KR20100109429A - Curable paint, scratch resistant resin sheet and protective sheet for display windows of portable information devices - Google Patents

Abstract

PURPOSE: A curable paint, a scratch resistant resin plate, and a display window protective plate are provided to form the curable paint with the superior antifouling property, and to effectively protect a display window of a portable digital device. CONSTITUTION: A curable paint contains the following: a compound including at least six (meth)acryloyloxy groups; a compound including four or five (meth)acryloyloxy groups; and reaction products of the previous components. The compound including at least six (meth)acryloyloxy groups is a triisocyanate compound obtained by trimerizing a diisocyanate compound.

Description

Curable Paint, Scratch Resistant Resin Plate and Portable Display Terminal Protection Plate {CURABLE PAINT, SCRATCH RESISTANT RESIN SHEET AND PROTECTIVE SHEET FOR DISPLAY WINDOWS OF PORTABLE INFORMATION DEVICES}

The present invention relates to a scratch resistant resin plate having a curable coating material, a cured coating formed of the curable coating material, and a display window protective plate of a portable information terminal comprising the scratch resistant resin plate.

In recent years, with the spread of the Internet, portable telephones such as mobile phones and PHS (Personal Handy-phone System) have been widely used as portable information terminals having a function of displaying text information and image information in addition to a simple voice transmission function. Has been. In addition to such portable telephones, PDAs (Personal Digital Assistants) having an Internet function and an e-mail function in addition to functions such as an address book are also widely used. In this specification, such a mobile phone, PHS, PDA, etc. will be collectively referred to as a "portable information terminal". In other words, in the present specification, the term "portable information terminal" refers to a terminal having a window (display) for displaying character information, image information, etc., which is large enough to be carried by a person.

In these portable information terminals, character information and image information are displayed by methods, such as a liquid crystal and EL (electroluminescence), but the board of transparent resin is generally used for the display window as a protective plate. In order to prevent the surface from being scratched, it is proposed to form a scratch-resistant hardened film with a curable paint. As this curable coating material, what contains the compound which has at least 2 (meth) acryloyloxy group in a molecule | numerator, ie, polyfunctional (meth) acrylate, is mainly examined (refer patent documents 1-9). For example, Patent Document 4 discloses a curable paint or a molecule containing a compound having at least six (meth) acryloyloxy groups in a molecule and a compound having four or five (meth) acryloyloxy groups in a molecule. By the curable paint containing the compound which has at least seven (meth) acryloyloxy group, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator, it can form a hardening film with high scratch resistance Is disclosed.

Japanese Unexamined Patent Publication No. 2004-143365 Japanese Laid-open Patent Publication 2004-299199 Japanese Unexamined Patent Publication No. 2007-190794 Japanese Unexamined Patent Publication No. 2008-6811 Japanese Unexamined Patent Publication No. 2008-49697 Japanese Laid-Open Patent Publication No. 2008-36927 Japanese Unexamined Patent Publication No. 2008-207467 Japanese Unexamined Patent Publication No. 2008-279650 Japanese Unexamined Patent Publication No. 2008-297350

When the display window protection plate of a portable information terminal is used as a touch panel, for example, it is often in direct contact with a finger. Therefore, in addition to abrasion resistance, antifouling property, especially anti-fingerprint property is calculated | required by this hardened film. Then, the objective of this invention is providing the curable coating material which can form the cured film which is high in scratch resistance and excellent in antifouling property.

In order to achieve the above object, the present invention provides a compound having at least six (meth) acryloyloxy groups in a molecule, a compound having four or five (meth) acryloyloxy groups in a molecule, and the following components The curable coating material containing the reaction product of (A), a component (B), and a component (C) is provided.

Component (A): Triisocyanate compound formed by trimerizing a diisocyanate compound.

Component (B): Polyether compound which has at least 1 group chosen from the group which consists of a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkylidene group in a molecule | numerator.

