JPH01225551A - Hard coat film and its preparation - Google Patents

Abstract

PURPOSE:To enhance scratch resistance, abrasion resistance, flexibility and bendability, by coating a film with a resin composition containing a specific amount of an urethane compound having specific diol and a polymerizable unsaturated group in the skeletal thereof and a specific amount of a monomer having a radical polymerizable unsaturated group and irradiating the coated film with electron beam. CONSTITUTION:A coating solution 3 composed of a resin composition is applied to a support film 1 using a coating apparatus 2. Next, a mirror surface material 4 is laminated to the support film 1 so that the mirror surface thereof is turned to said film 1 and the coating film is cured by an electron beam irradiation device 5 and, at last, the mirror surface material 4 is released. The resin composition is prepared by containing 50-400 pts.wt. of a monomer having at least one radical polymerizable unsaturated group in one molecule thereof in 100 pts.wt. of an urethane oligomer prepared by bonding isocyanate, diol having hydroxyl groups at both terminals thereof and a wt. average MW of 200-300 and an acrylate compound having a hydroxyl group at the terminal thereof and a radical polymerizable unsaturated group. Further, by using a sheet or panel having a matte surface in place of the mirror surface material, non-glare properties are obtained.

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 be made to 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 are each contained in specific amounts. By applying a resin composition to a film and irradiating it with an electron beam,
It was discovered that a hard coat film with excellent scratch resistance, abrasion resistance, etc. can be obtained, and the present invention was conceived.

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. (5) 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. 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) 50 to 1,000 parts having at least one radically polymerizable unsaturated group in one molecule; A resin layer obtained by curing a resin composition containing 400 parts by weight by electron beam irradiation;
It is characterized by having a film that supports 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. For 100 M of the urethane acrylate oligomer bonded with an acrylate compound, 50 to 7 polymers having at least one radically polymerizable unsaturated group in one molecule
Adding 400 parts by weight to produce a resin composition;
a step of applying the obtained resin composition to a support film;
The method comprises the steps of: laminating a release film thereon; curing the resin composition by irradiating the release film with an electron beam; and peeling off the release film. do.

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 incyanate groups in one molecule, and examples thereof include 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, 1.3-
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.

Examples of 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 (c) a ring-opened polyester compound derived from a cyclic ester compound, and these may be used alone or in combination of two or more.

The diol compound having an aromatic or spiro ring skeleton used in the addition reaction product (a) is, for example, C:H. There are H9 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-phthanediol, 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 Crl-220 (molecular weight 2000) manufactured by Nippon Polyurethane Industries, Ltd. Examples include polycarbonate diols having a molecular weight of 1000).

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 cannot be obtained in a hardening machine. The preferred weight average molecular weight range is 500 to 2000, particularly 500 to 1
It is 500.

In addition, in the falling sand abrasion test and the taper abrasion test (
In order to exhibit good wear resistance properties, polytetramethylene ether glycol, polybutylene adipate, polycarbonate diol and the like 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 incyanate group of the urethane compound, and also easily generate radicals when irradiated with an electron beam to form an unsaturated group that causes a crosslinking reaction. It is a so-called radically polymerizable compound. Such radically polymerizable acrylate compounds having a hydroxyl group at the end are ester compounds of acrylic acid or meccrylic acid, particularly derivatives thereof, and have hydroxyl groups at both ends, such as hydroquinoethyl acrylate, hydroxyl group, etc. Propyl acrylate, hydroquine butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxychlorohexyl 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: (where R and It' are CH or H, and R4 is Epoxy acrylates represented by short chain diols such as ethylene glycol, propylene glycol, diethylene glycol, phthanediol, and 1,6-hexanediol 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-R, -NCO+ 110-R2-l-〇〇11j OCN-R, -NHCO-R, -0CNH-R, -NC
O-...(1) However, R3 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.

0CN-R1-N11[[1-R2-0[:N)1-1
t, -NCO+2110-1t3-q, 0
0 Q.

(l □: R3-0CHN-R, -N1(CO-R2-OCNII
-R, -NHCO-113 (2) However, R3 is an acrylate residue (acrylic ester group or methacrylic ester group).

Note that instead of reacting all of the isocyanate residues with the 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 kneading, it is preferably carried out in a solvent such as ketone.

In addition, in the reaction system of the second step, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, etc. is added to protect the (meth)acrylic acid ester group in the radically polymerizable acrylate compound.
- di-t-butyl-p-cresol etc. 100-110
001) It is preferable to add about I1. Further, triethylamine, piperazine, triethanolamine, dibutyltin dilaurate, stannath octoate, stannath slaurate, dioctyl tin 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,
Methacrylic acid esters such as ethyl methacrylate, propyl methacrylate, methoxyethyl 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, 2
(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)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di Examples include polyfunctional (meth)acrylates such as (meth)acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, and sorbitol tetraglycidyl ether tetraacrylate.

