JPH01244848A - Hard coat film and its manufacture - Google Patents

Abstract

PURPOSE:To obtain the hard coat film excellent in scratch resistance and abrasion resistance by a method in which a film is coated with the resin composition containing respectively specified amounts of the urethane compound into which the diol having a specified molecular weight and the compound having polymerizable unsaturated group are introduced, and the monomer having radical polymerizable unsaturated group, and then electron beam is applied to said film. CONSTITUTION:50-400pts.wt. of the monomer having at least one radical polymerizable unsaturated group in one molecular is added to 100pts.wt. of urethane acrylate oligomer obtained by combining diisocyanate and the diol having hydroxyl groups on both terminals and 200-3,000 of weight average molecular weight with the acrylate compound having two hydroxyl group and one or more radical polymerizable unsaturated group. Thus resin composition is generated. After the upper surface of a substrate film 1 has been coated with the coating liquid 3 of the resin composition by using a coating device 2, mirror surface-material 4 is laminated on the substrate film 1 by directing the surface of mirror state to said film 1. The coated film is cured by an electron beam radiator 5, and then the mirror surface material 4 is separated lastly.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hard coat film for use on the surface of articles such as electrical products and OA equipment, and a method for producing the same. The present invention relates to a hard coat film which is excellent in properties such as the like, and also has appropriate flexibility and flexibility, and a method for producing the same.

[Conventional technology and problems]

In recent years, plastic materials, including engineering plastics, have been widely used as substitutes for inorganic materials such as metal materials and glass, taking advantage of their properties such as toughness and workability. However, since the surface hardness and scratch resistance are poor, it is necessary to provide a surface protective layer.

Conventional techniques for hardening plastic surfaces include:
Coatings with thermosetting resins such as organosiloxane or melamine or photocuring polyfunctional acrylic resins, or forming metal thin films by vacuum evaporation, sputtering, etc. have been practiced.

However, conventional scratch-resistant surface protective layers using thermosetting resins or photocuring resins lack flexibility and are prone to cracking. Therefore, when a surface protective layer is formed on a curved molded article or synthetic resin film, it is difficult to process the surface into a curved shape, and cracks occur due to bending, making the surface protective layer unsatisfactory. Furthermore, since the surface protective layer made of a metal thin film is processed in a vacuum system, it has the drawbacks of low productivity and difficulty in processing large shapes.

In addition, with the recent development of electrical products and OA equipment, CR
It has good scratch resistance and abrasion resistance, as well as appropriate flexibility and bendability, and is used for the anti-reflection filter of T-displays, the front protective layer of LCD displays, and the surface of pressure-sensitive keyboards. Furthermore, it is desired to develop a hard coat film that can have a non-glare surface if necessary.

Therefore, an object of the present invention is to provide a hard coat film having excellent scratch resistance and abrasion resistance, as well as appropriate flexibility and flexibility, and a method for producing the same.

[Means for solving problems]

In view of the above problems, a urethane compound having a diol having a specific molecular weight and a compound having a polymerizable unsaturated group introduced into the skeleton, and a monomer having at least one radically polymerizable unsaturated group, respectively. The present inventors have discovered that a hard coat film with excellent scratch resistance, abrasion resistance, etc. can be obtained by applying a resin composition containing a specific amount to a film and irradiating it with electron beams, and has conceived the present invention. .

That is, the hard coat film of the present invention comprises (a) a diisocyanate, a diol having a hydroxyl group at both ends and a weight average molecular weight of 200 to 3,000, and an acrylate type having a hydroxyl group at both ends and a radically polymerizable unsaturated group. (b) A resin composition containing 50 to 400 parts by weight of a monomer having at least one radically polymerizable unsaturated group in one molecule, to 100 parts by weight of a urethane acrylate oligomer bonded with a compound. It is characterized by having a resin layer cured by radiation and a film supporting the cured resin layer.

The method for producing the hard coat film includes (a) a diisocyanate, a diol having a hydroxyl group at both ends and a weight average molecular weight of 200 to 3,000, and an acrylate compound having a hydroxyl group at both ends and a radically polymerizable unsaturated group. (b) 50 parts by weight of a urethane acrylate oligomer having at least one radically polymerizable unsaturated group in one molecule.
A step of adding ~400 parts by weight to produce a resin composition, a step of applying the obtained resin composition to a support film, a step of laminating a release film thereon, and a step of laminating the release film from the side of the release film. The method is characterized by comprising a step of curing the resin composition by irradiating the resin composition with an electron beam, and a step of peeling off the release film.