Component (C): A compound having a hydroxyl group and a polymerizable carbon-carbon double bond in a molecule.

The present invention also provides a compound having at least seven (meth) acryloyloxy groups in a molecule, a compound having 3 to 6 (meth) acryloyloxy groups in a molecule, and a curable paint containing the reaction product. do.

Moreover, this invention provides the scratch resistant resin board which consists of a resin substrate and the hardened film which uses the said curable coating material formed in at least one surface of this resin substrate.

Moreover, this invention provides the display window protection board of the portable information terminal which consists of this scratch resistant resin board.

According to the curable coating material of this invention, the hardening film which is high in scratch resistance and excellent in antifouling property can be formed. By using the scratch resistant resin plate which has this hardened film as a display window protective plate of a portable information terminal, the display window can be protected effectively.

In one aspect of the present invention, the curable paint includes a compound having at least six (meth) acryloyloxy groups in a molecule, a compound having four or five (meth) acryloyloxy groups in a molecule, and It contains the reaction product of a component (A), a component (B), and a component (C) (Hereinafter, it may be called curable paint (1).).

Component (A): Triisocyanate compound formed by trimerizing a diisocyanate compound.

Component (B): The polyether compound which has a group chosen from the group which consists of a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkylidene group in a molecule | numerator.

Component (C): A compound having a hydroxyl group and a polymerizable carbon-carbon double bond in a molecule.

Moreover, in another form of this invention, a curable coating material is a compound which has at least 7 (meth) acryloyloxy group in a molecule | numerator, the compound which has 3-6 (meth) acryloyloxy groups in a molecule | numerator, It contains the said reaction product [Hereinafter, it may be called curable paint (2)].

By using these curable paints, a cured film with high scratch resistance and excellent antifouling property can be formed.

In addition, in this specification, a (meth) acryloyloxy group refers to an acryloyloxy group or methacryloyloxy group, and in addition, it is "(meth)" when it is referred to as (meth) acrylate, (meth) acrylic acid, etc. Is the same meaning.

Examples of the compound having at least seven (meth) acryloyloxy groups in the molecule include tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate.

Examples of the compound having six (meth) acryloyloxy groups in the molecule include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and the like.

In addition, examples of the compound having four or five (meth) acryloyloxy groups in the molecule include pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth) acrylate, and the like.

Examples of the compound having three (meth) acryloyloxy groups in the molecule include glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tris [(meth ) Acryloyloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, etc. are mentioned.

Moreover, m halocarbonyl groups in a urethane (meth) acrylate compound or molecule obtained by reaction of the compound which has m isocyanato groups in a molecule, and the compound which has a hydroxyl group and n (meth) acryloyloxy groups in a molecule | numerator An ester (meth) acrylate compound obtained by the reaction of a compound having a compound and a compound having a hydroxyl group and n (meth) acryloyloxy groups in the molecule has m x n (meth) acryloyloxy groups in the molecule. Examples of the compound may be mentioned.

In curable coating material (1), the ratio of the compound which has at least 6 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 4 or 5 (meth) acryloyloxy group in a molecule | numerator is the total amount of both 100 Based on the weight part, the former is usually 5 to 95 parts by weight, the latter is 95 to 5 parts by weight, preferably the former is 30 to 70 parts by weight, and the latter is 70 to 30 parts by weight. In addition, the curable coating material (1) is a compound having three (meth) acryloyloxy groups and / or ethylene glycol di (meth) acrylate and diethylene glycol in the curable compounds other than the above, for example, the molecules exemplified above. You may contain the compound which has two (meth) acryloyloxy groups in molecules, such as di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. When curable coating material 1 contains curable compounds other than the said both, the quantity of curable compounds other than the said both is 20 weight part or less normally with respect to 100 weight part of total amounts of the said both.