In order to obtain good scratch resistance, among the monofunctional or polyfunctional (meth)acrylates mentioned above, the (meth)acrylic equivalent (molecular weight/number of functional groups) is from 90 to 200, especially 10.
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, the monofunctional or polyfunctional monomer is 5 parts by weight per 100 parts by weight of the urethane acrylate oligomer.
It is necessary that the amount is 0 to 400 parts by weight. In this case, the resulting cured film has a high surface hardness, and a node coat is obtained which has not only extremely high scratch resistance but 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, benzo) IJ azoles, such as 2--
(2-hydroxy-5methylphenyl)benzotriazole, 2-(2-hydroxy-3,5 ditertiary)
amyl phenyl) benzotriazole, 3-[3(benzotriazol-2-yl-
Examples include 5-t-butyl-4-hydroxyphenyl propionate. The light stabilizer is a hindered amine type, for example, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2'-n-butylmalonate bis(1,2,2,6-bentamethyl-4 -piperidyl), bis-(1,2゜2.6.6-bentamethyl-4-piperidyl) sebacate, tetrakis-(2,2,
6,6-tetramethyl-4-piperidyl)-1,2,3
, 4-butanetetracarboxylate 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 abrasion resistance, 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 5 to 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. Solvents that can be used include alcohols such as methanol, ethanol, in-propyl alcohol, methyl cellosolve, and ethylene cellosolve, ethers such as tetrahydrofuran, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ethyl acetate, and acetic acid. Examples include esters such as butyl, aromatic hydrocarbons such as toluene and xylene, and mixed solvents thereof.

As a coating method, blade coating method, gravure coating method, rod coating method, knife coating method, reverse roll coating method, offset gravure coating method, etc. can be used, but gravure has excellent coating thickness accuracy and coating surface smoothness. A coating method, a reverse roll coating method, and an offset gravure coating method are preferred.

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, preheating may be performed using heaters 6 and 7 before electron beam irradiation, and postheating 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.
．． Preheating and postheating may be performed according to 7.8.

Materials such as gold, fence plates, metal sheets, plastic films, resin-coated paper, films, metallized films, metallized paper, and glass can be used as mirror materials, but in particular, materials with low temperature curing characteristics of electron beams can be used. It is preferable to use a plastic film that is soft and has a dead point of 200° C. or lower.

Furthermore, by using a sheet or panel (for example, a polyethylene terephthalate sheet) having a cloak-like surface instead of a mirror material, a cloak-like surface, that is, a surface having fine irregularities can be obtained. These fine surface irregularities provide antiglare properties (non-glare properties). In this case, for example, unlike a non-glare layer containing silica particles, 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, the image will not deteriorate. Without a doubt,
preferable.

FIG. 3 shows an example of a method for obtaining a matte resin layer having such fine surface irregularities.
After coating the coating liquid 13 on the substrate, it is pressed and brought into close contact with a forming roll 14 having fine irregularities in advance, and in this state, an electron beam is irradiated 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 cloak-like film having fine irregularities on the surface is obtained.

The electron beam used for curing the resin composition can be emitted from various electron beam accelerators such as Conocroft-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 irradiation range of the electron beam is generally 3 to 30 Mrad.

The hard coat film of the present invention must be transparent when it is provided on the front surface of a display, but in other cases, a colored layer and/or metal layer may be added between the resin layer and the support film as necessary. It is possible to have a vapor deposited layer. 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.

Furthermore, the hard coat film of the present invention is convenient because it can be easily 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 to 5 Into a 1β glass reaction vessel equipped with a stirrer, thermometer, condenser, and dropping port, 89 g of inphoron diisocyanate and 0.3 g of di-n-butyl tin dilaure) were added.
While stirring at 60°C, 150 g of polybutylene adipate (Niraporan 4056 manufactured by Nippon Polyurethane, molecular weight 1750) was mixed with 11 g of methyl ethyl ketone.
00g 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 (I) was obtained with a yield of approximately 100%.

7 g of urethane acrylate oligomer (1).

A coating solution containing 14 g of dipentaerythritol hexaacrylate (Kayarad DPHAJ, manufactured by Nippon Kayaku@) and 46 g of methyl ethyl ketone was applied to a thickness of 50 μm.
It was coated with a bar coater on a polyethylene terephthalate film (ml (p7) manufactured by Kijin@) which had been subjected to an easy-adhesion treatment and dried at 100°C for 1 minute to obtain a coating film with a thickness of 6 μm.Then, the following coating was applied to this. A polyethylene terephthalate film (thickness: 25 μm) with a matte surface shown in Table 1 was laminated so that the cloak surface (irregular surface) was in contact with the coating film.

(Note) *: Sandblasted polyethylene telescrate film Next, apply the above coating film at an accelerating voltage of 180 KV and a beam current of 36
10 mA electron beam! It was irradiated with an irradiation dose of J.rad. to obtain a Bartco coating. The obtained film was evaluated as follows.

(a) Gross value: JIS28741 Nyor 60'
Light R degree.

(Ron total light transmittance: Measured by JfSK6714.

(c) Haze 1st shift: 〃 (d) IT abrasion: Falling sand wear f) (AST!J
D673-44), 1000 g of #80 coarse particles were dropped onto the cured film.

