JP2003057402A - Hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film which hardly causes peeling or cracks and has sufficient hardness and scratching resistance. SOLUTION: The hard coat film has a hard coating layer of >=10 μm film thickness on a base material and has a layer having <=0.4 coefficient of dynamic friction on its surface as the outermost surface.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a dynamic friction coefficient of 0.
It relates to a hard coat film having a layer of 4 or less on the outermost surface. From another point of view, the present invention relates to a hard coat film which is less likely to cause film peeling or cracking and has excellent scratch resistance and surface hardness. The hard coat film of the present invention can be used as a surface protective film having an optical function for displays such as CRT, LCD, PDP and FED, touch panels and glass.

[0002]

2. Description of the Related Art It is widely known that when a filler is filled in a resin, the hardness of the resin becomes high. There has been extensive research on methods for obtaining kneadability. As the kneading and extruding method, a single screw type kneading extruder or a twin screw kneading extruder is known,
Widely used in general. Further, not only the hardness due to the high filling but also the transparency of the resin is imparted, so that the filler is required to be finely divided and highly dispersed. Further, as disclosed in JP-A-7-207129, a method of filling particles during polymerization is also known.

In recent years, plastic products are being replaced by glass products from the viewpoints of workability and weight saving. However, since the surfaces of these plastic products are easily scratched, a hard coat comprising a cured resin layer for the purpose of imparting scratch resistance. In many cases, a layer is directly applied or a plastic film with a hard coat layer (referred to as a hard coat film) is laminated and used. Further, even in the case of conventional glass products, the number of cases in which a plastic film is laminated to prevent scattering is increasing, and it is useful to form a hard coat layer on the surface of the film in order to strengthen the hardness of the film surface. Yes, it is widely practiced.

As a conventional hard coat paint, a thermosetting paint or an ultraviolet curable paint is used. The plastic film itself is used for a hard coat film obtained by coating and curing this on a plastic film. Because of its low heat resistance, UV-curable coatings that can be cured at low temperatures are widely used. Generally, the curable component used in the ultraviolet curable coating composition has 2 to 2 molecules in the molecule.
A compound called a polyfunctional acrylate monomer having 6 acrylic acid ester groups or urethane acrylate,
Oligomers having a molecular weight of several hundred to several thousand and having several acrylate groups in the molecule, which are called polyester acrylate and epoxy acrylate, are used. However, since many of these oligomer compounds have a small amount of acrylic groups introduced, and sufficient hardness cannot be obtained by themselves, polyfunctional acrylate monomers are widely used as hard coat paints requiring higher hardness. There is.

Generally, a hard coat film has 3 to 10 of the above hard coat paints directly on a plastic film or through a primer layer of about 1 μm.
It is manufactured by forming a thin coating film of about μm. However, the conventional hard coat film has insufficient hardness of the hard coat layer, and when the underlying plastic substrate film is deformed due to its thin coating film thickness, The hard coat layer is also deformed accordingly, and the hardness of the hard coat film as a whole is low,
I was not completely satisfied. For example, when it is widely used as a plastic substrate film, a hard coat film obtained by applying an ultraviolet-curable coating material on a triacetyl cellulose or polyethylene terephthalate film with the above-mentioned thickness generally has a pencil hardness of 2H to 3H level. And is completely inferior to 9H, which is the pencil hardness of glass.

Further, such a film is used for CRT, PD
It is used as a surface protection film for displays such as P and LCD, and is also attached to windows as a glass shatterproof film, but if the surface is wiped with a cloth or the like, it will be difficult to see images and scenery through the film. There was a problem. To solve such a problem, Japanese Patent Laid-Open No.
It has been proposed to reduce the coefficient of friction as shown in Japanese Patent Application Laid-Open No. 333404, Japanese Patent Application Laid-Open No. 8-286001, and Japanese Patent Application Laid-Open No. 11-258405. By this method, scratches are less likely to wear, but none have improved pencil hardness at the same time, and none have been satisfactory.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hard coat film which is resistant to film peeling and cracking and has sufficient hardness and scratch resistance.

[0008]

The above objects have been achieved by the following means. 1. A hard coat film having a hard coat layer having a film thickness of 10 μm or more on a substrate and having a layer having a dynamic friction coefficient of 0.4 or less on the outermost surface. 2. The hard coat film as described in 1 above, which has an average reflectance at 2450 to 650 nm of 2% or less. 3. 3. The hard coat film as described in 1 or 2 above, wherein the hard coat film has a low reflection layer containing SiO ₂ . 4. Low reflection layer, lubricant 5mg / m ² or more 100mg
/ M ² or less, the hard coat film as described in 3 above. 5. The hard coat layer of the hard coat film is formed by applying and curing a curable composition containing a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule. The hard coat film according to any one of 1 to 4 above, which is a hard coat layer. 6. The hard coat film as described in any one of 1 to 5 above, wherein the compound having a ring-opening polymerizable group is a crosslinkable polymer having a repeating unit represented by the following general formula (1). General formula (1)

[0009]

[Chemical 2]

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P ¹ is a monovalent group containing a ring-opening polymerizable group, and L ¹ is a single bond or a divalent group. It is a valent linking group.) 7. 7. The hard coat film as described in any one of 1 to 6 above, wherein the ring-opening polymerizable group is a cationically polymerizable group. 8. 8. The hard coat film as described in any one of 1 to 7 above, wherein the curable composition contains crosslinked fine particles. 9. 9. The hard coat film as described in any one of 1 to 8 above, wherein the surface has a pencil hardness of 4H to 9H. 10. 10. The hard coat film as described in any one of 1 to 9 above, wherein the substrate is a polyester film and the film thickness of the hard coat layer is 20 to 200 μm.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. As described above, the hard coat film of the present invention has a hard coat layer having a film thickness of 10 μm or more on a base material and a layer having a surface dynamic friction coefficient of 0.4 or less on the outermost surface. The hard coat layer is formed by applying a curable composition containing a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule onto a substrate and curing the composition. It is preferable that the
The hard coat layer may be a single layer or may be composed of a plurality of layers, but it is preferable that the hard coat layer is a single layer which is simple in the manufacturing process. In this case, the single layer is a hard coat layer formed of the same composition, and may be formed by coating a plurality of times as long as the composition after coating and drying has the same composition. On the other hand, the plurality of layers means that the layers are composed of a plurality of compositions having different compositions. For multiple layers,
At least one layer is a hard coat layer formed by applying and curing a curable composition containing both a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule. It is preferable that the outermost layer of the plurality of layers is coated and cured with a curable composition containing both a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule. It is particularly preferable that the hard coat layer is formed as described above.

The compound containing a ring-opening polymerizable group that can be used in the hard coat layer will be described below. The compound having a ring-opening polymerizable group is a compound having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical or the like, and among these, cationic ring-opening polymerization of a heterocyclic compound is preferable. Such compounds include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives,
Examples thereof include cyclic imino ethers such as cyclic lactone derivatives, cyclic carbonate derivatives and oxazoline derivatives, and epoxy derivatives, oxetane derivatives and oxazoline derivatives are particularly preferable. The compound having 3 or more ring-opening polymerizable groups in the same molecule is not particularly limited as long as it is a compound having 3 or more cyclic structures as described above in the same molecule. Preferred examples of such compounds include, for example, 3
Functional glycidyl ethers (trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), 4-functional or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, pentaerythritol tetra Glycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc., trifunctional or higher functional cycloaliphatic epoxies (Eporide GT-301, Epolide GT-401, EHPE (above, Daicel Chemical Industries Ltd. )), Polycyclohexylepoxy methyl ether of phenol novolac resin, etc.) trifunctional or higher functional oxetanes (OX-S) , PNOX-1009 (or more,
Toagosei Co., Ltd.) etc., but the present invention is not limited thereto.

On the other hand, a compound having one or two ring-opening polymerizable groups in the same molecule can be used in combination if necessary, and preferable compounds are monofunctional or bifunctional glycidyl ethers and monofunctional compounds. Alternatively, bifunctional alicyclic epoxies and monofunctional or bifunctional oxetanes can be mentioned. Moreover, these are commercially available and can be used.

The curable composition for forming the hard coat layer is a cross-linking composition containing a repeating unit represented by the above general formula (1) as a compound having three or more ring-opening polymerizable groups in the same molecule. It is particularly preferable to contain a hydrophilic polymer. The crosslinkable polymer will be described in detail below. In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom or a methyl group. L ¹ is a single bond or a divalent linking group, preferably a single bond, —O—,
Alkylene group, arylene group and * -COO-, * -CONH-, * -OCO-, *-linked to the main chain at * side
NHCO-. P ¹ is a monovalent group containing a ring-opening polymerizable group, and preferable P ¹ is a monovalent group containing an imino ether ring such as an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring or an oxazoline ring. Examples of the monovalent group include a monovalent group including an epoxy ring, an oxetane ring, and an oxazoline ring.