Moreover, in curable coating material (2), the ratio of the compound which has at least 7 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator is the total amount of both 100 Based on the weight part, the former is usually 5 to 95 parts by weight, the latter is 95 to 5 parts by weight, preferably the former is 30 to 70 parts by weight, and the latter is 70 to 30 parts by weight. Moreover, curable coating material 2 may contain the compound which has two (meth) acryloyloxy groups in curable compounds other than the said, for example, the molecule | numerator illustrated above. When curable coating material 2 contains curable compounds other than the above, the quantity of curable compounds other than the said both is 20 weight part or less normally with respect to 100 weight part of said total amounts of both.

Curable paint contains the reaction product of following component (A), component (B), and a component (C). Therefore, the cured film formed using the curable coating material of this invention is excellent in antifouling property.

Component (A): Triisocyanate compound formed by trimerizing a diisocyanate compound.

Component (B): Polyether compound which has at least 1 group chosen from the group which consists of a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkylidene group in a molecule | numerator.

Component (C): A compound having a hydroxyl group and a polymerizable carbon-carbon double bond in a molecule.

As a diisocyanate compound which is a trimer raw material of a component (A), for example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate And diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate and naphthalene diisocyanate.

In the component (B), as a perfluoroalkyl group, for example, a perfluoromethyl group, a perfluoroethyl group, a (n- or iso) perfluoropropyl group, (n-, iso, s- or t- ) Perfluoro butyl group is mentioned. As a perfluoroalkylene group, a perfluoroethylene group, a perfluoropropylene group, a perfluoro trimethylene group is mentioned, for example. Examples of the perfluoroalkylidene group include a perfluoromethylene group, a perfluoroethylidene group, and a (n- or iso) perfluoropropylidene group.

As component (B), the compound which has one hydroxyl group in a molecule | numerator is preferable, For example, it has a hydroxyl group at one terminal of a molecule | numerator, has a perfluoroalkyl group at the other terminal of a molecule | numerator, and oxygen of a polyether chain Preference is given to compounds having a perfluoroalkylene group and / or a perfluoroalkylidene group between the atom and the oxygen atom.

As component (C), the compound which has one hydroxyl group in a molecule | numerator is preferable, and the compound which has a (meth) acryloyloxy group in a molecule | numerator is preferable, For example, pentaerythritol tri (meth) acrylate and dipenta Erythritol penta (meth) acrylate, glycerindi (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, trimethylolmethanedi (meth) acrylate, ethylene glycol mono (Meth) acrylate, diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, etc. are mentioned.

The reaction product is in a ratio of 1 to 2 moles of component (B), 1 to 2 moles of component (C), and 2 moles of the total of component (B) and component (C) per 1 mole of component (A). It is preferable that it is a product obtained by making it react.

The said reaction product can be prepared, for example by the method of the international publication 03/002628 pamphlet or Unexamined-Japanese-Patent No. 2006-37024.

Content of the said reaction product in curable paint (1) is 100 weight in total of the compound which has at least 6 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 4 or 5 (meth) acryloyloxy group in a molecule | numerator. The amount is usually 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight. In addition, content of the said reaction product in curable paint (2) is a total of 100 of the compound which has at least 7 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator. It is 0.01-5 weight part normally with respect to a weight part, Preferably it is 0.1-2 weight part.

Curable coating material may contain electroconductive fine particles. When a curable coating material contains electroconductive fine particles, the cured film which has antistatic performance and antistatic performance can be obtained.

Examples of the conductive fine particles include metal oxides such as antimony oxide, composite oxides of indium / tin (ITO), composite oxides of tin / antimony (ATO), composite oxides of antimony / zinc, tin oxide doped with phosphorus, and the like. Each fine particle is mentioned.