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

(e) Hardness: Evaluated by pencil hardness test according to J[5K5400.

(f) Abrasion resistance: Evaluated by the degree of damage after sheaving 30 times with a twisting load of 300 g on Nisteel wool #0000.

○: No scratches △: Slight scratches X: 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 obtained in Example 1 (1
) 7g, diolintaerythritol hexaacrylate (
``Kayarad 0P) IA J Nippon Kayaku ■) 14g 1 methyl ethyl ketone 46g mixed coating liquid was applied to a thickness of 50.
It was coated with a bar coater on a polyethylene terephthalate film (lp 7 J, manufactured by Ondai) that had been subjected to a μm adhesive treatment, and dried at 100° C. for 1 minute to obtain a coating film with a thickness of 6 μm. This is coated with a 25 μm thick transparent polyethylene terephthalate film ("Lumirror T-60J").
(manufactured by Toshi ■) are stacked, and an electron beam with a heating voltage of 180 kV and a beam current of 36 mA is applied to 10! A hard coat coating film was obtained by irradiating with an irradiation dose of J.R.A.D.

Example 7 Urethane acrylate oligomer (IHOg.

Example 6 was prepared using a coating solution containing 5 g of dipentaerythritol monohydroxy pentaacrylate (rSR-399J manufactured by Satomer Co., Ltd.) and 50 g of methyl methyl ketone.
A hard coat film was obtained using the same method.

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 Into a 1β glass reaction vessel equipped with a stirrer, a thermometer, a condenser and a dropping funnel, 89 g of isophorone diisocyanate (1 di-n-butyl tin dilaure) 0.3
130 g of polytetramethylene glycol (rPTG650, manufactured by Hodogaya Chemical Co., Ltd., molecular weight 650) and 25 g of methyl ethyl ketone while stirring at 60°C.
was added dropwise and stirred at 60°C for 4 hours. As a result, urethane acrylate oligomer (II) was obtained with a yield of approximately 100%.

10 g of urethane acrylate oligomer (II).

Example 6 was prepared using a coating solution containing 30 g of pentaerythritol triacrylate (Kayaland PET-30J manufactured by Nippon Kayaku) and 50 g of methyl ethyl ketone.
A hard coat film was obtained using the same method.

Example 10 In 11 glass reaction vessels equipped with a stirrer, thermometer, condenser and addition funnel, 134 g of inphoron diisocyanate, di-n-butyltin dilaure) were added.
0.4 g of polybutylene adipate (Niraporan 4056) was added while stirring at 60°C.

Made of Japanese polyurethane, molecules! 750) 150g
, and glycerol methacrylate (“Blemmer G
A solution of 64 g of L M JB (manufactured by Hon Yushi ■) dissolved in 10 notes of methyl ethyl ketone was added dropwise. Next, 51 g of sea hydroxyethyl acrylate was added to 25 g of methyl ethyl ketone.
The mixture was added dropwise and stirred at 60°C for 4 hours.

As a result, urethane acrylate oligomer (■) was obtained with a yield of approximately 100%.

Using a coating solution containing urethane acrylate oligomer (III) Log, 15 g of dipentaerythritol hexaacrylate (Kayarad 0P IA J Nippon Kayaku), and 40 g of methyl ethyl ketone, hard coating was performed in the same manner as in Example 6. A coating film was obtained.

Comparative Example 4 Using a coating solution containing 20 g of dipentaerythritol hexaacrylate (1-Kayarad DP) IA (manufactured by Nippon Kayaku) and 40 g of methyl ethyl ketone, a Bartco cloth was coated in the same manner as in Example 6. I got it.

Comparative Example 5 Pentaerythritol triacrylate (Kayarad PUT-30j Nippon Kayaku ■) Log, photoinitiator (r
lRGAcURE 184J CIBA-GtEIGY
Co., Ltd.) was dissolved in 20 g of methyl ethyl ketone and applied to a 50 μm thick easily adhesive treated polyethylene terephthalate film (rHρ7J Teijin Ondai Bar Coater) and dried at 100°C for 1 minute to a thickness of 6 μm. obtained a coating.

Next, the above coating was irradiated by passing an ultraviolet lamp having an output of 160 kW/m 10 cm downward 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: Expressed as the diameter of the mandrel that does not cause cracking or peeling according to a mandrel test according to J[5K5400.

(B) Resistance to 41J: Tested using a 1M Sunshine Weather Meter (black panel temperature 63°C, water shower cycle 18 minutes/120 minutes) to evaluate appearance (yellowing, cracking, etc.).

The results were as shown in Table 4.

〔Effect of the invention〕

As described in detail above, according to the present invention, a hard coat film can be obtained which has excellent scratch resistance, abrasion resistance, etc., 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 of electrical products, OA 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. FIG. 2 is a schematic diagram showing yet another method of forming the hard coat film of the present invention. ■, IO...Support film 2...Coating device 3.13...Coating liquid 4...Mirror material 5.15...Electron beam irradiation machine 6.7.8...Heater 214...Irregularities Forming roll 16 having...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 layer 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; A hard coat film comprising a film supporting a resin 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.