Another hard coat film of the present invention is (a
) A diisocyanate, a diol having a hydroxyl group at both ends and a weight average molecular weight of 200 to 3000, a curable compound having two hydroxyl groups and one or more radically polymerizable unsaturated groups, and a curable compound having a hydroxyl group at both ends. For 100 parts by weight of a urethane acrylate oligomer bonded with an acrylate compound having a radically polymerizable unsaturated group, (b) a monomer having at least one radically polymerizable unsaturated group in one molecule; It is characterized by having a resin layer obtained by curing a resin composition containing 50 to 400 parts by weight by electron beam irradiation, and a film supporting the cured resin layer.

The method for producing the hard coat film includes (a) a diisocyanate, a diol having a hydroxyl group at both ends and a weight average molecular weight of 200 to 3000, and a diol having two hydroxyl groups and one or more radically polymerizable unsaturated groups. With respect to 100 parts by weight of the urethane acrylate oligomer formed by bonding with an acrylate compound, (b) at least 1 part per molecule
Monomer having 50 to 4 radically polymerizable unsaturated groups
00 parts by weight to produce a resin composition, a step of applying the obtained resin composition to a support film, a step of laminating a release film thereon, and a step of laminating an electronic release film from the release film side. The method is characterized by comprising a step of curing the resin composition by irradiating the resin composition with a beam, and a step of peeling off the release film.

The hard coat film of the present invention will be explained in detail below.

The diisocyanate that is a component of the resin composition that can be used in the present invention is an aliphatic or aromatic diisocyanate compound having two isocyanate groups in one molecule, such as tetramethylene diisocyanate,
hexamethylene diisocyanate, 2.4-) lylene diisocyanate, 2.6-) lylene diisocyanate,
4,4-diphenylmethane diisocyanate, 1.5-
Naphthalene diisocyanate, 3,3-dimethyl-4,
4”-diphenylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate, ■, 3-
Bis(isocyanitomethyl)cyclohexane, trimethylhexamethylene diisocyanate, etc. alone or in combination
Can be used in combination of more than one species.

In particular, inphorone diisocyanate, hexamethylene diisocyanate, etc. are preferred in order to have weather resistance.

Diols having hydroxyl groups at both ends include polyester prepolymers, polyether prepolymers and polycarbonate prepolymers having hydroxyl groups at both ends.

Examples of polyester prepolymers having hydroxyl groups at both ends include (a) addition reaction products of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or its derivative or an epoxy compound; (b) an addition reaction product of a polybasic acid and a polyol; and (iii) open-circuit polyester compounds derived from cyclic ester compounds, which may be used alone or in combination of two or more.

Examples of the diol compound having an aromatic or spiro ring skeleton used in the addition reaction product (a) include CH3C-CHJ(CH2CH20), tl.

CH3 -0 (CH, CH20) meter.

etc.

Representative examples of lactone compounds include ε-caprolactone and δ-valerolactone.

Further, typical examples of epoxy compounds include ethylene oxide and propylene oxide.

Next, the polybasic acids used in the condensation product (b) include saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, and sepacic acid, maleic acid, fumaric acid, and itaconic acid. There are unsaturated polybasic acids such as acid and citraconic acid, and polyols include ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexane glycol.

Examples of polyether prepolymers having hydroxyl groups at both ends include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol.

Examples of polycarbonate prepolymers having hydroxyl groups at both ends include Plaxel CD-210 (molecular weight: 1000) manufactured by Daicel Chemical Industries, Ltd., Plaxel CD-220 (molecular weight: 2000), and 0N-983 manufactured by Nippon Polyurethane Industries, Ltd. (molecule 11000)
Polycarbonate diols such as

The diol having hydroxyl groups at both ends needs to have a weight average molecular weight of 200 to 3,000. If the weight average molecular weight is less than 200, the abrasion resistance measured by the falling sand abrasion test and the taper abrasion test will be poor, and if it exceeds 3000, sufficient hardness will not be obtained after curing. The preferred weight average molecular weight range is 500 to 2000, particularly 500 to 1
It is 500.