It is preferable that the particle diameters of electroconductive fine particles are 0.001-0.1 micrometer. When the particle diameter is too small, industrial production is difficult, and when the particle diameter is too large, the transparency of the cured coating film may be lowered. The content of the conductive fine particles in the curable coating material (1) is 100 parts by weight in total of the compound having at least six (meth) acryloyloxy groups in the molecule and the compound having four or five (meth) acryloyloxy groups in the molecule. It is preferable that it is 1-100 weight part with respect to. In addition, content of the electroconductive fine particle in curable coating material (2) is 100 weight in total of the compound which has at least 7 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator. It is preferable that it is 1-100 weight part with respect to a part. When this content is too small, the antistatic effect of the obtained cured film may become inadequate, and when too large, the scratch resistance of the obtained cured film may fall, or film forming property may fall.

Moreover, in order to adjust a viscosity, the thickness of a cured film, etc., curable coating material may contain a solvent. As this solvent, for example, methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol ), Alcohols such as 2-methyl-2-propanol (tert-butyl alcohol), 2-ethoxyethanol, 2-butoxyethanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, Alkoxy alcohols such as 1-ethoxy-2-propanol, ketols such as diacetone alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, acetic acid Ester, such as butyl, etc. are mentioned. Although content of a solvent is adjusted suitably according to the material of a board | substrate, a shape, the coating method of a curable paint, the thickness of the cured coating made into the objective, etc., in the curable paint (1), at least 6 (meth) acryloyloxy groups in a molecule | numerator It is 20-10000 weight part normally with respect to a total of 100 weight part of the compound which has four or five (meth) acryloyloxy groups in the compound which has and a molecule | numerator. Moreover, in curable coating material (2), with respect to a total of 100 parts by weight of the compound having at least seven (meth) acryloyloxy groups in the molecule and the compound having 3 to 6 (meth) acryloyloxy groups in the molecule, Usually 20-10000 weight part.

Moreover, curable coating material may contain additives, such as a stabilizer, antioxidant, a coloring agent, and a leveling agent. When the curable coating material contains a leveling agent, the smoothness and scratch resistance of the resulting cured film are increased.

As the leveling agent, at least one silicone oil is preferably used. Examples of the silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, alkyl aralkyl modified silicone oil, fluoro silicone oil, polyether modified silicone oil, fatty acid ester modified silicone oil, methyl hydrogen silicone oil, and silanol group-containing silicone oil. , Alkoxy group-containing silicone oil, phenol group-containing silicone oil, methacryl modified silicone oil, amino modified silicone oil, carboxylic acid modified silicone oil, carbinol modified silicone oil, epoxy modified silicone oil, mercapto modified silicone oil, fluorine modified Silicone oil, a polyether modified silicone oil, etc. are mentioned.

The content of the silicone oil in the curable paint (1) is 100 parts by weight in total of the compound having at least six (meth) acryloyloxy groups in the molecule and the compound having four or five (meth) acryloyloxy groups in the molecule. It is 0.01-20 weight part normally. In addition, content of the silicone oil in curable coating material (2) is 100 weight in total of the compound which has at least 7 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator. It is 0.01-20 weight part normally with respect to a part. When the content is too small, the desired effect is hardly observed, and when too large, the strength of the resulting cured film may be lowered.

By forming a cured film on at least one surface of a resin substrate using the curable coating material demonstrated above, the scratch resistant resin board which has a high scratch resistance and the excellent antifouling property can be obtained.

It is preferable that resin which comprises a resin substrate is a transparent thermoplastic resin. Examples of the thermoplastic resins include methacryl resins, polyester resins, polycarbonate resins, polycyclic olefin resins, polystyrene resins, methacryl-styrene copolymers (MS resins), acrylonitrile-styrene copolymers (AS resins), Polyvinylidene fluoride resin (PVDF resin) is mentioned.

Especially, methacryl resin is preferable because it is easy to form the hardened film which has high surface hardness and high scratch resistance, and since polycarbonate resin is high in impact resistance and does not crack easily, it is preferable.

The resin substrate may be a substrate having a flat surface like a conventional plate (sheet) or a film, or may be a substrate having a curved surface such as a convex lens or a concave lens.

