JP2002069333A - Film bearing cured coating film from radiation-curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film bearing a cured coating film made from a radiation- curable resin composition good in adhesion to plastics, thick-coatable with low curling and suitable for hard coating with no cracking occurrence. SOLUTION: This film bears a cured coating film layer made from a radiation-curable resin composition characterized by comprising (A) a polyfunctional urethane (meth)acrylate made by reaction between a polyisocyanate and a radiation-curable polyfunctional (meth)acrylate having in the molecule at least two (meth)acryloyl groups and active hydrogen atom, (B) a radiation-curable bifunctional (meth)acrylate having in the molecule two (meth)acryloyl groups and (C) colloidal silica 1-200 nm in primary particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a film having a cured film of a radiation-curable resin composition. More specifically, the hardness of plastics such as polyester, acrylic, polycarbonate, and polyether sulfone (pencil hardness,
The present invention relates to a film having a cured film of a radiation-curable resin composition having improved scratch resistance) and less curl due to curing shrinkage.

[0002]

2. Description of the Related Art At present, plastics are widely used in various industries including the automobile industry, the home appliance industry, the electric and electronic industry, and the like. The reason why plastics are used in large quantities is because of their light weight, low cost, optical characteristics, and the like, in addition to their workability and transparency. However, it has drawbacks such as being softer than glass or the like and easily scratching the surface. In order to remedy these drawbacks, it is common practice to coat a surface with a hard coat agent. As the hard coat agent, a thermosetting hard coat agent such as a silicone paint, an acrylic paint, and a melamine paint is used. Among them, silicon-based hard coat agents have been used frequently because of their high hardness and excellent quality. Most high-value-added products such as glasses and lenses use this type of coating agent. However, the curing time is long, expensive and not suitable for a hard coat of a film to be processed continuously.

[0003] In recent years, radiation-curable acrylic hard coat agents have been developed and used. Radiation-curable hard coat agents are hardened immediately by irradiating radiation such as ultraviolet rays to form a hard film.
Since it has a high processing speed, has excellent performance such as hardness and abrasion resistance, and is inexpensive in terms of total cost, it is now the mainstream in the field of hard coating. It is particularly suitable for continuous processing of films such as polyester. Plastic films include polyester film, polyacrylate film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, polyethersulfone film, etc., and polyester film is most widely used due to its various excellent characteristics. Is a kind of film. This polyester film is a glass shatterproof film, or a car light-shielding film, a surface film for a white board, a system kitchen surface antifouling film, a touch panel, a liquid crystal display for electronic materials,
It is widely used as a functional film for CRT flat televisions and the like. These are all coated with a hard coat so that their surfaces are not damaged.

Further, in a display such as a CRT or an LCD provided with a film coated with a hard coat agent, the display screen becomes difficult to see due to reflection, and the eye is easily tired. Hard coat treatment with antireflection ability is required. As a method for preventing surface reflection, a method in which an inorganic filler or an organic fine particle filler is dispersed in a radiation-curable resin is coated on a film, and the surface is made uneven to prevent reflection (AG treatment); A method of providing a multilayer structure on a film in the order of a high refractive index layer and a low refractive index layer to reflect the difference in refractive index and prevent reflection (LR or AR treatment), or AG / LR combining the above two methods (Or AR) processing method.

[0005]

While a hard coat having a functional property is required, many studies have been made to further improve the hardness which is the original purpose of the hard coat. However, while the thickness of the base film is limited, various studies have been made to develop a harder hard coating agent. However, problems such as the occurrence of curl due to an increase in the degree of crosslinking and the occurrence of cracks have arisen. That is the fact. The present invention improves the above-mentioned drawbacks, enables a thick film coating with low curl, does not generate cracks, and has a cured film of a radiation-curable resin composition having a pencil hardness of more than 4H on PET. The purpose is to provide.