Further, in order to show excellent wear resistance properties in the sand drop abrasion test and the taper abrasion test, polytetramethylene ether glycol, polybutylene adipate, polycarbonate diol, etc. are particularly preferred. Further, in order to provide a cured product having good flexibility, it is preferable to use a linear aliphatic diol.

Acrylate compounds that have a hydroxyl group at the end and a radically polymerizable unsaturated group bond to the isocyanate group of a urethane compound, and easily generate radicals when irradiated with an electron beam, resulting in a so-called unsaturated group that causes a crosslinking reaction. It is a radically polymerizable compound. Such radically polymerizable acrylate compounds having a hydroxyl group at the terminal are ester compounds of acrylic acid or methacrylic acid, particularly derivatives thereof, and have one hydroxyl group at both ends, such as hydroquine ethyl acrylate, Hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxycyclohexyl acrylate.

5-hydroxycyclooctyl acrylate, 5-hydroxycyclooctyl acrylate, 2-hydroxy-
Including (meth)acrylic acid ester compounds having one polymerizable unsaturated group such as 3-phenyloxypropyl acrylate, ester compounds having two polymerizable unsaturated groups represented by the formula 0, etc. are used. be able to.

Examples of the curable compound having two hydroxyl groups and one or more radically polymerizable unsaturated groups include glycerol methacrylate and the following general formula: % formula % (where R, R' are CH, or H) , R4 is a short chain diol such as ethylene glycol, propylene glycol, diethylene glycol, phthanediol, 1,6-hexanediol, etc.) can be used. The amount of the curable compound in the urethane acrylate oligomer is preferably 50 to 400 parts by weight from the viewpoint of softness and curability.

Next, a method for producing the above urethane acrylate oligomer will be explained.

The first step using a diisocyanate and a diol having hydroxyl groups at both ends can generally be represented by the following reaction formula.

20CN-R1-NCO+, HO-L-OH-However,
R1 is a hydrocarbon group having 4 to 14 carbon atoms, and R2 is a diol residue.

The reaction temperature in the first step is 40-60℃ and the reaction time is 1-4
It's time. Although the reaction may be carried out without a solvent, it is preferably carried out in a solvent such as a ketone that has no reactivity with incyanate groups.

The second step is to react the reaction product of the first step with an acrylate compound having a hydroxyl group at the end and a radically polymerizable unsaturated group, and can typically be represented by the following formula.

However, R3 is an acrylate residue (acrylate ester group or methacrylate ester group).

Note that instead of reacting all isone anate residues with a radically polymerizable compound, one end is reacted with a triol such as trimethylolpropane so that three residues of the radically polymerizable compound are contained in one molecule. You can also do it.

The reaction temperature in the second step is 40-60℃ and the reaction time is 2-6
It's time. Although it may be carried out without a solvent as in the first step, it is preferably carried out in a solvent such as a ketone.

In addition, in the reaction system of the second step, in order to protect the (meth)acrylic acid ester group in the radically polymerizable acrylate compound, a polymerization inhibitor such as nihydroquinone, hydroquinone monomethyl ether, benzoquinone, etc.
-di-t-butyl-p-cryol, etc. 100 to 1
It is preferable to add about 1000 pp. Further, triethylamine, piperazine, triethanolamine, dibutyltin dilaurate, stannath octoate, stannath laurate, dioctyltin dilaurate, etc. can be added to the reaction system for the purpose of promoting the reaction.

Among the monomers mixed into the urethane acrylate oligomer, methyl acrylate, 2-
Acrylic acid esters such as ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate; methyl methacrylate,
Mecrylic acid esters such as ethyl methacrylate, propyl methacrylate, methacrylic ethyl methacrylate, ethoxyethyl methacrylate, phenyl methacrylate, lauryl methacrylate; unsaturated carboxylic acid amides of acrylamide and methacrylamide; 2-(N, N
-dimethylamino)ethyl acrylate, 2-(N,N
-dimethylamino)ethyl methacrylate, l-(N,
N-dibenzylamino)ethyl acrylate, (N,N
-dimethylamino)methyl methacrylate), 2-(N.