Furthermore, fine structures, such as fine unevenness | corrugation, may be formed in the surface.

The resin substrate may be colored with a dye, a pigment, or the like. The resin substrate may contain antioxidant, ultraviolet absorber, rubber particles and the like. The thickness of the resin substrate is preferably 0.1 mm or more and 3.0 mm or less.

The resin substrate may have a single layer structure or may have a multilayer structure. As a resin substrate of a multilayered structure, the laminated body by which the methacryl resin layer is laminated | stacked on at least one surface of a polycarbonate resin layer is preferable, and it is preferable that at least one layer of this methacryl resin layer contains rubber particle. Do.

Formation of a cured film can be performed by apply | coating a curable coating material to the at least one surface of a resin substrate, drying the coating film formed as needed, and then hardening the formed coating film.

Application of a curable coating material can be performed by methods, such as the microgravure coating method, the roll coating method, the dipping coating method, the spin coating method, the die coating method, the cast transfer method, the flow coating method, and the spray coating method, for example. .

Curing of a coating film can be performed by irradiating an activation energy ray. As an activation energy ray, an electron beam, an ultraviolet-ray, a visible ray, etc. are mentioned, for example, It selects suitably according to the kind of curable compound. In the case of using ultraviolet rays and / or visible rays as the activation energy rays, the curable paint usually contains a photopolymerization initiator.

As a photoinitiator, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4- Chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy- 2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholi Nopropane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- On, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoisopropyl ether, benzophenone, myhilerketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra-tert-butylperoxy Carbonylbenzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2- (phen And methyl) -1-butanone, 4-benzoyl-4'-methyl diphenyl sulfide, benzyl.

Commercially available photoinitiators include, for example, "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "Sold by Chiba Specialty Chemicals Co., Ltd., respectively. DAROCUR 1173 "," IRGACURE 907 "," IRGACURE 369 "," IRGACURE 1700 "," IRGACURE 1800 "," IRGACURE 819 "and" IRGACURE 784 "," KAYACURE ITX "," KAYACURE DETX-S "," KAYACURE BP-100 "," KAYACURE BMS "," KAYACURE 2-EAQ ", etc. are mentioned.

You may use a photoinitiator in combination with a dye sensitizer. As a dye sensitizer, xanthene, thioxanthene, coumarin, ketocoumarin, etc. are mentioned, for example. As a combination of a photoinitiator and a dye sensitizer, the combination of BTTB and xanthene, the combination of BTTB and thioxanthene, the combination of BTTB and coumarin, the combination of BTTB and ketocoumarin, etc. are mentioned, for example.

The content of the photopolymerization initiator in the curable paint (1) is 100 parts by weight in total of the compound having at least six (meth) acryloyloxy groups in the molecule and the compound having four or five (meth) acryloyloxy groups in the molecule. It is 0.1-10 weight part normally with respect to. In addition, content of the photoinitiator in curable coating material (2) is 100 weight part of compounds which have at least 7 (meth) acryloyloxy group in a molecule | numerator, and the compound which has 3-6 (meth) acryloyloxy group in a molecule | numerator. It is 0.1-10 weight part normally. When this content is too small, hardening speed may not become fast compared with the case where a photoinitiator is not used.

In addition, the intensity | strength and irradiation time of an activation energy ray can be suitably adjusted according to the kind of curable compound, the thickness of the coating film, etc. The activation energy ray can be irradiated in an inert gas atmosphere. Nitrogen gas, argon gas, etc. can be used as this inert gas.

It is preferable that the thickness of the cured film formed in this way is 1-10 micrometers, More preferably, it is 2-6 micrometers. If the thickness is too thin, the scratch resistance of the cured film may be insufficient. If the thickness is too thick, cracks tend to occur when the cured film is exposed under high temperature and high humidity. The thickness of a cured film can be adjusted by adjusting the quantity per area of the curable paint apply | coated to the surface of a resin substrate, and / or the density | concentration of solid content contained in a curable paint.