The crosslinkable polymer containing the repeating unit represented by the general formula (1) is preferably synthesized simply by polymerizing a corresponding monomer. As the polymerization reaction in this case, radical polymerization is the most simple and preferable.

Specific preferred examples of the repeating unit represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

The crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention may be a copolymer composed of plural kinds of repeating units represented by the general formula (1), and A copolymer containing a repeating unit other than the formula (1) (for example, a repeating unit not containing a ring-opening polymerizable group) may be used. In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or for the purpose of controlling the content of the ring-opening polymerizable group of the crosslinkable polymer, a method of using a copolymer containing a repeating unit other than the general formula (1) is preferable. Is. The method of introducing a repeating unit other than the general formula (1) is
A method of introducing the corresponding monomer by copolymerization is preferable.

When a repeating unit other than the general formula (1) is introduced by polymerizing a corresponding vinyl monomer, acrylic acid or α-alkylacrylic acid (eg methacrylic acid) is preferably used as a monomer. Derived esters or amides (eg, N-i-propylacrylamide, Nn-
Butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamide-
2-Methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetoneacrylamide, acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, methyl acrylate, ethyl acrylate, hydroxyethyl acrylate, n-propyl acrylate, i -Propyl acrylate, 2-hydroxypropyl acrylate, 2-methyl-2-nitropropyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2
-Ethoxyethyl acrylate, 2-methoxymethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2-dimethylbutyl acrylate,
3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-octyl Acrylate, 2-ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptadecafluorodecyl acrylate, n
-Octadecyl acrylate, methyl methacrylate,
2,2,2-trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, se
c-Butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate, heptadecafluorodecyl methacrylate, n-octadecyl methacrylate, 2-isobornyl methacrylate, 2- Norbornylmethyl methacrylate, 5-norbornen-2-ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethylaminoethyl methacrylate, etc.),

Acrylic acid or α-alkyl acrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.), vinyl esters (for example, vinyl acetate), maleic acid or esters derived from fumaric acid (dimethyl maleate, maleic acid) Dibutyl, diethyl fumarate, etc.), maleimides (N-phenylmaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg, butadiene, cyclopentadiene, isoprene, etc.) ), Aromatic vinyl compounds (for example, styrene, p-chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinyl. Formamide, N-vinyl-N-
Methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinylsulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium methallylsulfonate, vinylidene chloride,
Vinyl alkyl ethers (for example, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene, etc. are mentioned. You may use these vinyl monomers in combination of 2 or more types. Other vinyl monomers are Research Disclosure No. 1955 (1
980, July) can be used. In the present invention, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

As repeating units other than the general formula (1),
Repeating units having a reactive group other than the ring-opening polymerizable group can also be introduced. In particular, when it is desired to increase the hardness of the hard coat layer, or to improve the adhesion between layers when another functional layer is used on the substrate or hard coat, a copolymer containing a reactive group other than the ring-opening polymerizable group. Is preferable. The method for introducing the repeating unit having a reactive group other than the ring-opening polymerizable group is the corresponding vinyl monomer (hereinafter,
A method of copolymerizing a reactive monomer) is simple and preferable.

Preferred specific examples of the reactive monomer are shown below, but the present invention is not limited thereto.

Hydroxyl group-containing vinyl monomer (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomer (eg,
Isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N-methylol group-containing vinyl monomer (eg, N-methylolacrylamide, N-
Methylol methacrylamide, etc.), carboxyl group-containing vinyl monomers (eg acrylic acid, methacrylic acid,
Itaconic acid, carboxyethyl acrylate, vinyl benzoate, etc.), alkyl halide-containing vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-)
Chloropropylmethacrylate etc.), acid anhydride-containing vinyl monomers (eg maleic anhydride etc.), formyl group-containing vinyl monomers (eg acrolein, methacrolein etc.), sulfinic acid group-containing vinyl monomers (eg potassium styrenesulfinate etc.), Active methylene-containing vinyl monomers (eg acetoacetoxyethylmethacrylate etc.), acid chloride-containing monomers (eg acrylic acid chloride, methacrylic acid chloride etc.), amino group-containing monomers (eg allylamine etc.), alkoxysilyl group-containing monomers (eg methacryloyloxypropyl). Trimethoxysilane, acryloyloxypropyltrimethoxysilane) and the like.

In the crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention, the proportion of the repeating unit represented by the general formula (1) is preferably from 1% by mass to 100% by mass. Or less, more preferably 30 mass% or more 1
00% by mass or less, particularly preferably 50% by mass or more and 100
It is not more than mass%.

The preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by the general formula (1) is 1,000 to 1,000,000, more preferably 300 in terms of number average molecular weight.
It is 0 or more and 200,000 or less. Most preferably, it is 5,000 or more and 100,000 or less. Here, the number average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (the same applies hereinafter).

Preferred examples of the crosslinkable polymer containing the repeating unit represented by the general formula (1) are shown in Table 1 below.
The present invention is not limited to these. In addition, the repeating unit represented by the general formula (1), which is a specific example, is represented by the number of the specific example, and the repeating unit derived from a copolymerizable monomer is a monomer name. The copolymerization composition ratio was added in mass%.

[0029]

[Table 1]

The hard coat layer of the hard coat film of the present invention comprises a curable composition containing both a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule. It can be formed by applying and curing it on a desired substrate.

The compound containing an ethylenically unsaturated group which can be used in the present invention is described below. Preferred types of the ethylenically unsaturated group are an acryloyl group, a methacryloyl group, a styryl group and a vinyl ether group, and an acryloyl group is particularly preferred. The compound containing an ethylenically unsaturated group may have one or more ethylenically unsaturated groups in the molecule, but preferably two or more, more preferably three or more. Among them, a compound having an acrylic group is preferable, and a compound called a polyfunctional acrylate monomer having 2 to 6 acrylic acid ester groups in the molecule, a urethane acrylate, a polyester acrylate, or a molecule called an epoxy acrylate is included in the molecule. An oligomer having several hundred acrylate groups and having a molecular weight of several hundreds to several thousands can be preferably used.

Specific examples of the compound having two or more acryl groups in the molecule include ethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate and diester. Polyol polyacrylates such as pentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, epoxy acrylates such as diacrylate of bisphenol A diglycidyl ether, diacrylate of hexanediol diglycidyl ether, polyisocyanate and hydroxyethyl acrylate Examples include urethane acrylates obtained by the reaction of hydroxyl group-containing acrylates. That.

In the present invention, a crosslinkable polymer containing a repeating unit represented by the following general formula (2) can be preferably used as a compound having a plurality of ethylenically unsaturated groups in the molecule. Hereinafter, the crosslinkable polymer containing the repeating unit represented by the general formula (2) will be described in detail. General formula (2)

[0034]

[Chemical 6]

In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. P ² is a monovalent group containing an ethylenically unsaturated group. L ² is a single bond or a divalent linking group, preferably a single bond, −
O-, alkylene group, arylene group and * -COO-, * -CONH-, * -OCO linked to the main chain at * side
-, * -NHCO-. P ² is a monovalent group containing an ethylenically unsaturated group. P ² is preferably a monovalent group containing an acryloyl group, a methacryloyl group or a styryl group, and most preferably a monovalent group containing an acryloyl group.

The crosslinkable polymer containing a repeating unit represented by the general formula (2) may be synthesized by polymerizing a corresponding monomer to directly introduce an ethylenically unsaturated group. You may synthesize | combine by the method of introduce | transducing an ethylenically unsaturated group to the polymer obtained by superposing | polymerizing the monomer which has a polymer reaction. Also, the methods of and can be combined and synthesized. Examples of the polymerization reaction include radical polymerization, cationic polymerization and anionic polymerization. When the above method is used, it is necessary to utilize the difference in the polymerizability between the ethylenically unsaturated group consumed by the polymerization reaction and the ethylenically unsaturated group left in the crosslinkable polymer. For example, when a monovalent group containing an acryloyl group or a methacryloyl group is used among the preferred P ² 's in the general formula (2), the polymerization reaction for forming a crosslinkable polymer is carried out by the cationic polymerization as described above. The crosslinkable polymer of the invention can be obtained. On the other hand, when P ² is a monovalent group containing a styryl group, radical polymerization,
Since gelation is likely to proceed regardless of whether the method is cationic polymerization or anionic polymerization, the crosslinkable polymer of the present invention is usually synthesized by the above-mentioned method.