[0006]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a radiation-curable resin composition having a specific composition can solve the above-mentioned problems. The present invention has been completed. That is, the present invention
(1) Radiation-curable polyfunctional (meth) having at least two (meth) acryloyl groups and active hydrogen in the molecule
A polyfunctional urethane (meth) acrylate (A) obtained by reacting an acrylate with a polyisocyanate, a radiation-curable bifunctional (meth) acrylate (B) having two (meth) acryloyl groups in the molecule, and Primary particle size is 1 to 200
A film having a cured film layer of a radiation-curable resin composition, which comprises nanometer colloidal silica (C);

(2) a film having a cured coating layer of the resin composition according to (1), wherein the primary particle size of the colloidal silica (C) is 30 to 60 nanometers; (3) a bifunctional (meth) acrylic resin (B) is dicyclopentanyl dimethylene diacrylate and / or 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadiacrylate A film having a cured film layer of the resin composition according to (1) or (2), (4) a photopolymerization initiator (D) contained in the radiation-curable resin composition (1) to (3) The film having a cured film layer of the resin composition according to any one of (1) to (5), wherein the content of the polyfunctional urethane (meth) acrylate (A) is such that the total solid content of the composition is 100 parts by weight. Sometimes 10-4 Film according to any one of to is in the range of parts by weight (1) to (4), (6) 2
The content of the functional (meth) acrylate (B) is in the range of 1 to 20 parts by weight, when the total solid content of the composition is 100 parts by weight, any one of (1) to (5). The film according to item (7), wherein the content of the colloidal silica (C) is such that the total solid content of the composition is 100 parts by weight;
The film according to any one of (1) to (6), wherein the content of the photopolymerization initiator (D) is in the range of 20 to 60 parts by weight, and the total solid content of the composition is 100%. (1) The film according to any one of (1) to (7), wherein the base film is made of polypropylene, polyethylene, polyester, or triacetyl cellulose. The film according to any one of (1) to (8), which is a polyacrylate, a polycarbonate or a polyether sulfone,

(10) The thickness of the base film is 100 to
The film according to any one of (1) to (9), wherein the film has a thickness of 500 μm and a thickness of the cured film layer of 5 to 50.
(11) A polyfunctional urethane (meth) acrylate (A) obtained by reacting a radiation-curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups and active hydrogen in a molecule with a polyisocyanate. A radiation hardened bifunctional (meth) acrylate (B) having two (meth) acryloyl groups in the molecule and a primary particle size of 1 to 20
(12) a colloidal silica (C) having a primary particle size of 30 to 60 nanometers (1) a hard coating agent for a film containing 0 nanometer colloidal silica (C);
The present invention relates to a film hard coat agent according to 1).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups and active hydrogen in the molecule used in the present invention is pentaerythritol tri (meth) acrylate. Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate,
Examples thereof include trimethylolpropane di (meth) acrylate, isocyanuric acid EO-modified diacrylate, and epoxy acrylate. Preferred specific examples include pentaerythritol triacrylate and dipentaerythritol pentaacrylate. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

[0010] As the polyisocyanate, a polyisocyanate composed of a chain saturated hydrocarbon, a cyclic saturated hydrocarbon, or an aromatic hydrocarbon can be used. Examples of such polyisocyanates include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylene bis (4-cyclohexyl). Isocyanate), hydrogenated diphenylmethane diisocyanate,
Cyclic saturated hydrocarbon isocyanates such as hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate;
-Tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,
3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate,
Aromatic polyisocyanates such as 5-naphthalenediisocyanate can be mentioned. Preferred specific examples include isophorone diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

The polyfunctional urethane acrylate (A) is obtained by reacting the above-mentioned radiation-curable polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate. The polyisocyanate is used as an isocyanate group equivalent of 0.1 to 1 equivalent to 1 equivalent of active hydrogen group in the radiation-curable polyfunctional (meth) acrylate having active hydrogen.
It is in the range of 50, preferably in the range of 0.1 to 10. The reaction temperature is usually 30 to 150 ° C., preferably,
It is in the range of 50-100 ° C. The end point of the reaction is confirmed by the decrease in the amount of isocyanate.

A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, amines such as ammonia,
Phosphines such as tributylphosphine and triphenylphosphine can be exemplified. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate,
Metal alkoxides such as zinc naphthenate, tributoxy aluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexane tin, octyl tin trilaurate, dibutyl tin dilaurate, octyl tin diacetate, etc. Tin compounds can be mentioned. Among these catalysts, an acidic catalyst is preferable, and a tin compound is more preferable. These catalysts are added in an amount of 0.1 to 1 with respect to 100 parts by weight of the polyisocyanate.
Parts by weight.

Component (A) is used in an amount of 10 to 40 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of the total solid content of the composition.

