JP2013001714A - Active energy ray curable coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable coating composition capable of providing a cured film with excellent fingerprint resistance, hard coating properties and transparency with respect to various substrates, in particular, plastic substrates.SOLUTION: The active energy ray curable coating composition includes (A) a compound having two or more (meth)acrylic groups, (B) a copolymer having as constituent monomer units (b-1) fluoroethylene, (b-2) a hydroxyl group-containing vinyl ether and (b-3) a vinyl monomer not including a hydroxyl group, and (C) an organic solvent. The contents of the components (A)-(C) are preferably 90-99.9 pts.wt. of the (A) component, 0.1-10 pts.wt. of the (B) component and 1-1,000 pts.wt. of the (C) component with respect to 100 pts.wt. of the total of the (A) and (B) components.

Description

  The present invention relates to an active energy ray-curable coating composition capable of forming a cured film having fingerprint resistance, hard coat property and transparency on various substrates, particularly plastic substrates.

Conventionally, for various substrates such as metal, glass and plastic, a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design. The forming method is used.
In particular, the plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, it is required that the surface of the plastic substrate is coated with a coating composition and is subjected to a so-called hard coat treatment to impart hard coat properties (such as scratch resistance and pencil hardness) to improve the surface hardness. In addition, when used for optical members such as displays and touch panels, it is applied in order not to impair fingerprinting, such as fingerprints, sebum, sweat, etc. There is a need to maintain the transparency of the film.

  As a technique for imparting fingerprint resistance, there is a technique that makes a fingerprint inconspicuous by adding a compound containing a long-chain alkyl group and making the surface of the coating film oleophilic to reduce the contact angle of fingerprint fat ( Patent Documents 1 and 2). However, these hardened products cannot be obtained with sufficient hard coat properties such as scratches in the scratch resistance test and low pencil hardness. In addition, there is a technique for repelling fingerprint fat (increasing the contact angle) and facilitating wiping by adding a compound containing a polyfluoroalkyl group or polyfluoroether group to make the surface of the coating film water and oil repellency (Patent Document 3). 4, 5). However, since the contact angle of the fingerprint fat on these cured products is large, the light is scattered and the fingerprint is white and easily noticeable. There is also a technique to reduce the contact area with the finger, make it difficult to attach a fingerprint, make it less noticeable, and make it easier to wipe by mixing two or more types of metal oxide fine particles with different particle sizes into the paint and forming irregularities on the coating surface. (Patent Documents 6 and 7). However, these cured products have large haze and lose transparency, so that the image is white and the visibility is lowered.

JP 2001-353808 A (Claims) JP 2010-77282 A (Claims) JP-A-1985-49079 (Claims) JP 4556151 A (Claims) JP 2008-537557 A (Claims) Japanese Patent No. 4464449 (Claims) JP 2010-25734 (Claims)

  The inventors of the present invention have an active energy ray that is excellent in fingerprint resistance (fingerprints are not noticeable and easy to wipe off), hard coat properties and transparency with respect to various substrates, particularly plastic substrates. In order to find a curable coating composition, intensive studies were conducted.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a fingerprint resistance-imparting agent, which is a polymer of polyfunctional (meth) acrylate, fluoroethylene and a hydroxyl group-containing vinyl ether monomer, has a fingerprint resistance. The present invention was completed by discovering excellent properties, hard coat properties and transparency.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, the cured film is excellent in fingerprint resistance, hard coat property, and transparency with respect to various substrates, particularly with respect to plastic substrates.

The present invention relates to a compound (A) having two or more (meth) acrylic groups (hereinafter referred to as “component (A)”), fluoroethylene (b-1), hydroxyl group-containing vinyl ether (b-2), and no hydroxyl group. A copolymer (B) [hereinafter referred to as “component (B)”] and an organic solvent (C) (hereinafter referred to as “component (C)”) having vinyl monomer (b-3) as a constituent monomer unit. The present invention relates to a contained active energy ray-curable coating composition.
Hereinafter, the detail of each component and a composition is demonstrated.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

1. (A) component (A) component of this invention is a compound which has 2 or more of (meth) acryl groups.
As the component (A), either a monomer or an oligomer can be used.
As the component (A), a compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”] and a compound having three or more (meth) acryloyl groups [hereinafter referred to as “trifunctional or more ( Meth) acrylate ”.