Substituted amino alcohol esters of unsaturated acids such as N-diethylamino)propyl acrylate; N-methylcarbamoyloxyethyl acrylate, N-ethylcarbamoyloxyethyl acrylate, N-butylcarbamoyloxyethyl acrylate, N-phenylcarba Examples include carbamoyloxyalkyl acrylates such as moyloxyethyl acrylate, 2-(N-methylrubamoyloxy)ethyl acrylate, and 2-carbamoyloxypropyl acrylate.

Further, the polyfunctional monomer has two or more radically polymerizable unsaturated groups, and particularly preferred is a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups. Specific examples include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate1. Ethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di(meth)acrylate, polybrobylene glycol diglycidyl ether di(meth)acrylate, sorbitol tetragrindyl Examples include polyfunctional (meth)acrylates such as ether tetra(meth)acrylate and melamine (meth)acrylate.

Among the above-mentioned monofunctional or polyfunctional (meth)acrylates, those having a (meth)acrylic equivalent (molecular weight/number of functional groups) of 90 to 200, especially 10 to obtain good scratch resistance.
It is preferably 0 or less.

Addition of monofunctional or polyfunctional monomers changes the surface properties after curing, but in order to obtain the hard coat film of the present invention, it is necessary to add a relatively large amount of the monomers. Specifically: It is necessary that the amount of the monofunctional or polyfunctional monomer be 50 to 400 parts by weight per 100 parts by weight of the urethane acrylate oligomer. In this case, the resulting cured film has high surface hardness, resulting in a hard coat that has extremely high scratch resistance and also relatively high flexibility. If the monomer content is less than 50 parts by weight, the scratch resistance, abrasion resistance, and hardness necessary for a hard coat cannot be obtained, and if it exceeds 400 parts by weight, although it has excellent scratch resistance, sufficient flexibility cannot be obtained, resulting in cracks, etc. becomes more likely to occur. The desirable monomer content for the hard coat is 100 to 300 parts by weight.

The resin composition used in the present invention may also contain an ultraviolet absorber or a light stabilizer, if necessary. As ultraviolet absorbers, benzotriazoles such as 2-(2-
hydroxy-5-methylphenyl)benzo)IJ azole, 2-(2-hydroxy-3,5 ditertiary-amylphenyl)benzotriazole, 3-[3(benzotriazol-2-yl-5-
Examples include t-butyl-4-hydroxyphenyl]propionic acid ester. In addition, the light stabilizer is a hindered amine type, for example, 2-(3,5-di-t-butyl 7-butyl
Bis(1,2,2,6-bentamethyl-4-piperidyl), bis-(1,2゜2.6.6-bentamethyl-4-4-hydroxybenzyl)-2'-n-butylmalonate
piperidyl) sebacate, tetrakis-(2,2,6,
6-tetramethyl-4-piperidyl)-1,2,3,4
-butane tetracarboxylate and the like.

A significant improvement in weather resistance can be obtained by using a UV absorber and a light stabilizer together. Addition of only a UV absorber has no effect of reducing deterioration and hardly improves weather resistance. Furthermore, although the addition of only a light stabilizer has the effect of reducing deterioration, it is not sufficient to improve weather resistance. The amount of the ultraviolet absorber added and the amount of the light stabilizer added are 0.01 to 10 parts by weight, respectively, per 100 parts by weight of the resin composition, particularly 0.1 to 2 parts by weight of the ultraviolet absorber and the light stabilizer. It is desirable to add 0.5 to 4 parts by weight at the same time. If the amount added is too small, there will be no effect of improving weather resistance, and if it is too large, adverse effects such as a decrease in curability and adhesion will appear.

The electron beam curable resin composition thus obtained has tackiness before curing. It is important to have tackiness because the physical properties (abrasion resistance, etc.) of the resulting coating film will not be sufficient if there is no tackiness before curing.

Further, as the supporting film used in the present invention, polyester film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polycarbonate film, nylon film, polystyrene film, ethylene-vinyl acetate copolymer film, etc. are used. However, polyester film is particularly preferred.

The thickness of the support film used in the present invention is not particularly limited and can vary from as thin as 2 μm to as thin as several cm. However, when the support film of the present invention is applied to curved products such as electrical products, Relatively thin 6-250μm
A certain degree is used.