As described above, the above-described method utilizing the polymer reaction can obtain a crosslinkable polymer regardless of the kind of the ethylenically unsaturated group introduced in the general formula (2). It is useful. Polymer reactions include, for example:
(I) Functional group conversion (elimination reaction, oxidation reaction, reduction reaction) after producing a polymer containing a functional group in which an ethylenically unsaturated group is made into a precursor, such as elimination of hydrochloric acid from a 2-chloroethyl group Etc.) to form an ethylenically unsaturated group, and (II) after forming a polymer containing an arbitrary functional group, a bond forming reaction proceeds with a functional group in the polymer to form a covalent bond. And a compound having both an ethylenically unsaturated group (hereinafter referred to as a reactive monomer). In addition, these methods (I) and (II) may be combined. The bond forming reaction referred to here can be used without particular limitation as long as it is a reaction forming a covalent bond among bond forming reactions generally used in the field of organic synthesis. Further, when the method (II) is carried out, the ethylenically unsaturated group contained in the crosslinkable polymer may be thermally polymerized during the reaction to cause gelation, so that the temperature is as low as possible (preferably 60 ° C. or less, particularly preferably). Is preferably room temperature or less), and the reaction proceeds preferably. A catalyst may be used for the purpose of promoting the progress of the reaction,
A polymerization inhibitor may be used for the purpose of suppressing gelation.

Examples of preferable combinations of functional groups in which the polymer bond-forming reaction proceeds are given below, but the present invention is not limited thereto.

Examples of the combination of functional groups in which the reaction proceeds by heating or at room temperature include (a) hydroxyl group, epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid chloride , An active ester group (eg sulfate),
Formyl group, acetal group, (b) hydroxyl group, mercapto group, amino group for isocyanate group, carboxyl group, N-methylol group, (ha) carboxyl group for epoxy group, isocyanate group, amino group,
With respect to the N-methylol group and (d) N-methylol group, an isocyanate group, an N-methylol group, a carboxyl group,
For amino group, hydroxyl group, (e) epoxy group, hydroxyl group, amino group, mercapto group, carboxyl group, N-methylol group, (f) vinyl sulfone group for sulfinic acid group, amino group, (to ) A hydroxyl group, a mercapto group, an active methylene group for a formyl group, a formyl group, a vinyl group (an allyl group, an acryl group, etc.), an epoxy group, an isocyanate group, an N-methylol group for a (thio) mercapto group Carboxyl group, alkyl halide, acid anhydride acid chloride, active ester group (for example, sulfate ester), (ri) amino group, formyl group, vinyl group (allyl group, acrylic group, etc.), epoxy group, isocyanate group, N-methylol group, carboxyl group, alkyl halide, acid anhydride, acid chloride, active ester group ( Example, if sulfuric acid ester), and a combination of such.

Preferred specific examples of the reactive monomer are shown below, but the present invention is not limited thereto.

Hydroxyl group-containing vinyl monomer (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomer (eg,
Isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N-methylol group-containing vinyl monomer (eg, N-methylolacrylamide, N-
Methylol methacrylamide, etc.), epoxy group-containing vinyl monomers (eg, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, C
YCLOMER-M100, A200 (manufactured by Daicel Chemical Industries, Ltd.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate, etc.), alkyl halide-containing vinyl monomers (for example, Chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate, etc.), acid anhydride-containing vinyl monomers (eg, maleic anhydride), formyl group-containing vinyl monomers (eg, acrolein, methacrolein, etc.), sulfinic acid group-containing vinyl monomers. (Eg potassium styrenesulfinate), vinyl monomer containing active methylene (eg acetoacetoxyethyl methacrylate), vinyl monomer containing vinyl group (eg allyl methacrylate, allyl) Acrylate, etc.), acid chloride-containing monomer (e.g., acrylic acid chloride, methacrylic acid chloride), and an amino group-containing monomer (e.g., allyl amine, etc.).

The polymer containing any functional group described in the above (II) can be obtained by polymerizing a reactive monomer having both a reactive functional group and an ethylenically unsaturated group. It can also be obtained by polymerizing a precursor monomer having low reactivity such as polyvinyl alcohol obtained by modifying polyvinyl acetate and then converting the functional group.
In these cases, radical polymerization is the most simple and preferable as the polymerization method.

Preferred specific examples of the repeating unit represented by the general formula (2) are shown below, but the invention is not limited thereto.

[0044]

[Chemical 7]

[0045]

[Chemical 8]

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

The crosslinkable polymer containing the repeating unit represented by the general formula (2) of the present invention may be a copolymer composed of plural kinds of repeating units represented by the general formula (2), and The copolymer may include a repeating unit other than the general formula (2) (for example, a repeating unit not containing an ethylenically unsaturated group). In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or for the purpose of controlling the content of the ethylenically unsaturated group of the crosslinkable polymer, a method of using a copolymer containing a repeating unit other than the general formula (2) is preferable. Is. As a method of introducing a repeating unit other than the general formula (2), (a) a method of copolymerizing a corresponding monomer and directly introducing it may be used, and (b) polymerizing a precursor monomer capable of converting a functional group, A method of introducing by a polymer reaction may be used. Also, (a) and (b)
It is also possible to introduce a combination of the above methods.

When a repeating unit other than the general formula (2) is introduced by polymerizing the corresponding vinyl monomer by the method (a), the monomer preferably used is acrylic acid or α-alkylacrylic acid (for example, Esters or amides derived from methacrylic acid (eg, N-i-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide,
N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride,
Methacrylamide, diacetone acrylamide, acryloyl morpholine, N-methylol acrylamide, N
-Methylol methacrylamide, methyl acrylate,
Ethyl acrylate, hydroxyethyl acrylate,
n-propyl acrylate, i-propyl acrylate, 2-hydroxypropyl acrylate, 2-methyl-2-nitropropyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl Acrylate, 2-ethoxyethyl acrylate, 2-
Methoxymethoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2-dimethylbutyl acrylate, 3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octa Fluoropentyl acrylate, n
-Hexyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2
-Propylpentyl acrylate, heptadecafluorodecyl acrylate, n-octadecyl acrylate,
Methyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, n
-Octyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, benzyl methacrylate, heptadecafluorodecyl methacrylate, n-octadecyl methacrylate, 2-isobornyl methacrylate, 2-norbornyl methyl methacrylate, 5-
Norbornen-2-ylmethylmethacrylate, 3-methyl-2-norbornylmethylmethacrylate, dimethylaminoethylmethacrylate, etc.),

Acrylic acids or α-alkylacrylic acids (eg acrylic acid, methacrylic acid, itaconic acid etc.), vinyl esters (eg vinyl acetate etc.), esters derived from maleic acid or fumaric acid (dimethyl maleate, Dibutyl maleate, diethyl fumarate, etc., maleimides (N-phenylmaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (for example, butadiene, cyclopentadiene, Isoprene etc.), aromatic vinyl compounds (eg styrene, p-chlorostyrene, t-butylstyrene, α)
-Methylstyrene, sodium styrenesulfonate, etc.), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl- N-methylacetamide,
1-vinyl imidazole, 4-vinyl pyridine, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chloride, vinyl alkyl ethers (such as methyl vinyl ether), ethylene, propylene, 1- Examples include butene and isobutene. You may use these vinyl monomers in combination of 2 or more types. As the vinyl monomer other than these, those described in Research Disclosure No. 1955 (July, 1980) can be used. In the present invention, esters and amides derived from acrylic acid or methacrylic acid, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

When the repeating unit represented by the general formula (2) is introduced by a polymer reaction as described above and the reaction is not completed, a functional group obtained by converting an ethylenically unsaturated group into a precursor or a reactive functional group is used. Although it is a copolymer having a repeating unit containing a group, it can be used in the invention without particular limitation.

Most of the repeating units containing no ethylenically unsaturated group derived from the above-mentioned vinyl monomers are introduced by polymerizing the aforementioned (b) functional group-convertable precursor monomer and polymerizing it. It is also possible to do so. On the other hand, the crosslinkable polymer containing the repeating unit represented by the general formula (2) of the present invention may contain a repeating unit other than the general formula (2) which can be introduced only by a polymer reaction. Typical examples include polyvinyl alcohol obtained by modifying polyvinyl acetate, polyvinyl butyral obtained by the acetalization reaction of polyvinyl alcohol, and the like. Specific examples of these repeating units are shown below, but the present invention is not limited thereto.