The radiation-curable bifunctional (meth) acrylate (B) having two (meth) acryloyl groups in the molecule used in the present invention includes dicyclopentanyl dimethylene diacrylate and / or 5 -Ethyl-
2- (2-hydroxy-1,1-dimethylethyl) -5
In addition to-(hydroxymethyl) -1,3-dioxadiacrylate, for example, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, zinc diacrylate, bisphenol A diglycidyl ether diacrylate, neo Epoxy acrylates such as pentyl glycol diglycidyl ether diacrylate and 1,6-hexanediol diglycidyl ether diacrylate, etc., obtained by esterifying a polyhydric alcohol with a polycarboxylic acid and / or an anhydride thereof and acrylic acid. Urethane di obtained by reacting polyester diacrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl-containing acrylate Acrylate, and the like. The amount of the component (B) to be used is 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based on the total solid content of the composition.

The primary particle size used in the present invention is 1 to 1.
200 nm colloidal silica (C) is a colloidal solution in which colloidal silica is dispersed in a solvent.
Alternatively, it can be used as fine powder colloidal silica containing no dispersion solvent. As a dispersion medium of colloidal silica, water, methanol, ethanol, isopropanol, alcohols such as n-butanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like, polyhydric alcohols such as ethylene glycol and derivatives thereof, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone,
Ketones such as dimethylacetamide, esters such as ethyl acetate and normal butyl acetate, nonpolar solvents such as toluene and xylene, acrylates such as 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate, and others General organic solvents can be used. The amount of the dispersion medium is usually 100 to 900 parts by weight based on 100 parts by weight of the colloidal silica.

As these colloidal silicas, commercially available ones manufactured by a known method can be used.
It is necessary to use a particle size of 1 to 200 nm, preferably 5 to 100 nm, more preferably 5 to 60 nm. More preferably, it is 30 to 60 nanometers.

The use of 5 to 20 nanometers has an effect on curling, and the use of 40 to 50 nanometers increases the hardness. If the particle size is too large, the film will be fogged, and there is a high possibility that the optical characteristics will be adversely affected.
Further, by not intentionally having cross-linking points on the silica surface, curing shrinkage can be further reduced, which is extremely advantageous for curling. In the present invention, it is preferable to use colloidal silica having a pH of 2 to 6.

Component (C) is used in an amount of 20 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the total solid content of the composition.

The photopolymerization initiator (D) is usually added when the radiation for curing is ultraviolet light. The component (D) is not particularly limited, and may be, for example, Irgacure 18
4,907,651,1700,1800,819,3
69 (Ciba Specialty Chemicals), Darocur 1173 (Merck), Ezacure KIP
150, TZT, KK, KTO46, 1001, 75 /
B (manufactured by Nippon Siber Hegner), Lucirin TPO (B
ASF) and Kayacure BMS (manufactured by Nippon Kayaku).

When these photopolymerization initiators (D) are used, when the total solid content of the composition is 100 parts by weight,
It is in the range of 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, and more preferably 1 to 3 parts by weight. (D)
The components may be used alone or as a mixture of two or more. Those with low molecular weight, low melting point and low boiling point
Because it is gasified by heat, if there is a heat treatment step,
Careful attention must be paid to the amount used since it may adversely affect post-processing. Ezacure KIP-150, KK, Lucirin TPO
Is preferred.

The above photopolymerization initiator (D) can be used in combination with a curing accelerator. Examples of the curing accelerator that can be used in combination include amines such as triethanolamine, diethanolamine, N-methyldiethanolamine and EPA, and hydrogen donors such as 2-mercaptobenzothiazole. The use amount of these curing accelerators is 0 to 5 parts by weight based on the total solid content of the composition.

The radiation-curable resin composition used in the present invention can be used as a hard coat agent.
In addition to the components (B), (C) and (D), radiation-curable acrylates and solvents other than those described above can be added as necessary.

Examples of the radiation-curable acrylate include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and tris (2-hydroxyethyl) isocyanurate triacrylate. Ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and the like.

The radiation-curable acrylate is used in an amount of 0 to 40 parts by weight, based on the total solid content of the composition.
Preferably it is 10 to 30 parts by weight.

Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and normal butyl acetate, aromatic solvents such as toluene and xylene, alcohol solvents such as isopropanol, methanol and ethanol. Various organic solvents such as glycol-based agents such as propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are used. Careful attention must be paid to the selection of these solvents, since there is a possibility that the base material used will erode and adversely affect the hardness and the like depending on the base material used.

The amount of these solvents used is preferably 10 to 70 parts by weight, when the total weight of the composition is 100 parts by weight,
More preferably, it is 20 to 60 parts by weight.

Further, in addition to the above components, a leveling agent and an antifoaming agent can be added as required.