In the present invention, the thickness of the electron beam cured resin coating film is not particularly limited, and the thicker the coating, the better the hardness, but if it is thinner than 3 μm, the scratch resistance will be insufficient. Furthermore, if the thickness is too large, the hard coat film tends to undergo curling or other distortions due to curing, which may be unfavorable in terms of appearance. From this point of view, the preferred thickness is about 3 to 50 μm, and the particularly preferred thickness is about 5 μm.
~10 μm.

The formation of the electron beam-cured resin coating film is performed as follows.

First, a paint is prepared by adding a solvent to the resin composition as required. Usable solvents include alcohols such as methanol, ethanol, isopropanol, methyl cellosolve, and ethylene cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. and aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.

Blade coating method, gravure coating method, rod coating method, knife coach ink method, reverse roll coating method, offset gravure coating method, etc. can be used as coating methods, but these methods have excellent coating thickness accuracy and coating surface smoothness. Preferred are gravure coating method, reverse roll coating method, and offset gravure coating method.

The coating film may be directly irradiated with electron beams, but in the case of obtaining a mirror finish, the method disclosed in JP-A-57-22204 is used.

In the method using the apparatus schematically shown in FIG. 1, a coating liquid 3 of the resin composition of the present invention is applied onto a support film 1 using a coating apparatus 2, and then a mirror material 4 is applied to the surface in a mirror state. Laminate it on the support film 1, and use the electron beam irradiation machine 5.
The coating film is cured, and finally the mirror material 4 is peeled off. Furthermore, if necessary, pre-heating may be performed using heaters 6 and 7 before electron beam irradiation, and post-heating may be performed using heater 8 after electron beam irradiation.

In FIG. 2, after coating the mirror material 4 with the coating liquid 3 using the coating device 2, the support film 1 is laminated,
The coating film is cured with an electron beam irradiator 5, and finally the cured product is peeled off from the mirror material 4. In this case as well, heater 6 if necessary.
．． Pre-heating and post-heating may be performed according to 7.8.

Mirror materials include metal plates, metal sheets, plastic films, resin coated paper, films, metallized films,
Materials such as metallized paper and glass can be used, but
In particular, as a method that utilizes the low temperature curing characteristics of electron beams,
It is preferable to use a plastic film having a softening point of 200'l or less.

Further, by using a sheet or panel having a matte surface (for example, a polyethylene terephthalate sheet) instead of a mirror material, a matte surface, that is, a surface having fine irregularities can also be obtained. The fine surface irregularities provide anti-glare properties. In this case, unlike a non-glare layer containing phosphor particles, for example, there is no light scattering and it can be made to have a uniform surface unevenness pattern, so even if it is provided in front of a display such as a CRT or liquid crystal display, the image will not change in quality. Without a problem,
preferable.

FIG. 3 shows an example of a method for obtaining a matte resin layer having such fine surface irregularities.
After applying the coating liquid 13 to the surface, it is pressed and brought into close contact with a forming roll 14 having fine irregularities in advance, and in this state is irradiated with an electron beam from an electron beam irradiation device 15. As a result, coating film 1
3 is cured, and the fine irregularities of the forming roll 14 are transferred to the surface of the cured coating film.

Next, by peeling the film from the forming roll 14 using the roll 16, a my)-shaped film having fine irregularities on the surface is obtained.

Electron beams used for curing the resin composition include those emitted from various electron beam accelerators such as Kosocroft-Walton type, bumpgraph type, resonant transformer type, insulated core transformer type, linear type, dynamidron type, and high frequency type. 50-1000K
An electron beam with an energy in the range eV, preferably 100 to 300 Kev can be used. The amount of electron beam irradiation is generally 3 to 30 Mrad.

The hard coat film of the present invention needs to be transparent when provided on the front surface of a display, but in other cases, a colored layer and/or metal vapor deposition may be applied between the resin layer and the support film as necessary. It is possible to have layers. These colored layers and metal vapor deposited layers are applied or vapor deposited onto the support film in a conventional manner. Thereafter, a resin layer is applied, and a hard coat film is obtained by the method described above.

Because it has a colored layer and/or a metal vapor deposited layer, it exhibits a variety of colors and patterns, so it not only has scratch resistance, abrasion resistance, and anti-glare properties, but also has decorative properties. A hard coat film having the following properties is obtained.