[0054]

[Chemical 12]

In the crosslinkable polymer containing the repeating unit represented by the general formula (2) of the present invention, the proportion of the repeating unit represented by the general formula (2) is from 1% by mass to 100% by mass, It is preferably 30% by mass or more and 100% by mass or less, and particularly preferably 50% by mass or more and 100% by mass or less.

The crosslinkable polymer containing the repeating unit represented by the general formula (2) preferably has a number average molecular weight of 1,000 or more and 1,000,000 or less, more preferably 30.
It is from 00 to 200,000. Most preferably, it is 5,000 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing the repeating unit represented by the general formula (2) are shown in Table 2 below.
The present invention is not limited to this. In addition, the repeating unit represented by the general formula (2) and the repeating unit such as polyvinyl alcohol, which are mentioned above as specific examples, are represented by the numbers of the specific examples described above, and the repeating unit derived from a copolymerizable monomer is used. Indicates the monomer name, and the copolymerization composition ratio is additionally indicated by mass%.

[0058]

[Table 2]

As the compound having a ring-opening polymerizable group which can be used in the present invention, a polymer containing both repeating units represented by the general formulas (1) and (2) can be mentioned. In this case, preferable repeating units of the general formulas (1) and (2) are the same as those described above. Further, even a copolymer containing a repeating unit other than the general formulas (1) and (2) is a copolymer containing a repeating unit having a reactive group other than an ethylenically unsaturated group and a ring-opening polymerizable group. May be.

In the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2), the general formula (1)
The proportion of the repeating unit represented by is 1% by mass or more and 99% by mass or less, preferably 20% by mass or more and 80% by mass or less, particularly preferably 30% by mass or more and 70% by mass or less, and the general formula (2 The proportion of the repeating units represented by 1) is 1% by mass or more and 99% by mass or less, preferably 2% by mass or more.
It is 0% by mass or more and 80% by mass or less, particularly preferably 30% by mass or more and 70% by mass or less.

The number average molecular weight of the crosslinkable polymer containing the repeating units represented by the general formulas (1) and (2) is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 200,000 or less. . Most preferably, it is 5,000 or more and 100,000 or less.

Preferred examples of the crosslinkable polymer containing both repeating units represented by the general formulas (1) and (2) are shown in Table 3, but the present invention is not limited thereto. In addition, the repeating units represented by the general formulas (1) and (2) and the repeating units such as polyvinyl alcohol, which are mentioned above as specific examples, are represented by the numbers of the specific examples described above and are derived from a copolymerizable monomer. For the repeating unit to be used, the monomer name was described, and the copolymerization composition ratio was additionally indicated by mass%.

[0063]

[Table 3]

The hard coat layer of the hard coat film of the present invention comprises a curable composition containing both a compound containing an ethylenically unsaturated group and a compound containing three or more ring-opening polymerizable groups in the same molecule. It can be formed by applying and curing it on a desired substrate. In the present invention, the preferable mixing ratio of the compound containing an ethylenically unsaturated group and the compound containing three or more ring-opening polymerizable groups in the same molecule varies depending on the kind of the compound used and is not particularly limited. The ratio of the compound containing a saturated group is preferably 30% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less.

In the present invention, it is preferable that the crosslinking reaction of both the compound containing the ethylenically unsaturated group and the compound containing the ring-opening polymerizable group proceeds when forming the hard coat layer. A preferable crosslinking reaction of the ethylenically unsaturated group is a radical polymerization reaction, and a preferable crosslinking reaction of the ring-opening polymerizable group is a cationic polymerization reaction. In either case, the polymerization reaction can be advanced by the action of heat and / or light. Usually, a method of adding a small amount of a cation generator including a radical generator or an acid generator, which is called a polymerization initiator, and decomposing them by heat and / or light to generate radicals or cations to proceed polymerization. Is common. The radical polymerization and the cationic polymerization may be performed separately, but it is preferable to proceed at the same time. There is a method of simply heating as a method of advancing the crosslinking reaction without adding a radical generator, but a method of irradiating with an electron beam is preferably used.

In the present invention, when a plastic film is used as the substrate, the plastic film itself has low heat resistance, and therefore, when it is cured by heating, it is preferable to cure at a temperature as low as possible. The heating temperature in that case is 1
The temperature is 40 ° C or lower, more preferably 100 ° C or lower. On the other hand, curing by the action of light is often used because the crosslinking reaction often proceeds at low temperature. Further, a method utilizing active energy rays such as radiation, gamma rays, alpha rays, electron rays, and ultraviolet rays is preferable, and among them, a method of adding a polymerization initiator capable of generating radicals or cations by ultraviolet rays and curing by ultraviolet rays is particularly preferable. . In addition, there are cases where curing can be further promoted by heating after irradiation with ultraviolet rays, and therefore it can be preferably used. The preferred heating temperature in this case is 1
It is 40 ° C or lower.

Examples of photoacid generators that generate cations by ultraviolet rays include ionic compounds such as triarylsulfonium salts and diaryliodonium salts, and nonionic compounds such as nitrobenzyl ester of sulfonic acid. "Organic Materials for Imaging", edited by Materials Research Society, published by Bushin Publishing Co. (1997)
Various known photoacid generators such as the compounds described in, etc. can be used. Of these, a sulfonium salt or an iodonium salt is particularly preferable, and the counter ion is P.
F ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like are preferable.

Examples of polymerization initiators that generate radicals by ultraviolet rays include acetophenones, benzophenones, Michler's ketone, benzoylbenzoates, benzoins, α-acyloxime esters, tetramethylthiuram monosulfide and thioxanthone. Further, as mentioned above, the sulfonium salt, iodonium salt and the like which are usually used as the photo-acid generator also act as a radical generator upon irradiation with ultraviolet rays, and therefore they may be used alone in the present invention. Further, a sensitizer may be used in addition to the polymerization initiator for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like.

The polymerization initiators may be used in combination, or may be used alone in the case of a compound which alone generates both a radical and a cation. The addition amount of the polymerization initiator is 0.1 to 15% by mass based on the total mass of the ethylenically unsaturated group-containing compound and the ring-opening polymerizable group-containing compound contained in the curable composition. It is preferable to use it in a range of 1 to 10% by mass.

In the present invention, a crosslinkable polymer having a repeating unit represented by the general formula (1) and a crosslinkable polymer having a repeating unit represented by the general formula (2) (hereinafter, referred to as
(These are collectively referred to as the polymer of the present invention) is usually
It is a solid or high-viscosity liquid and difficult to apply alone. When the polymer is water-soluble or when it is an aqueous dispersion, it can be applied in an aqueous system, but it is usually dissolved in an organic solvent and applied. Any organic solvent can be used without particular limitation as long as it can dissolve the polymer of the present invention. Preferred organic solvents include ketones such as methyl ethyl ketone, alcohols such as isopropanol,
Examples thereof include esters such as ethyl acetate. Also,
When the monofunctional or polyfunctional vinyl monomer or the compound having a monofunctional, difunctional, or trifunctional or higher functional ring-opening polymerizable group is a low molecular weight compound, when these are used in combination, the viscosity of the curable composition is adjusted. It is also possible to apply it without using a solvent.

Further, in the present invention, crosslinked fine particles can be added to the curable composition, if necessary. The addition of the crosslinked fine particles is preferable because the amount of curing shrinkage of the hard coat layer can be reduced and thus the adhesion to the substrate can be improved and curling can be reduced when the substrate is a plastic film. As the crosslinked fine particles, inorganic fine particles, organic fine particles,
Any of the organic-inorganic composite fine particles can be used without particular limitation. Examples of the inorganic fine particles include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like. Such inorganic finely crosslinked particles are generally hard, and by filling the hard coat layer, not only the shrinkage at the time of curing can be improved but also the surface hardness can be increased.

In general, the inorganic fine particles have a low affinity for the organic components such as the polymer of the present invention and the polyfunctional vinyl monomer, and therefore, if they are simply mixed, an aggregate is formed or the hard coat layer after curing is easily cracked. There are cases. In the present invention, in order to increase the affinity between the inorganic fine particles and the organic component, the surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment. The surface modifier preferably has a functional group capable of forming a bond with or adsorbing to the inorganic fine particles and a functional group having a high affinity for the organic component in the same molecule. As the compound having a functional group capable of binding to or adsorbing to the inorganic fine particles, a metal alkoxide compound such as silane, aluminum, titanium, zirconium, or a compound having an anionic group such as phosphoric acid, sulfonic acid or carboxylic acid group is preferable. Further, as the functional group having a high affinity with the organic component, it is possible to simply combine the organic component and the hydrophilicity / hydrophobicity, but a functional group capable of being chemically bonded to the organic component is preferable, and particularly an ethylenically unsaturated group, Alternatively, a ring-opening polymerizable group is preferable. In the present invention, the preferred inorganic fine particle surface modifier is a compound having a metal alkoxide or an anionic group and an ethylenically unsaturated group or a ring-opening polymerizable group in the same molecule.