Further, it is also possible to add an ultraviolet absorber, a light stabilizer, various kinds of inorganic and organic fillers, a polymer and the like to impart functionality.

The radiation-curable resin composition used in the present invention comprises the components (A), (B), (C) and (D) described above.
It can be obtained by mixing the components, solvent and other components in any order. The resin composition used in the present invention is stable over time.

The film of the present invention is prepared by applying the above radiation-curable resin composition to a film base (base film) on a film base (base film) and weighing 5 to 50 g / m ² , preferably 10 to 30 g after drying. / M ² (5 to 50 μm in film thickness,
(Preferably 10 to 30 μm), dried, and then irradiated with radiation to form a cured film. Examples of the film substrate include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, and polyethersulfone. The film may be in the form of a sheet. Its thickness is 100-500
μm is preferred.

Examples of the method of applying the radiation-curable resin composition include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, die coating, offset printing, flexographic printing,
Screen printing and the like. At this time, the film to be used is provided with an easy-adhesion layer, a pattern, etc., a frame treatment,
It may be one subjected to corona treatment or the like.

The radiation to be applied includes, for example, ultraviolet rays and electron beams. In the case of curing by ultraviolet rays, a xenon lamp, a high-pressure mercury lamp, an ultraviolet irradiation device having a metal halide lamp is used as a light source, and the light amount and the arrangement of the light source are adjusted as necessary. 2000 mJ / cm ^2, preferably preferably cured at 500~1000mJ / cm ^2. Curling is reduced by irradiating ultraviolet rays from the back side and then irradiating from the front side. On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

[0033]

Next, the present invention will be described more specifically with reference to preparation examples and examples, but the present invention is not limited to these examples. In addition, in a preparation example, a part means a weight part.

Synthesis Example Pentaerythritol triacrylate 1 in a drying vessel
020 parts, 0.6 parts of di-n-butyltin dilaurate,
0.6 part of methoquinone was added and heated and stirred to 80 ° C.
177.8 parts of isophorone diisocyanate was added to 1
After dropwise addition over a period of time, the isocyanate value after stirring for 1 to 2 hours was 0.3 or less, indicating that the reaction was almost quantitatively completed.

Formulation Example 1 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
4 parts of KAYARAD R-684 (manufactured by KK), 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals), and 0.2 part of lucilin TPO (manufactured by BASF).
Part, colloidal silica methyl ethyl ketone dispersion (solid content 30%, Nissan Chemical Industry Co., Ltd. organosilica sol M)
(EK-ST: particle size 10 to 20 nanometers) was mixed to obtain a radiation-curable resin composition used in the present invention.

Formulation Example 2 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30)
Ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadiacrylate (KAYARAD R-6 manufactured by Nippon Kayaku Co., Ltd.)
04), 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and Lucirin TPO (B
0.2 part of colloidal silica in methyl isobutyl ketone (solid content 30%, Nissan Chemical Industry)
Organokilica sol MIBK-ST manufactured by K.K.
70 parts (20 nanometers) were mixed to obtain a radiation-curable resin composition used in the present invention.

Formulation Example 3 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 manufactured by K.K., 4 parts of bisphenol A type epoxy acrylate (KAYARADR-115 manufactured by Nippon Kayaku Co., Ltd.), Irgacure 1
84 (Ciba Specialty Chemicals)
Parts, 0.2 part of Luciline TPO (manufactured by BASF), a dispersion of colloidal silica in normal butyl acetate (solid content 30
%, An organosilica sol NBAC- manufactured by Nissan Chemical Industries, Ltd.
ST: particle size of 10 to 20 nanometers)
A radiation-curable resin composition used in the present invention was obtained.

Formulation Example 4 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.)
X8101), 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals), Lucirin TP
0.2 parts of O (manufactured by BASF), a dispersion of colloidal silica in methyl isobutyl ketone (solid content: 30%, organosilica sol MIBK-ST manufactured by Nissan Chemical Industries, Ltd .: particle size: 1)
(0 to 20 nanometers) was mixed to obtain a radiation-curable resin composition used in the present invention.

Formulation Example 5 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
4 parts of KAYARAD R-684 (manufactured by KK), 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals), and 0.2 part of lucilin TPO (manufactured by BASF).
Part, colloidal silica methyl ethyl ketone dispersion (solid content 30%, Nissan Chemical Industry Co., Ltd. organosilica sol M)
(EK-ST-S: particle size 8 to 11 nanometers) was mixed to obtain a radiation-curable resin composition used in the present invention.