Further, the hard coat film of the present invention can be conveniently attached to the surface of an article by providing an adhesive layer on the back surface of the support film.

〔Example〕

The present invention will be explained in further detail by the following examples.

Examples 1-5 In 11 glass reaction vessels equipped with a stirrer, a thermometer, a condenser and a dropping port, 89 g of inphorone diisocyanate and 0.3 g of di-n-butyltin dilaure) were added.
of polybutylene adipate (Niraporan 4056 J Japan Polyurethane ■) while stirring at 60°C.
A solution of 150 g of Molecule 1750 (Molecular 1750) dissolved in 100 g of methyl ethyl ketone was added dropwise.

After the dropwise addition was completed, stirring was continued at 60°C for 3 hours, and then a solution of 51 g of 2-hydroxyethyl acrylate dissolved in 25 g of methyl ethyl ketone was added dropwise, followed by stirring at 60°C for 4 hours. As a result, urethane acrylate oligomer (1) was obtained with a yield of approximately 100%.

7 g of urethane acrylate oligomer (I).

A coating solution containing 14 g of dipentaerythritol hexaacrylate (Kayarad DP I8, manufactured by Nippon Kayaku@) and 46 g of methyl ethyl ketone was applied to a thickness of 50 μm.
It was coated on a polyethylene terephthalate film (R)lp7" (manufactured by Kijin ■) which had been subjected to an adhesion treatment to facilitate adhesion, using a Noku-Cocoo, and dried at 100 DEG C. for 1 minute to obtain a coating film with a thickness of 6 .mu.m. Next, a polyethylene terephthalate film (thickness 25 μm) with a matte surface shown in Table 1 below was added to this.
were laminated so that the cloak surface (irregular surface) was in contact with the coating film.

(Note) *: Sandblasted polyethylene terephthalate film Next, apply the above coating film at an accelerating voltage of 180 KV and a beam current of 36
A hard coat coating film was obtained by irradiating with an electron beam of mA at an irradiation dose of 10 Mrad. The obtained film was evaluated as follows.

(a) Gloss value: 60° gloss according to JIS Z8741.

(b) Total light transmittance: Measured according to JIS 6714.

(c) Haze value: 〃 (d) Abrasion resistance: falling sand abrasion test (ASTMD673-
44), 1000 g of #80 coarse particles were dropped onto the cured film.

The degree of surface wear is expressed as a change in haze (%).

(E) Hardness: Evaluated by pencil hardness test according to JISK5400.

(F) Scratch Resistance Evaluated by the degree of scratches after sieving 30 times with a load of 300 g using steel wool #0OOO.

○: No scratches △: Slight scratches ×: Significant scratches (G) Adhesiveness: A substrate grain test was conducted according to JIS K5400, and the adhesiveness was evaluated based on the number of remaining pieces.

The results were as shown in Table 3.

Comparative Examples 1 to 3 The same evaluations as in Examples 1 to 5 were performed using the commercially available non-glare films shown in Table 2 below.

The results are also shown in Table 3.

Table 2 Example 6 Urethane acrylate oligomer (1) obtained in Example 1
7g, dipentaerythritol hexaacrylate ("
Apply a coating solution containing 14 g of Kayarad DPHA (manufactured by Nippon Kayaku) and 46 g of methyl methyl ketone to a thickness of 50 μm.
It was coated with a bar coater on a polyethylene terephthalate film (manufactured by rHp7" i) which had been subjected to an adhesion treatment, and dried at 100° C. for 1 minute to obtain a coating film with a thickness of 6 μm.

Next, a transparent polyethylene terephthalate film with a thickness of 25 μm ("Lumirror T-60J manufactured by Toshi ■)" was then applied to this.
stacked, heating voltage 180kV and beam current 36mA
A hard coat coating film was obtained by irradiating with an electron beam of 1° Mrad at an irradiation dose of 1°.

Example 7 Urethane acrylate oligomer (IHOg.

A hard coat coating film was obtained in the same manner as in Example 6 using a coating solution containing 5 g of dipentaerythritol monohydroxypenacrylate (rSR-399, manufactured by Sartomer Co., Ltd.) and 50 g of methyl methyl ketone.