Preferred examples of these surface modifiers include the following coupling agents having unsaturated double bonds and phosphoric acid,
Examples thereof include sulfonic acid and carboxylic acid compounds, but the present invention is not limited thereto. _{S-1 H 2 C = C} (X) COOC 3 H 6 Si (OCH 3) 3 S-2 H 2 C = C (X) COOC 2 H 4 OTi (OC 2 H 5) 3 S-3 H 2 C _{= C (X) COOC 2 H} 4 OCOC 5 H 10 OPO (OH) 2 S-4 (H 2 C = C (X) COOC 2 H 4 OCOC 5 H 10 O) 2 POOH S-5 H 2 C = C (X) COOC ₃ H ₆ OSO ₃ K S-6 H ₂ C = C (X) COO (C ₅ H ₁₀ COO) ₂ H S-7 H ₂ C = C (X) COOC ₅ H ₁₀ COOH (X = H or CH ₃ )

The surface modification treatment of these inorganic fine particles is preferably performed in a solution. When mechanically finely dispersing the inorganic fine particles, a surface modifier is present together,
Alternatively, after finely dispersing the inorganic fine particles, a surface modifier is added and stirred, or further, surface modification is performed before finely dispersing the inorganic fine particles (heating, drying, heating, or pH change if necessary). May be performed), followed by fine dispersion. In this case, the solvent is preferably a highly polar organic solvent. Specifically, alcohols,
Known organic solvents such as ketones and esters can be mentioned. As the disperser, it is preferable to use an ultrasonic disperser, a disperser, a homogenizer, a dissolver, a polytron, a paint shaker, a sand grinder, a kneader, an Eiger mill, a dyno mill, a coball mill, or the like.

The organic crosslinked fine particles include polyethylene, polypropylene, polytetrafluoroethylene, nylon, polyethylene terephthalate, polystyrene, poly (meth) acrylic acid esters and amides, polyvinyl chloride, acetylcellulose, nitrocellulose, polydimethylsiloxane, etc. The crosslinked rubber fine particles of SBR, NBR and the like, which are obtained by crosslinking the general-purpose resin, can also be preferably used. The organic fine particles can be arbitrarily selected from soft rubber particles to hard particles. For example, the above-mentioned inorganic crosslinked fine particles having a high hardness may be fragile and fragile although the curing shrinkage amount and the hardness are improved by increasing the addition amount to the hard coat layer. In such a case, it is preferable to add organic crosslinked fine particles whose hardness is arbitrarily adjusted at the same time so as to make it difficult to break. Further, core-shell particles such as a core having a high hardness and a shell having a low hardness, or a core having a low hardness and a shell having a high hardness can be used. Further, it is also preferable to use core-shell particles having different hydrophilicity / hydrophobicity for the purpose of ensuring dispersion stability in the hard coat layer or in the coating solvent. It is also possible to use organic-inorganic composite fine particles using inorganic crosslinked fine particles in the core. When these crosslinked fine particles are used as core-shell particles, both the core part and the shell part may be crosslinked, or either one of them may be crosslinked.

The average particle size of the crosslinked fine particles that can be used in the present invention is 1 to 20000 nm, and is 2 to 1000.
nm is more preferable, 5 to 500 nm is still more preferable, and 10 to 200 nm is most preferable. The shape of the crosslinked fine particles may be spherical, rod-shaped, needle-shaped, plate-shaped, etc. without particular limitation. The average particle size described in the present invention is the average value of the diameters of circles having the same area as the projected area of each particle.

When these crosslinked fine particles are added, the addition amount thereof is preferably 1 to 60% by volume of the hard coat layer after curing, and more preferably 3 to 40% by volume.

In the present invention, even when the hardness of the substrate itself is low, the hardness of the hard coat film can be increased by increasing the thickness of the hard coat layer after the hard coat film is cured. The film thickness of the hard coat layer in the present invention varies depending on the hardness of the substrate and is not particularly limited, but by increasing the film thickness of the hard coat layer, the hardness, which is a feature of the present invention, is high and cracks and film peeling occur. The effect of hardly occurring appears remarkably. The preferred film thickness is 1
5 to 200 μm, more preferably 20 to 150 μm
m, more preferably 25 to 80 μm, and particularly preferably 30 to 60 μm.

The base material used in the present invention may be metal, plastic, glass, wood, paper, etc. without particular limitation. Among them, a plastic substrate is particularly preferable, and when a plastic film is used as a substrate, the effect of the present invention is remarkably exhibited, and thus it is preferable. The types of plastic film are polyethylene terephthalate,
Films of polyester such as polyethylene naphthalate, polycarbonate, cellulose resins such as triacetyl cellulose and diacetyl cellulose are preferable. If the thickness of the film is too thin, the film strength will be weak, and if it is thick, the stiffness will be too large.
m is preferable, and 80 to 200 μm is more preferable.

The hard coat film of the present invention preferably has a high surface hardness. The hardness of the surface of the hard coat film referred to in the present invention can be expressed by a pencil hardness defined in JIS K5400, and the pencil hardness can be evaluated by directly scratching the hard coat-treated surface of the hard coat film with a pencil. The pencil hardness in this case is not particularly limited because it depends on the type of substrate,
It is preferably 3H to 9H, more preferably 4H to 9H, particularly preferably 5H to 9H.

In the hard coat film of the present invention, a curable composition comprising an ethylenically unsaturated group-containing compound, a ring-opening polymerizable group-containing compound, a polymerization initiator, crosslinked fine particles, a solvent and the like is applied onto a substrate. It can be obtained by curing. In addition to the curable composition, conventionally known additives such as an ultraviolet absorber, a surfactant for improving coating properties, and an antistatic agent may be added. Examples of the coating method include known coating methods such as curtain coating, dip coating, spin coating, printing coating, spray coating, roll coating, slide coating, blade coating, gravure coating, and wire bar method.

Further, for the purpose of improving the adhesiveness between the base material and the hard coat layer, one surface or both surfaces may be subjected to a surface treatment by an oxidation method or a textured method, if desired. Examples of the surface treatment method include chemical treatment, mechanical treatment,
Corona discharge treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, high frequency treatment, hot air treatment, ozone treatment,
Examples include ultraviolet irradiation treatment, active plasma treatment, and mixed acid treatment. Furthermore, more than one undercoat layer can be provided. Examples of the material for the undercoat layer include copolymers of vinyl chloride, vinylidene chloride, butadiene, (meth) acrylic acid ester, styrene, vinyl ester and the like, and latexes thereof, water-soluble polymers such as polyester, polyurethane and gelatin. .

As already described, the hard coat film of the present invention has a layer having a coefficient of dynamic friction of 0.4 or less on the outermost surface. The dynamic friction coefficient is preferably 0.3 or less, and particularly preferably 0.25 or less. The outermost surface layer having a low dynamic friction coefficient can be preferably formed by forming a low-friction lubricant layer on the outermost surface of the hard coat film. As the lubricant, any lubricant having a small coloring in the visible region can be used. As a lubricant, for example, "Introduction to Tribology"
Lubricating oils and greases described in (Okamoto Junzo et al., Koshobo) are mentioned, and more preferably lubricant paraffin hydrocarbons, naphthene hydrocarbons, aromatic hydrocarbons, polyolefins, polyalkylene glycols, polyol esters. , Phosphoric acid ester, silane, silicic acid ester, silicone, and fluorine-containing compound, and particularly preferably silicone. Examples of the silicone include those described in "Silicone Material Handbook" (edited by Toray Dow Corning Silicon Co., Ltd.). More preferably, it is a polysiloxane compound (silicone oil). Examples of the polysiloxane compound include polydimethylsiloxane (KF96 manufactured by Shin-Etsu Chemical Co., Ltd.) and amino-modified silicone oil (X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.).
S, KF-861, KF-864, etc.), epoxy modified silicone oil (KF-105, KF manufactured by Shin-Etsu Chemical Co., Ltd.)
-101, X-22-169-B, KF-103 etc.), carboxyl modified silicone oil (X-22-162A, X-22-3701E manufactured by Shin-Etsu Chemical Co., Ltd.), carbinol modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) KF-6001, X-22-4015, etc.), methacryl-modified silicone oil (X-22 manufactured by Shin-Etsu Chemical Co., Ltd.)
-164C, X-22-980, etc.), phenol-modified silicone oil (X-22-165B manufactured by Shin-Etsu Chemical Co., Ltd.)
Etc.), one end reactive modified silicone oil (X-22-170B, X-22-173B, X- manufactured by Shin-Etsu Chemical Co., Ltd.)
22-174D, X-22-176B, etc.), polyether modified silicone oil (KF-35 manufactured by Shin-Etsu Chemical Co., Ltd.)
1, KF-354, KF-945, etc.) and mercapto-modified silicone oil (SMS-022 etc. manufactured by Chisso), and more preferably polydimethylsiloxane, amino-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, A mercapto-modified silicone oil, particularly preferably polydimethylsiloxane, a carboxyl-modified silicone oil,
It is a polyether-modified silicone oil. Specifically, KF-96, X-22-162 manufactured by Shin-Etsu Chemical Co., Ltd.
A, X-22-3701E, KF-351, KF-35
4, KF-945 and the like are preferable.