Formulation Example 6 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
4 parts of KAYARAD R-684 (manufactured by KK), 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals), and 0.2 part of lucilin TPO (manufactured by BASF).
Part, colloidal silica methyl ethyl ketone dispersion (solid content 30%, Nissan Chemical Industry Co., Ltd. organosilica sol M)
EK-ST-ZL: particle size 40 to 50 nanometers) 70
Were mixed to obtain a radiation-curable resin composition used in the present invention.

Formulation Example 7 The polyfunctional urethane acrylate obtained in the synthesis example was mixed with 12
Part, pentaerythritol triacrylate (Nippon Kayaku
12 parts of KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.
4 parts of KAYARAD R-684 (manufactured by K.K.) and 1 part of Ezacure KIP-150 (manufactured by Nippon SiberHegner)
Parts, 0.2 parts of Lucilin TPO (manufactured by BASF), a dispersion of colloidal silica in methyl isobutyl ketone (solid content: 30%, organosilica sol MIB manufactured by Nissan Chemical Industries, Ltd.)
(K-ST: particle diameter of 10 to 20 nanometers) was mixed to obtain a radiation-curable resin composition used in the present invention.

Comparative Example 1 72 parts of dipentaerythritol hexaacrylate (Kayarad DPHA manufactured by Nippon Kayaku Co., Ltd.), 3 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 37.5 parts of toluene, methyl ethyl ketone 37.5 parts were mixed to obtain a radiation-curable resin composition for comparative test.

Comparative Example 2 36 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
-Hexanediol diepoxy acrylate (Nippon Kayaku
36 parts of KAYARAD R-167 (manufactured by KK), 3 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 37.5 parts of toluene, and 37.5 parts of methyl ethyl ketone were mixed, and then radiation-cured for a comparative test. A mold resin composition was obtained.

Comparative Example 3 40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 3 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals), and a dispersion of colloidal silica in methyl ethyl ketone (solid) For 30 minutes, 107 parts of an organosilica sol MEK-ST (manufactured by Nissan Chemical Industries, Ltd.) were mixed to obtain a radiation-curable resin composition for a comparative test.

Comparative Example 4 The polyfunctional urethane acrylate obtained in the synthesis example was used for 20.
7 parts, pentaerythritol triacrylate (KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd.) at 20.7 parts
Part, dicyclopentanyl dimethylene diacrylate (KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd.) as 7.4
Parts, 1 part of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 0.2 parts of lucilin TPO (manufactured by BASF) and 50 parts of methyl ethyl ketone were mixed to obtain a radiation-curable resin composition for a comparative test. Was.

Example (1) Method of Forming Coating Film The radiation-curable resin composition obtained in each of the above Formulation Examples and Comparative Examples was subjected to an easily-adhesive treated polyester film (A-I manufactured by Toyobo Co., Ltd.) using a bar coater (No. 30). 4300, film thickness 188
μm), left in a drying oven at 80 ° C. for 1 minute, and then irradiated with ultraviolet light at a conveyor speed of 5 m / min from a distance of 10 cm of a high-pressure mercury lamp of 120 W / cm in an air atmosphere to a cured film (15 to 20 μm). ) Was obtained.

(2) Measurement of Pencil Hardness According to JIS K 5400, the pencil hardness of the coated film was measured using a pencil scratch tester. Specifically, a pencil of about 5 mm was applied to a PET film having a cured film (20 μm) to be measured at a 45 ° angle by applying a load of 1 kg from above, and the degree of scratching was confirmed with a microscope. Five measurements were made. Evaluation Five measurements were made, and the results were represented by a pencil that was not scratched four or more times. Judgment A slight dent was evaluated as ○.

(3) Scratch resistance test A steel wool # 0000 was reciprocated 10 times under a load of 200 g / cm ² , and the condition of the scratch was visually determined.

(4) Adhesion According to JIS K 5400, 1 mm
Make 100 grids by making 11 vertical and horizontal cuts at intervals. After the cellophane tape was brought into close contact with the surface, the number of squares remaining without peeling at a stretch was indicated.

(5) Curling Measurement by Curing Shrinkage A film having a cured film (15 to 20 μm) to be measured was cut into 5 cm × 5 cm, left in a drying oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four raised sides was measured on a horizontal table, and the average value was taken as a measured value (unit: mm). At this time, the curl of the substrate itself is 0 m.
m.

(6) Appearance The state of the surface such as cracks, whitening, and cloudiness was visually judged. The evaluation results are shown in Table 1.