Example 8 0.02 g of a benzotriazole-based ultraviolet absorber (“Tinuvin 144” manufactured by Ciba Geigy) was added to the coating solution of Example 6.
, bindard amine light stabilizer (tinuvin 1130)
A hard coat coating film was obtained in the same manner as in Example 6 using a coating solution in which 0.03 g of J.Ciba-Geigy Co., Ltd.) was dissolved.

Example 9 In a 1β glass reaction vessel equipped with a stirrer, thermometer, condenser and dropping funnel, 89 g of isophorone diisocyanate and 0.3 g of di-butyl tin dilaurate were added.
of polytetramethylene glycol (rPTG65 (b Odogaya Kagaku ■, Molecule 1) while stirring at 60°C.
650) dissolved in 90 g of methyl ethyl ketone was added dropwise. Next, 51 g of hydroxyethyl acrylate dissolved in 25 g of methyl ethyl ketone was added dropwise, and the mixture was stirred at 60° C. for 4 hours. As a result, urethane acrylate oligomer (n) was obtained with a yield of approximately 100%.

Using a coating solution containing 10 g of urethane acrylate oligomer (II), 30 g of Benchrythritol triacrylate (Kayarad PET-30J manufactured by Nippon Kayaku), and 50 g of methyl ethyl ketone, hard coating was applied in the same manner as in Example 6. A coating film was obtained.

Example 10 In two glass reaction vessels equipped with a stirrer, a thermometer, a condenser and a dropping rotor, 134 g of isoporone diisocyanate and 0.4 g of di-n-butyltin dilaurate were added.
of polybutylene adipate ("Niphoran 4o56" manufactured by Nippon Polyurethane ■,
molecular weight 750) 150g, and glycerol methacrylate (“Blemmer GL!,” manufactured by IJ NOF ■)
A solution of 64 g dissolved in 100 g of methyl ethyl ketone was added dropwise. Then, a solution of 51 g of hydroxyethyl acrylate dissolved in 25 g of methyl ethyl ketone was added dropwise, and the mixture was stirred at 60° C. for 4 hours. This results in almost 100
Urethane acrylate oligomer (I) was obtained with a yield of %.

Urethane acrylate oligomer (I[[HOg.

A hard coat coating film was obtained in the same manner as in Example 6 using a coating solution containing 15 g of dipentaerythritol hexaacrylate ("Kayarad DPH" manufactured by Nippon Kayaku ■) and 40 g of methyl ethyl ketone.

Comparative Example 4 A hard coat coating was obtained in the same manner as in Example 6 using a coating solution containing 20 g of dipentaerythritol hexaacrylate (Kayaland DPIIA J manufactured by Nippon Kayaku@) and 40 g of methyl ethyl ketone.

Comparative Example 5 10 g of pentaerythritol triacrylate (Kayarad PET-30j manufactured by Nippon Kayaku), photoinitiator (r
lRGAc[IRE 184J C[BA-GEIGY
A coating solution prepared by dissolving 0.3 g of methyl ethyl ketone in 20 g of methyl ethyl ketone was applied using a bar coater to a 50 μm thick easily adhesive treated polyethylene terephthalate film (rHf17J manufactured by Teijin@), and dried at 100°C for 1 minute to form a 6 μm thick film.
obtained a coating.

Next, the above coating was irradiated by passing an ultraviolet lamp having an output of 160 kW/m 10 cm below the surface three times at a running speed of 10 m/min to obtain a hard coat film.

The obtained film was evaluated as follows.

(a) Flexibility: It is expressed as the diameter of the mandrel that does not cause cracking or peeling according to a mandrel test according to JIS K5400.

(b) Weather resistance: W, OoM Sunshine Weather
A test was conducted using a meter (black panel temperature: 63°C, water sprinkling/lower cycle: 18 minutes/120 minutes), and the appearance (yellowing, occurrence of cranks, etc.) was evaluated.

The results were as shown in Table 4.

〔Effect of the invention〕

As detailed above, according to the present invention, a hard coat film can be obtained which has excellent IC properties such as abrasion resistance and abrasion resistance, and also has appropriate softness and flexibility.