As for the amount of the lubricant blended, if the amount is small, there is no effect of lowering the coefficient of friction, and if the amount is too large, the surface becomes coated and the appearance is unfavorable.
It is preferably m ² or more and 100 mg / m ² or less, more preferably 5 mg / m ² or more and 50 mg / m ² or less, and particularly preferably 10 mg / m ² or more and 50 mg / m ² or less. The lubricant layer may be included in the low reflection layer described below, or may be provided on the low reflection layer.

In the hard coat film of the present invention, an antireflection layer can be provided on the hard coat layer. The reflectance (regular reflectance) of the optical filter provided with the antireflection layer is
The average value of 450 nm to 650 nm is preferably 2.0% or less, and more preferably 1.5% or less. It is particularly preferably 1.0% or less. As the antireflection layer, a system provided with a low refractive index layer or a system using a light absorption layer is used. The low refractive index layer has a refractive index lower than that of a layer provided therebelow. The refractive index of the low refractive index layer is preferably 1.20 to 1.55,
More preferably, it is 1.20 to 1.50. The thickness of the low refractive index layer is preferably 50 to 400 nm, more preferably 50 to 200 nm.

Examples of the low refractive index layer are layers made of a fluoropolymer having a low refractive index (JP-A-57-34526, JP-A-3-130103, JP-A-6-115023 and JP-A-6-15023).
Nos. 313702 and 7-168004), and layers obtained by the sol-gel method (Japanese Patent Laid-Open No. 5-208).
No. 811, No. 6-299091, No. 7-168003.
No. 6), or a layer containing fine particles (Japanese Examined Patent Publication 6)
0-59250, JP-A-5-13021, and 6-5.
6478, 7-92306, 9-288201
(Described in each gazette of the issue). In the layer containing fine particles,
Voids can be formed in the low refractive index layer as microvoids between or within the fine particles. The layer containing fine particles preferably has a porosity of 3 to 50% by volume, and more preferably a porosity of 5 to 35% by volume.

In order to prevent reflection in a wide wavelength range,
A layer having a high refractive index (middle / high refractive index layer) is preferably laminated below the low refractive index layer. The high refractive index layer preferably has a refractive index of 1.65 to 2.40.
It is more preferably 70 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.90. The thickness of the medium / high refractive index layer is preferably 5 nm to 100 μm, more preferably 10 nm to 10 μm, and most preferably 30 nm to 1 μm. The haze of the medium / high refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less.

The medium / high refractive index layer can be formed by using a polymer binder having a relatively high refractive index. Examples of high refractive index polymer binders include polystyrene, styrene copolymers, polycarbonates, melamine resins, phenolic resins, epoxy resins and polyurethanes obtained by the reaction of cyclic (alicyclic or aromatic) isocyanates with polyols. Be done. Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups,
A polymer having a halogen atom other than fluorine as a substituent also has a high refractive index. A polymer binder may be formed by a polymerization reaction of a monomer that has been introduced with a double bond to enable radical curing.

In order to obtain a higher refractive index, inorganic fine particles may be dispersed in the polymer binder. The refractive index of the inorganic fine particles is preferably 1.80 to 2.80. The inorganic fine particles are preferably formed from a metal oxide or sulfide. Examples of metal oxides or sulfides include titanium dioxide (eg, rutile, mixed crystals of rutile / anatase, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, zirconium oxide and zinc sulfide. Among them, titanium oxide, tin oxide and indium oxide are particularly preferable. The inorganic fine particles are mainly composed of oxides or sulfides of these metals, and can further contain other elements. Here, the main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb,
Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Z
n, Al, Mg, Si, P and S are included. Inorganic materials that are film-forming and can be dispersed in a solvent or are themselves liquid, for example, alkoxides of various elements, salts of organic acids,
It is also possible to form a medium / high refractive index layer by using a coordination compound (eg, chelate compound) bonded to a coordination compound and an active inorganic polymer.

When a light absorbing layer is used as the antireflection layer,
As a light absorber, silver colloid, titanium nitride, SiOx
(0 <x <2), carbon black and the like can be mentioned, and silver colloid and carbon black are preferable. The thickness of the light absorption layer is preferably 2 to 200 nm,
More preferably, it is 5 to 100 nm. A layer having a refractive index of 1.2 to 1.6 is provided on the light absorption layer. The layer to be provided has the same meaning as the low reflection layer or the hard coat layer. Above all, Si produced by the sol-gel method
An O ₂ layer or a polyfunctional (meth) acrylate polymer is preferable in terms of refractive index and strength.

The hard coat film of the present invention has various functions on the hard coat layer such as an ultraviolet / infrared absorbing layer, a selective wavelength absorbing layer, an electromagnetic wave shielding layer and an antifouling layer in addition to the antireflection layer. A conductive layer can be provided.
These functional layers can be produced by a conventionally known technique. Further, for the purpose of improving the adhesion between the functional layer and the hard coat layer of the hard coat film of the present invention, a surface treatment is performed on the hard coat layer, or an adhesive layer,
An adhesive layer can be provided. As the surface treatment method, the methods mentioned above as the surface treatment method of the substrate can be preferably used. Further, as the adhesive layer and the adhesive layer, the above,
The materials mentioned for the undercoat layer applied on the substrate can be preferably used.

When a plastic film is used as a substrate, the hard coat film of the present invention provided with these functional layers serves as a high-hardness functional film, and is used as a cathode ray tube display device (CRT) or liquid crystal display device ( It is suitable for a display such as an LCD), a plasma display panel (PDP), a field emission display (FED), a touch panel for home electric appliances, and a protective film for glass.

The synthesis examples of the polymer of the present invention are shown below, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of Exemplified Compound K-1 275 ml of methyl ethyl ketone (MEK) was stirred under a nitrogen stream at 60 ° C. for 1 hour, and 0.5 g of V-65 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added to 8.3 ml of MEK. The total amount of the dissolved product was added. Then, glycidyl methacrylate (5
0 g) was added dropwise over 2 hours, and after completion of the addition, V-65
(0.5 g) in MEK (8.3 ml) was added and 2
Reacted for hours. Then, the reaction temperature was set to 80 ° C. and the reaction was carried out for 2 hours, and after the reaction was completed, it was cooled to room temperature. The obtained reaction solution was added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 35 ° C. for 8 hours to obtain 45 g of K-1.

Synthesis Example 2 Synthesis of Exemplified Compound P-1

[0095]

[Chemical 13]

The above 1b (3.0 mol) was dissolved in 1400 ml of tetrahydrofuran (THF), and the reactor was charged with 5
Cooled to ° C. 1 a (3.15 mol) of the above
The solution was added dropwise over a period of time and then reacted for 6 hours. The resulting reaction solution was concentrated under reduced pressure at 30 ° C. and then distilled under reduced pressure. 1
Fractions at 118 to 121 ° C. were collected under reduced pressure of 33 Pa and purified by silica gel column chromatography (eluent: acetone / hexane = 5/95 (volume ratio)) to obtain 1 above.
362 g of c was obtained. Next, methyl ethyl ketone (MEK)
After stirring 275 ml under a nitrogen stream at 60 ° C. for 1 hour, V-
0.5 g of 65 (Wako Pure Chemical Industries, Ltd. polymerization initiator) was added to MEK8.3.
All that was dissolved in ml was added. After that, 1c (5
0 g) was added dropwise over 2 hours, and after completion of the addition, V-65
(0.5 g) in MEK (8.3 ml) was added and 2
Reacted for hours. Then, the reaction temperature was set to 80 ° C. and the reaction was carried out for 2 hours, and after the reaction was completed, it was cooled to room temperature. The obtained reaction solution was added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 35 ° C. for 8 hours to obtain 43 g of the above 1d. Then 1d (43 g) was dissolved in acetone (390 ml) and cooled to 5 ° C. Triethylamine (39
(0 mmol) was added dropwise over 1 hour, and after completion of the addition, reaction was performed at room temperature for 24 hours. Then, the reaction vessel was cooled to 5 ° C., 29.3 ml of a 6N aqueous hydrochloric acid solution was added dropwise over 1 hour, and after completion of the addition, the mixture was stirred for 1 hour. Ethyl acetate (1 L) and 10 mass% sodium chloride aqueous solution (1 L) were added to the obtained reaction solution, and the mixture was stirred and then the aqueous layer was separated. Furthermore, the organic layer was washed twice with a 10 mass% sodium chloride aqueous solution (1 L), 100 g of sodium sulfate was added, and the mixture was dried for 1 hour, and then sodium sulfate was filtered off. The obtained solution was concentrated to 500 ml and then added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 20 ° C for 8 hours to obtain 33 g of Exemplified compound P-1.