Table 1 Pencil Hardness Scratch Adhesion Curl Appearance Formulation Example 4H 100 100 5.5 Formulation Example 4H 100 100 5.5 Formulation Example 3 4H 100 100 5.0 Formulation Example 5 4H １００ 100 4.5 ○ Formulation Example 6 5H １００ 100 6.5 ○ Formulation Example 7 4H １００ 100 5.5 ○ Comparative Example 1 4H １００ 100 10.0 × Comparative Example 2 3H × 100 4.0 ○ Comparative Example 3 4H ○ 100 8.0 △ Comparative Example 4 4H ○ 100 7.0 ○

As is clear from Table 1, the film (hard coat film) having the cured film of the radiation-curable resin composition of the present invention had good pencil hardness and excellent curl. .

[0054]

The film having a cured film of the radiation-curable resin composition of the present invention has good pencil hardness, curl, and good adhesion to a substrate, especially plastic optical components, touch panels, flat displays, and film liquid crystals. It is a hard coat film suitable for a field requiring a high hardness using a thick base material such as an element.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/00 C09D 5/00 Z 175/16 175/16 // C08L 101: 00 C08L 101: 00 F term (Reference) 4F006 AA02 AA12 AA22 AA35 AA36 AA40 AB24 AB43 BA02 CA04 CA05 CA08 DA04 EA03 4F100 AA20H AJ06A AK01A AK01B AK04B AK07B AK25A AK41B AK45A AK51A AK55A01J14E46A01JE14A46E01AH AE02 AE04 AE07 AG12 AG14 AG23 AG24 AG27 BA13 BA19 BA23 BA24 BA26 BA29 CA18 CB10 CC05 CC06 CD08 4J038 FA151 FA152 FA281 FA282 HA446 KA03 KA06 NA11 PA17 PC08

Claims (12)

[Claims] A polyfunctional urethane (meth) acrylate obtained by reacting a radiation-curable polyfunctional (meth) acrylate having at least two or more (meth) acryloyl groups and active hydrogen in a molecule with a polyisocyanate. A), a radiation-curable bifunctional (meth) acrylate having two (meth) acryloyl groups in the molecule (B) and a primary particle size of 1
A film having a cured film layer of a radiation-curable resin composition, which contains colloidal silica (C) of from 200 to 200 nanometers. 2. The colloidal silica (C) has a primary particle size of 30.
A film having a cured film layer of the resin composition according to claim 1, which has a thickness of from 60 to 60 nanometers. 3. A bifunctional (meth) acrylate (B) comprising dicyclopentanyl dimethylene diacrylate and / or 5
The cured film layer of the resin composition according to claim 1, which is -ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadiacrylate. A film having: 4. A film having a cured film layer of the resin composition according to claim 1, wherein the radiation-curable resin composition contains a photopolymerization initiator (D). 5. The content of the polyfunctional urethane (meth) acrylate (A) is in the range of 10 to 40 parts by weight, when the total solid content of the composition is 100 parts by weight.
5. The film according to any one of items 4 to 4. 6. The content of the bifunctional (meth) acrylate (B) is in the range of 1 to 20 parts by weight, based on 100 parts by weight of the total solid content of the composition. The film according to any one of the above items. 7. The content of colloidal silica (C) is from 20 to 6 when the total solid content of the composition is 100 parts by weight.
The film according to any one of claims 1 to 6, which is in a range of 0 parts by weight. 8. The composition according to claim 1, wherein the content of the photopolymerization initiator (D) is in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition. The film according to claim 1. 9. The material of the base film is polypropylene,
The film according to any one of claims 1 to 8, which is polyethylene, polyester, triacetyl cellulose, polyacrylate, polycarbonate, or polyether sulfone. 10. A base film having a thickness of 100 to 500.
The film according to any one of claims 1 to 9, wherein the thickness of the cured film layer is 5 to 50 µm. 11. At least two or more (meth) molecules in a molecule
Polyfunctional urethane (meth) acrylate (A) obtained by reacting a radiation-curable polyfunctional (meth) acrylate having an acryloyl group and active hydrogen with a polyisocyanate, having two (meth) acryloyl groups in the molecule Radiation hardened bifunctional (meth) acrylate (B) and primary particle size is 1 to
A hard coating agent for a film containing 200 nanometers of colloidal silica (C). 12. The colloidal silica (C) having a primary particle size of 3
The hard coat agent for a film according to claim 11, which has a thickness of 0 to 60 nanometers.