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 grad.

When forming the hard coat layer, if necessary, a drying treatment may be performed before the coating film is cured or after the coating film is cured.
The drying treatment 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 by using the hard coat agent of the present invention, has high hardness, and is excellent in scratch resistance, antifouling property, and slipperiness.
The hard coat layer constituting the laminated film of the present invention usually exhibits a hardness of F or higher when a pencil scratch hardness test is performed according to the method described in Examples, and H or higher is preferable.
When the scratch resistance of the hard coat layer constituting the laminated film of the present invention is evaluated according to the method described in Examples, no scratches are usually observed.
The hard coat layer constituting the laminated film of the present invention is usually 90 to 105 °, preferably 99 to 102 °, when the contact angle of water is measured.
When the hard coat layer of the present invention is brought into contact with a stainless steel plate and the static friction coefficient is measured, it is usually 0.15 to 0.35, preferably 0.20 to 0.30, more preferably 0. It is 21 to 0.26, and when the dynamic friction coefficient is measured in the same manner, it is usually 0.15 to 0.38, preferably 0.18 to 0.30, and more preferably 0.18 to 0.23.

The laminated film of the present invention preferably has excellent transparency. The laminated film of the present invention preferably has 89% or more, more preferably 90% or more when the total light transmittance is measured. There is no particular upper limit, but it is usually 95% or less.
The laminated film of the present invention preferably has excellent bending resistance. The laminated film of the present invention is preferably 4 mmΦ or less, more preferably 2 mmΦ or less when a mandrel bending test is performed according to JIS K5600-5-1.
The laminated film of the present invention preferably has less 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 60 mm or less, preferably 20 mm or less, and more preferably 10 mm or less. There is no particular lower limit, but it is usually 2 mm or more.

In these laminated films having excellent optical properties, bending resistance, and curl property, the amounts of the (A) component, the (B) component, the (C) component, and the (D) component are adjusted as described above, and the (A) component is adjusted. It can be produced by preventing the reaction between the reactive functional groups of the component, the component (C) and the component (D) from occurring more than necessary.

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

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 specified, parts and% in each example are based on mass.

The compounds used in Examples and Comparative Examples are shown below.
Solution of organosilicon compound (vinyltriacetoxysilane) (A1) (manufactured by Sakai Chemical Co., Ltd., trade name: SHC-001B, concentration 90%)
Solution of polythiol compound [trimethylolpropane tris (3-mercaptopropionate)] (B1) (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, Ltd., trade name: AC-4130Y, concentration 30%, average particle size 40 to 50 nm)
Silicone acrylic polymer solution (D1) (manufactured by Taisei Fine Chemicals, trade name: 8SS-723, concentration 47%)

[Example 1]
A mixed solution obtained by mixing 110 parts of an organosilicon compound solution (A1), 150 parts of a polythiol compound solution (B1), 398 parts of an inorganic filler dispersion (C1), and 1 part of a silicone acrylic polymer solution (D1). Was diluted with methyl ethyl ketone to prepare a hard coat agent (1) having a solid content concentration of 45%.
A hard coat agent (1) is applied to a polyethylene terephthalate film with a single-sided primer layer (manufactured by Toyo Spinning Co., Ltd., trade name: PET50A4100, thickness 50 μm) using Meyerbar # 10 so that the film thickness after curing is 5 μm. The coating film was applied on the surface of the film and irradiated with ultraviolet rays (light intensity: 500 mJ / cm ² ) to cure the coating film. Next, the cured coating film was ^{dried at 120 o} C for 20 minutes to form a hard coat layer, and a laminated film (1) was obtained.

[Examples 2 to 3 and Comparative Examples 1 to 4]
Except that in Example 1, instead of the hard coating agent (1), the hard coating agents (2) to (7) having the compositions shown in Table 1 were prepared, and the laminated film was produced using the hard coating agents (2) to (7). , The laminated films (2) to (7) were obtained by using the obtained hard coating agents (2) to (7) in the same manner as in Example 1.

The laminated films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Table 1. In Table 1, "concentration" means "solid content concentration".

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

[Total light transmittance]
Using a haze meter (manufactured by 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., product name: No. 553-M), a pencil with a load of 750 g and a scratch speed of 0.5 mm / sec according to JIS K5600-5-4 (1999). A scratch hardness test was performed.

[Scratch resistance evaluation]
The hard coat layer of the laminated film is ^{rubbed 10 times in a range of 50 mm in length with a load of 250 g / cm 2} using steel wool # 0000, and then visually confirming the presence or absence of scratches, and scratch resistance according to the following criteria. Was evaluated.
◯: There are no scratches.
×: There are scratches.

[Flexibility evaluation]
A mandrel bending test was performed according to JIS K5600-5-1 (1999) to evaluate the bending resistance of the laminated film.

[Curl property evaluation]
The laminated film was cut into a square with a side of 10 cm, and this was used as a test piece. This test piece was allowed to stand on a horizontal table, the floats (mm) at the four corners at this time were measured, and the total value was calculated.

[Measurement of contact angle with water]
Using a fully automatic contact angle meter "DM-701" (manufactured by Kyowa Interface Science Co., Ltd.), the static contact angle when 2 μL of water was dropped onto the hard coat layer at 23 ° C. and 50% RH environment was measured. ..

[Anti-fouling property evaluation]
Using an oil-based pen (manufactured by Zebra, product name: McKee extra-fine, product number: MO-120-MC-BK), draw a line on the hard coat layer, and then draw a line on this non-woven fabric (product name: Bencot M-3II (product name: Bencot M-3II). It was wiped off with Asahi Kasei Fibers Co., Ltd.). The remaining condition of the line at this time was visually observed and evaluated according to the following criteria.
◯: Can be wiped clean.
X: A line remains.

[Slipperiness evaluation]
According to JIS K7125 (1999), the hard coat layer was brought into contact with the stainless steel plate, and the coefficient of static friction and the coefficient of dynamic friction were measured in this state.

From Table 1, the following can be seen.
The hard coat layers of the laminated films (1) to (3) obtained in Examples 1 to 3 are excellent in transparency, have high hardness, and have bending resistance, scratch resistance, stain resistance, and slippage. Excellent in sex.
On the other hand, the laminated films (4) to (7) obtained in Comparative Examples 1 to 4 are inferior in antifouling property and slipperiness.

Claims (6)

A laminated film having a base material layer and a hard coat layer.
The hard coat layer state, and are not formed by using the following (A), (B), a hard coating agent containing the component (C), and component (D),
The laminated film has a thickness of 4 mmΦ or less when a mandrel bending test is performed according to JIS K5600-5-1.
Laminated film that is used as a production material of a touch panel.
Component (A): Organosilicon compound having a reactive functional group and a hydrolyzable group
Component (B): Polythiol compound
Component (C): Inorganic filler having a reactive functional group
Component (D): Polymer having a reactive functional group and a polysiloxane side chain The laminated film according to claim 1, wherein the content of the component (B) in the hard coating agent is 50 to 120% by mass with respect to the component (A). The laminated film according to claim 1 or 2, wherein the content of the component (C) in the hard coating agent is 30 to 125% by mass with respect to the component (A). The laminated film according to any one of claims 1 to 3, wherein the content of the component (D) in the hard coating agent is 1 to 5% by mass with respect to the component (A). The laminated film according to any one of claims 1 to 4, wherein the component (D) is a polymer selected from the group consisting of an acrylic polymer, a polyester polymer, and a novolak polymer. The laminated film according to any one of claims 1 to 5, wherein the base material layer has a thickness of 10 to 500 μm.