The scratch resistant resin plate of the present invention thus obtained is composed of a resin substrate and a cured film having high scratch resistance and excellent antifouling properties formed on at least one surface of the resin substrate. The scratch-resistant resin plate of this invention can be used suitably as a display window protective plate of portable information terminals, such as a mobile telephone. Moreover, it can also be used as various members in the field | area where scratch resistance is required, such as finder parts, such as a digital camera and a handy video camera, and the display window protection board of a portable game machine.

In order to manufacture the display window protection plate of a portable information terminal from the scratch resistant resin board of this invention, you may process by printing, a hole, etc. as needed, and just cut | disconnect to required size. Then, if it sets to the display window of a portable information terminal, it can be set as the display window with high scratch resistance and excellent antifouling property.

Example

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the examples,% and parts are by weight unless otherwise specified. In addition, the measuring method or the evaluation method are as follows.

(Film thickness of hardened film)

The film thickness of a cured film was measured using the film thickness measuring apparatus [F-20 by Filmetrics company].

(Total light transmittance of the scratch resistant resin plate, haze)

The total light transmittance and the haze of the scratch resistant resin plate were measured using a haze transmittance and a reflectance meter (“HR-100” of Murakami Color Research Institute).

(Scratch resistance of the hardened film)

Using steel wool # 0000, the cured film is rubbed with a load of 2000 g / 4 cm 2 until the scratches can be visually identified every 10 round trips, 100 round trips, or less than 100 round trips. Was evaluated.

(Pencil hardness of the hardened film)

In accordance with JIS K 5600, the pencil hardness of the cured film was evaluated using a pencil hardness tester (Yasda Seiki Co., Ltd.).

(Contact angle of hardened film)

Using three types of water, oleic acid, and artificial fingerprint solution (based on JIS K 2246), the contact angle of the cured coating film was measured by a contact angle meter (contact angle meter "CA-X" of Kyowa Interface Science, Ltd.).

(Agglomeration and wiping of the magic ink of the hardened film)

Using the oil-based marker "piece" of Mitsubishi Pencil Co., Ltd., the characters were written at predetermined points on the cured film, and the written characters were wiped off. Writing a letter and wiping the letter were repeated three times at the same point on the cured film. The aggregating property of the magic ink of the cured film at the time of writing a character on a cured film, and the wipe-off property of the magic ink of the cured film at the time of wiping a character written on a cured film were evaluated based on the following reference | standard.

To wipe off, Asahi Kasei Co., Ltd. "Ken cotton" was used.

<Aggregation>

○: agglomeration

×: Do not bundle

<Wiping resistance>

○: can be wiped to the third time

△: can be wiped to the second time

×: Inability to wipe off

(Wipe of fingerprint of hard coating)

After a finger contacted the cured film, the fingerprint attached to the cured film was wiped off, and the wiping property of the fingerprint of the cured film was evaluated based on the following criteria.

To wipe off, Asahi Kasei Co., Ltd. "Ken cotton" was used.

○: well wiped

×: Hard to wipe off, but can be wiped off

×: can not be wiped

Example 1

CF ₃ -CF ₂ -CF ₂ -CF (with respect to 1 mole of the triisocyanate compound formed by trimerizing 10 parts of dipentaerythritol hexaacrylate, 10 parts of pentaerythritol tetraacrylate, and hexamethylene diisocyanate as the curable compound ( _{CF 3) - (O-CF} 2 -CF 2 -CF 2) n -OH (n = 3 ~ 20) to one mole of ethylene glycol monoacrylate was 0.4 parts of the reaction in a proportion of 2 moles of the reaction product of a photopolymerization initiator 0.75 parts of "IRGACURE 184" of Chiba Specialty Chemicals Co., Ltd., 0.25 parts of "IRGACURE 907" of Chiba Specialty Chemicals Co., Ltd., 0.02 parts of Silicone Oil [BYK-307 of Big Chemi Japan Co., Ltd.], and 40 parts of isobutyl alcohol and 40 parts of propylene glycol monomethyl ether were mixed as a solvent, and the curable coating material was prepared.