The hard coat film of the present invention takes advantage of the above characteristics,
It can be widely used as a surface layer for electrical products, ○A equipment, etc. In particular, when used as an anti-glare film, there is no deformation of the image placed on the front of a display such as a CRT or liquid crystal display.
It not only exhibits excellent anti-glare properties, but also has the advantage of good durability due to good scratch resistance and abrasion resistance.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing an example of the method for forming the hard coat film of the present invention, FIG. 2 is a schematic diagram showing another method for forming the hard coat film of the present invention, and FIG. , is a schematic diagram showing yet another method of forming the hard coat film of the present invention. 1.10...Support film 2...Coating device 3.13...Coating liquid 4...Mirror material 5.15...Electron beam irradiator 6.7.8...Heater 14...Improvement of unevenness Forming roll 16 having a roll

Claims (14)

[Claims] (1) (a) A diisocyanate, a diol having a hydroxyl group at both ends and a weight average molecular weight of 200 to 3000, and an acrylate compound having a hydroxyl group at both ends and a radically polymerizable unsaturated group are combined. (b) A resin obtained by curing a resin composition containing 50 to 400 parts by weight of a monomer having at least one radically polymerizable unsaturated group in one molecule by electron beam irradiation, based on 100 parts by weight of the urethane acrylate oligomer. What is claimed is: 1. A hard coat film comprising: a hard coat layer; and a film supporting the cured resin layer. (2) In the hard coat film according to item 1,
A hard coat film characterized in that the cured resin layer has fine irregularities on the surface thereof, thereby having anti-glare properties. (3) The hard coat film according to item 1 or 2, further comprising a colored layer between the cured resin layer and the support film. (4) The hard coat film according to any one of items 1 to 3, further comprising a metal vapor deposited layer between the cured resin layer and the support film. (5) The hard coat film according to any one of items 1 to 4, further comprising an adhesive layer on the back surface of the support film. (6) (a) diisocyanate, a diol having hydroxyl groups at both ends and a weight average molecular weight of 200 to 3000;
100 parts by weight of a urethane acrylate oligomer made of a curable compound having hydroxyl groups and one or more radically polymerizable unsaturated groups, and an acrylate compound having a hydroxyl group at the end and a radically polymerizable unsaturated group. (b) a resin layer obtained by curing a resin composition containing 50 to 400 parts by weight of a monomer having at least one radically polymerizable unsaturated group in one molecule by electron beam irradiation; and the cured resin. A hard coat film comprising a film supporting the layer. (7) In the hard coat film according to item 6,
A hard coat film characterized in that the cured resin layer has fine irregularities on the surface thereof, thereby having anti-glare properties. (8) The hard coat film according to item 6 or 7, further comprising a colored layer between the cured resin layer and the support film. (9) The hard coat film according to any one of items 6 to 7, further comprising a metal vapor deposited layer between the cured resin layer and the support film. (10) The hard coat film according to any one of items 6 to 9, further comprising an adhesive layer on the back surface of the support film. (11) (a) diisocyanate and a diol having hydroxyl groups at both ends and having a weight average molecular weight of 200 to 3000;
(b) At least one radically polymerizable unsaturated group in one molecule, based on 100 parts by weight of a urethane acrylate oligomer formed by bonding an acrylate compound having a hydroxyl group at the end and a radically polymerizable unsaturated group. a step of producing a resin composition by adding 50 to 400 parts by weight of a monomer having A method for producing a hard coat film, comprising the steps of: curing the resin composition by irradiating the resin composition; and peeling off the release film. (12) The method according to item 11, wherein the peeling surface of the peeling film has fine irregularities, thereby making the surface of the cured resin layer matte. (13) (a) diisocyanate and a diol having hydroxyl groups at both ends and having a weight average molecular weight of 200 to 3000;
Urethane acrylate oligomer 100 formed by bonding a curable compound having two hydroxyl groups and one or more radically polymerizable unsaturated groups and an acrylate compound having a hydroxyl group at the end and a radically polymerizable unsaturated group
(b) producing a resin composition by adding 50 to 400 parts by weight of a monomer having at least one radically polymerizable unsaturated group in one molecule, and the resulting resin composition; A step of applying the resin composition to a support film, a step of laminating a release film thereon, a step of curing the resin composition by irradiating the resin composition with an electron beam, and a step of peeling the release film. A method for producing a hard coat film characterized by: (14) The method according to item 13, wherein the peeling surface of the peeling film has fine irregularities, thereby making the surface of the cured resin layer matte.