Synthesis Example 3 Synthesis of Exemplified Compound P-19 Polyvinyl alcohol (PVA-10 manufactured by Kuraray Co., Ltd.)
5: Saponification degree 98.5%) (30 g) was dissolved in dimethyl sulfoxide (1000 ml), pyridine (200 ml) and nitrobenzene (10 ml) were added, and the mixture was cooled to 10 ° C. Thereafter, 100 ml of acrylic acid anhydride was added dropwise over 1 hour, and after completion of the addition, reaction was carried out at room temperature for 24 hours. The obtained reaction solution was added dropwise to 20 L of water over 1 hour to remove the precipitate by 1
Dissolve in L ethyl acetate and prepare a 2N aqueous hydrochloric acid solution (1 L)
It was washed twice with. Further, it was washed twice with a 10 mass% sodium chloride aqueous solution (1 L) to obtain 100 g of sodium sulfate.
After adding and drying for 1 hour, sodium sulfate was filtered off. Concentrate the resulting solution to 500 ml and then add hexane 1
The mixture was added dropwise to 0 L over 1 hour, and the precipitate was dried under reduced pressure at 20 ° C for 8 hours to obtain 28 g of Exemplified compound P-19.

Synthesis Example 4 Synthesis of Exemplified Compound C-1

[0099]

[Chemical 14]

The above 1b (3.0 mol) was dissolved in 1400 ml of tetrahydrofuran (THF), and the reaction vessel was heated at 5 ° C.
Cooled to. The above-mentioned 1a (3.15 mol) was added dropwise thereto over 1 hour, and then reacted for 6 hours. The resulting reaction solution was concentrated under reduced pressure at 30 ° C. and then distilled under reduced pressure. Thirteen
Fractions at 118 to 121 ° C were collected under reduced pressure of 3 Pa and subjected to silica gel column chromatography (eluent: acetone /
Purified with hexane = 5/95 (volume ratio), and above 1c
362g was obtained. Next, methyl ethyl ketone (MEK)
After stirring 275 ml under a nitrogen stream at 60 ° C. for 1 hour, V-
0.5 g of 65 (Wako Pure Chemical Industries, Ltd. polymerization initiator) was added to MEK8.3.
All that was dissolved in ml was added. After that, 1c (4
1.9 g) and glycidyl methacrylate (15.0 g)
Was added dropwise over 2 hours, and after completion of the addition, V-65
(0.5 g) in MEK (8.3 ml) was added and 2
Reacted for hours. Then, the reaction temperature was set to 80 ° C. and the reaction was carried out for 2 hours, and after the reaction was completed, it was cooled to room temperature. The obtained reaction solution was added dropwise to 10 L of hexane over 1 hour, and the precipitate was dried under reduced pressure at 35 ° C. for 8 hours to obtain 49 g of 2d. Next, 2d (49 g) was dissolved in acetone (390 ml),
Cooled to 5 ° C. Triethylamine (390mm)
ol) is added dropwise over 1 hour, and after completion of the addition, at room temperature, 2
The reaction was carried out for 4 hours. Then, cool the reaction vessel to 5 ° C,
29.3 ml of a 6N aqueous hydrochloric acid solution was added dropwise over 1 hour, and after completion of the addition, the mixture was stirred for 1 hour. Ethyl acetate (1 L) and 10 mass% sodium chloride aqueous solution (1 L) were added to the obtained reaction solution, and the mixture was stirred and then the aqueous layer was separated. Further, the organic layer is washed with a 10% by mass sodium chloride aqueous solution (1 L) to obtain 2
After washing twice, adding 100 g of sodium sulfate and drying for 1 hour, sodium sulfate was filtered off. The obtained solution was concentrated to 500 ml, then added dropwise to 10 L of hexane over 1 hour, the precipitate was dried under reduced pressure at 20 ° C. for 8 hours, and 36 g of Exemplified compound C-1 (x / y = 70/30 mass%). Obtained.

The present invention is further described below with reference to examples, but the present invention is not limited to these.

[0102]

EXAMPLES Examples 1 to 4 and Comparative Examples 1 to 4 1. Preparation and Application of Undercoat Liquid Using the following materials, an undercoat liquid for providing adhesion between the corona-treated 175 μm polyethylene terephthalate film and the hard coat layer was prepared and applied. (Undercoat liquid composition) UV3300B (Nippon Synthetic Chemical Industry Co., Ltd. terminal acrylic-modified urethane oligomer) 5 parts by weight _{C 9 H 19 -C 6 H 4} - (OCH 2 CH 2) 12 OH 0.05 parts by mass of toluene / acetic acid Methyl (1/1) 94.95 parts by mass This undercoating solution was applied at a rate of 7 ml / m ² using a bar coater, and 160 ° C. in a heating zone while being transported.
And heat dried for 5 minutes. Immediately before winding, it was cooled to 30 ° C. or lower with a cooling roller, and the prepared undercoated polyethylene terephthalate film (F-1) was wound.

2. Preparation of Hard Coat Layer Coating Liquid and Preparation of Hard Coat Layer As described below, a hard coat layer coating liquid containing inorganic particles was prepared, and subjected to coating, drying and ultraviolet curing treatments to form a hard coat layer. 2-1. Preparation of Inorganic Particle Dispersion Liquid (M-1) (Composition of Inorganic Particle Dispersion Liquid (M-1)) Methyl isobutyl ketone 234 g Aronix M5300 (oligo ester acrylate polymer manufactured by Toagosei Co., Ltd.) 36 g AKP-G015 (Sumitomo Chemical Co., Ltd.) Alumina) 180 g Ceramic coated sand mill (1/4)
The sand mill of G and the medium were 1 mmφ zirconia beads) and finely dispersed at 1600 rpm for 10 hours.

2-2. Preparation of Coating Solution for Hard Coat Layer 100 g of methyl ethyl ketone, 60 g of glycidyl methacrylate corresponding to repeating unit E-1 and a mixture of dipentaerythritol hexaacrylate (DPHA,
180 g of Nippon Kayaku Co., Ltd. was added and dissolved. Furthermore, 25 ml of the above-prepared inorganic particle dispersion liquid (M-1), a photopolymerization initiator (Irgacure 18
4.8 g (manufactured by Ciba-Geigy) and 7 g of methyl ethyl ketone. Furthermore, cationic polymerization initiator (UV
I-6990 (Union Carbide Japan Co., Ltd.) was mixed with methyl isobutyl ketone / methyl ethyl ketone mixed solution (1
After dissolution in 1/1), 13.4 g was added. The mixture was stirred for 30 minutes and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for hard coat layer.

2-3. Preparation of Hard Coat Film Polyethylene terephthalate film (F-1) provided with an undercoat layer was coated with a coating solution for a hard coat layer prepared in 2-2 above using a bar coater to a film thickness shown in the table. To be coated and dried so as to be irradiated with ultraviolet rays to prepare a film (H-1) having a hard coat layer.

3. Preparation of Low Reflection Layer 3-1. Preparation of silver-palladium colloid coating liquid: (Preparation of silver-palladium colloid dispersion liquid) 30% iron (II) sulfate FeSO ₄ .7H ₂ O and 40% citric acid were prepared.
Mix, hold at 20 ° C, and stir 10% silver nitrate and palladium nitrate (mixed at a molar ratio of 9/1) with stirring
The solution was added and mixed at a rate of 200 ml / min, and then washing of the silver-palladium colloid produced was repeated by centrifugation, and pure water was added so that the final concentration was 3% by weight.
A silver palladium colloidal dispersion was prepared. As a result of TEM observation, the particle size of the obtained silver colloidal particles was about 9 to 1
It was 2 nm. As a result of measurement by ICP, the ratio of silver to palladium was the same as the charging ratio of 9/1.