The paint was applied to one surface of a methacryl resin plate ["Smipex E" of Sumitomo Chemical Co., Ltd.) having a thickness of 2 mm and a size of 100 mm x 60 mm by a bar coater method, and then dried at room temperature for 1 minute. It dried again at 60 degreeC for 3 minutes, and formed the coating film on the surface of the methacryl resin plate. Subsequently, the coating film was hardened | cured by irradiating 0.5 J / cm <2> ultraviolet-rays using the 120 W high-pressure mercury lamp, and the scratch resistant resin board whose thickness of a cured film is 4 micrometers was obtained.

Table 1 shows the results of evaluating the scratch resistant resin plate.

Example 2

In the same manner as in Example 1, a scratch resistant resin plate having a thickness of the cured coating film was 5 μm.

Table 1 shows the results of evaluating the scratch resistant resin plate.

Comparative Example 1

When preparing curable paint, the same operation as in Example 1 was carried out except that the reaction product was not used, thereby obtaining a scratch resistant resin plate having a thickness of 4 µm. Table 1 shows the results of evaluating the scratch resistant resin plate.

Comparative Example 2

When preparing the curable paint, the same operation as in Example 1 was carried out except that 0.3 part of CF _3- (CF ₂ ) ₅ -CH ₂ -CH ₂ -OC (= 0) -CH = CH ₂ was used instead of 0.4 part of the reaction product. Thus, a scratch resistant resin plate having a thickness of the cured coating film was 5 μm. Table 1 shows the results of evaluating the scratch resistant resin plate.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Thickness (㎛) 4 5 4 5 Total light transmittance (%) 91.7 91.4 92.2 92.2 Haze (%) 0.9 0.7 0.2 0.2 Scratch Resistance (Returns) 500 750 10 10 Pencil strength 3H 4H 4H 4H Contact angle of water (°) 102 101 81 90 Contact angle of oleic acid (°) 63 65 38 43 Contact angle of artificial fingerprint solution (°) 78 76 56 64 Agglomeration of magic ink ○ ○ × × Wipe resistance of magic ink ○ ○ × △ Wipe of fingerprint ○ ○ △ △

Claims (4)

A compound having at least six (meth) acryloyloxy groups in a molecule, a compound having four or five (meth) acryloyloxy groups in a molecule, the following components (A), components (B) and components ( Curable paint containing the reaction product of C).
Component (A): Triisocyanate compound formed by trimerizing a diisocyanate compound.
Component (B): Polyether compound which has at least 1 group chosen from the group which consists of a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkylidene group in a molecule | numerator.
Component (C): A compound having a hydroxyl group and a polymerizable carbon-carbon double bond in a molecule. A compound having at least seven (meth) acryloyloxy groups in the molecule, a compound having three to six (meth) acryloyloxy groups in the molecule, the following component (A), component (B) and component (C Curable paint containing the reaction product of the following).
Component (A): Triisocyanate compound formed by trimerizing a diisocyanate compound.
Component (B): Polyether compound which has at least 1 group chosen from the group which consists of a hydroxyl group, a perfluoroalkyl group, a perfluoroalkylene group, and a perfluoroalkylidene group in a molecule | numerator.
Component (C): A compound having a hydroxyl group and a polymerizable carbon-carbon double bond in a molecule. The scratch resistant resin plate which consists of a resin substrate and the hardened film formed using the curable coating material of Claim 1 or 2 provided in at least one surface of this resin substrate. The display window protection plate of the portable information terminal which consists of a scratch-resistant resin board of Claim 3.