(Preparation of Silver Palladium Colloid Coating Solution) 100 g of the silver palladium colloid dispersion prepared above was i.
-Add propyl alcohol, ultrasonically disperse, pore size 1μm
To prepare a silver-palladium colloid coating solution.

3-2. Preparation of coating liquid 1 for transparent thin film layer on silver layer Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPH
A, manufactured by Nippon Kayaku Co., Ltd., 2 g, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 80 mg, and photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 30 m
g was added to a mixed solution of 38 g of methyl isopropyl ketone, 38 g of 2-butanol and 19 g of methanol and dissolved.
The mixture was stirred for 30 minutes and then filtered through a polypropylene filter having a pore size of 1 μm to prepare coating solution 1 for transparent thin film layer on silver layer.

3-3. Preparation of coating solution 2 for transparent thin film layer on silver layer 0.01 g of hydrochloric acid 24 in 0.01 g of tetraethoxysilane
g and stirred vigorously for 4 hours. After confirming that the liquid became uniform, leave it at room temperature for 18 hours and then add 40 g of this liquid.
On the other hand, 165 g of methyl ethyl ketone was added and stirred for 30 minutes to prepare coating solution 2 for a transparent thin film layer on a silver layer.

3-4. Preparation of coating liquid 3 for transparent thin film layer on silver layer
g and stirred vigorously for 4 hours. After confirming that the solution became uniform, leave it at room temperature for 18 hours, and then add 165 g of methyl ethyl ketone and 1 g of silicone oil KF-945 (manufactured by Shin-Etsu Chemical Co., Ltd.) to 40 g of this solution and stir for 30 minutes to clear on the silver layer. Coating solution 3 for thin film layer was prepared.

3-5. Application of silver-palladium colloid coating solution After corona-treating the film (H-1) with a hard coat layer, the silver colloid coating solution prepared in 3-1 above was hardened with a wire bar to a coating amount of 70 mg / m ^2. It was applied on the coat layer and dried at 40 ° C. to form a silver layer (Ag-1).

3-6. Coating of coating liquid 1 for transparent thin film layer on silver layer Coating liquid 1 for transparent thin film layer is coated and dried on Ag-1 silver layer, and is irradiated with ultraviolet rays under the condition of 3 Kw and 750 mJ. A coated film (AR-1) was produced. The film thickness of the transparent thin film layer on the silver layer was 90 nm.

3-7. Coating of Coating Liquid 2 for Transparent Thin Film Layer on Silver Layer Coating liquid 2 for transparent thin film layer was coated on the silver layer of Ag-1 and then dried at 110 ° C. for 30 minutes to obtain a hard coat film with a low reflection layer (AR-2). ) Was produced. The film thickness of the transparent thin film layer on silver was 80 nm.

3-8. The transparent thin film layer coating liquid 3 was applied onto the silver layer in the same manner as the coating 3-7 of the transparent thin film layer coating liquid 3 and dried to prepare a hard coat film (AR-3) with a low reflection layer. The film thickness of the transparent thin film layer on silver was 85 nm.

4. Preparation of Lubrication Layer To 300 g of methyl ethyl ketone, 3 g of silicone oil KF-945 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a slip agent, was added and stirred for 30 minutes to prepare a coating liquid for a lubrication layer. This solution was applied onto the hard coat films AR-1 and AR-2 with a low reflection layer so that the amount of KF-945 shown in Table 4 was obtained.

With respect to the prepared hard coat film, the dynamic friction coefficient, 450 to 650 nm average reflectance, steel wool resistance, pencil hardness and film peeling were measured. The results are shown in Table 4.

The dynamic friction coefficient was measured using a surface property measuring device HEIDON-14 manufactured by Shinto Kagaku.・ Steel wool resistance evaluation method After conditioning the film for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, the steel wool of # 0000 has a ground contact area of 1
The occurrence of scratches after 50 reciprocations under a cm ² load of 200 g was visually determined. ◯: No scratches were generated Δ: Scratches were slightly observed ×: Many scratches were generated

450 to 6 by using a reflectance spectrophotometer (manufactured by JASCO Corporation)
It was evaluated by the average reflectance of specular reflection at an incident light of 5 ° in the wavelength region of 50 nm. -Pencil hardness After the prepared hard coat film and hard coat glass sample were left for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, a pencil hardness specified by JIS K5400 was used by using a test pencil specified by JIS S6006. According to the evaluation method, scratching was repeated 5 times with a pencil of each hardness using a weight of 1 kg, and the number of times that no scratch was observed was shown. It is described that the scratches defined in JIS K5400 are coating film tears and scratches on the coating film, and dents on the coating film are not included. Deciding.・ Film peeling 1 mm x 1 mm with a cutter on the hard coat film surface of the hard coat film and hard coat glass sample.
Put 100 cross hatches (squares), temperature 25 ℃,
After standing for 2 hours under the condition of relative humidity of 60%, a cellophane tape (manufactured by Nichiban Co., Ltd.) was adhered on the cell, and when the cellophane tape was peeled off, the number of squares in which the cured coating was peeled off from the film substrate was measured. evaluated.

[0119]

[Table 4]

From the results shown in Table 4, the following is clear. The hard coat film of the present invention has excellent scratch resistance and high hardness. On the other hand, in the cases of Comparative Examples 1 and 2 in which the coefficient of dynamic friction of the surface exceeds 0.4 and is high, the scratch resistance is poor. Further, the hard coat films of Comparative Examples 3 and 4 in which the hard coat layer has a thickness of less than 10 μm have low hardness.

[0121]

EFFECTS OF THE INVENTION The hard coat film of the present invention is resistant to film peeling and cracking, and has sufficient hardness and scratch resistance. Utilizing this property, the hard coat film of the present invention can be used as a surface protective film having an optical function such as a display such as a CRT, LCD, PDP, FED, a touch panel, glass and the like.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 16, 2001 (2001.8.1)
6)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Added

[Correction content]

[Title of Invention] Hard coat film

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 67:00 G02B 1/10 A (72) Inventor Yasui Sakurai 210 Nakanuma, Minamiashigara City, Kanagawa Fuji photo film Co., Ltd. in the F-term (reference) 2K009 AA03 AA15 BB02 BB24 CC09 CC22 CC24 CC42 DD02 DD05 EE03 4F006 AA35 AB24 BA02 CA05 DA04 4F100 AA02 AA20C AK21B AK24B AK25 AK25B AK25J AK41A AR00C AT00A BA02 BA03 BA07 BA10A BA10C CA19C CC00B DE01B EH46B EJ05B EJ08B GB41 JK12 JK12B JK14 JK16B JK16C JN06 JN06C YY00 YY00B YY00C

Claims (10)

[Claims] 1. A hard coat film comprising a hard coat layer having a film thickness of 10 μm or more on a substrate, and a layer having a surface dynamic friction coefficient of 0.4 or less on the outermost surface. 2. The hard coat film according to claim 1, wherein the average reflectance at 450 to 650 nm is 2% or less. 3. The hard coat film according to claim 1 or 2, wherein the hard coat film has a low reflection layer containing SiO ₂ . 4. The hard coat film according to claim 3, wherein the low reflection layer contains a lubricant in an amount of 5 mg / m ² or more and 100 mg / m ² or less. 5. The hard coat layer of the hard coat film has 3 in the same molecule as the compound containing an ethylenically unsaturated group.
It is a hard-coat layer formed by apply | coating and hardening the curable composition containing both of the compound containing one or more ring-opening polymerizable groups, It is characterized by the above-mentioned. Hard coat film. 6. The compound containing a ring-opening polymerizable group is a crosslinkable polymer containing a repeating unit represented by the following general formula (1), wherein: Hard coat film. General formula (1) (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. P ¹ is a monovalent group containing a ring-opening polymerizable group, and L ¹ is a single bond or a divalent linkage. It is a base.) 7. The hard coat film according to claim 1, wherein the ring-opening polymerizable group is a cationically polymerizable group. 8. The hard coat film according to claim 1, wherein the curable composition contains crosslinked fine particles. 9. The hard coat film according to claim 1, wherein the surface has a pencil hardness of 4H to 9H. 10. The hard coat film according to claim 1, wherein the substrate is a polyester film and the film thickness of the hard coat layer is 20 to 200 μm.