  Examples of the monomer in the bifunctional (meth) acrylate include di (meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, and an alkylene oxide adduct of bisphenol Z. Di (meth) acrylate, di (meth) acrylate of bisphenol S alkylene oxide adduct, di (meth) acrylate of thiobisphenol alkylene oxide adduct, di (meth) acrylate of bisphenol A, di (meth) of bisphenol F Acrylate, di (meth) acrylate of bisphenol Z, di (meth) acrylate of bisphenol S, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (meth) acrylate , Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, di (meth) acrylate of glycerin alkylene oxide adduct, dimer acid diol di (meth) acrylate, cyclohexane dimethylol di (Meth) acrylate etc. are mentioned.

  In the bifunctional (meth) acrylate, examples of the oligomer include a urethane (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and the like, and a urethane (meth) acrylate oligomer is preferable.

Various compounds can be used as the tri- or higher functional (meth) acrylate, specifically, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, pentaerythritol tri or Tetra (meth) acrylate, pentaerythritol alkylene oxide adduct tri- or tetra (meth) acrylate, ditrimethylolpropane tri- or tetra (meth) acrylate, ditrimethylolpropane alkylene oxide adduct tri- or tetra (meth) acrylate , Dipentaerythritol tri, tetra, penta or hexa (meth) acrylate, dipentaerythritol alkylene oxide adduct tri, tetra, penta, hexa (meth) acrylate Tri (meth) acrylate of alkylene oxide adducts of over preparative and isocyanurate.
In this case, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the component (A), a reaction product of polyisocyanate and a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “urethane adduct”) is preferable.
Urethane adduct is an addition reaction product of (meth) acrylate having 2 or more (meth) acryloyl groups and 1 or more hydroxyl groups (hereinafter referred to as “hydroxyl-containing polyfunctional (meth) acrylate”) and polyisocyanate. Is more preferable.

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, and specifically, diisocyanate alkylene oxide adduct di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol diester. Alternatively, tri (meth) acrylate, ditrimethylolpropane di- or tri (meth) acrylate and dipentaerythritol di-, tri-, tetra- or penta (meth) acrylate may be used.
In this case, examples of the alkylene oxide include ethylene oxide and propylene oxide.
These (meth) acrylates may be further modified with caprolactone.

  Examples of polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, and their nurate type trimers.

Other examples of urethane adducts include addition reaction of a nurate type trimer of hexamethylene diisocyanate with a hydroxyalkyl (meth) acrylate or a modified caprolactone thereof.
In this case, examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

  Component (A) is commercially available. Specifically, it is manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Murasakitsu Series UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B. , UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV7510B, UV-7461TE, UV-2000B, UV-2010B, UV-2250EA, UV-2750B, DIC Corporation Unidic Series V-4000BA, V-4005, V-4018, V-4025, V-4026, V-4075, V-4200-70, V-4205, V-4260, V-4263, 15- 829, 17-813, 17-806, S2-371, Shin-Nakamura Chemical ( U-4HA, U-6HA, U-6LPA, UA-1100H, UA-53H, UA-33H, manufactured by Daicel Cytec Co., Ltd., EBECRYL series 204, 206, 220, 264, 265, 1259, 1290K, 5129, 8201, 8210, 8301, 294 / 25HD, 4820, 8405, UA-306H, UA-306I, UA-306T, UA-510H, manufactured by Kyoeisha Chemical Co., Ltd., beam set series manufactured by Arakawa Chemical Industries, Ltd. OT-1000 series manufactured by Toagosei Co., Ltd., Teslac series manufactured by Hitachi Chemical Co., Ltd., CN series manufactured by Sartomer, and the like.

  As the component (A), a tri- or higher functional (meth) acrylate is preferable in that the cured product has high hardness.

2. Component (B) Component (B) is composed of fluoroethylene (b-1) [hereinafter referred to as “(b-1)”], hydroxyl-containing vinyl ether (b-2) [hereinafter referred to as “(b-2)”]. And a vinyl monomer (b-3) not containing a hydroxyl group (hereinafter referred to as “(b-3)”) as a constituent monomer unit.
The component (B) is a component for imparting fingerprint resistance to the cured product of the composition.
As the component (B), various copolymers can be used as long as they are copolymers having (b-1), (b-2) and the monomer (b-3) as constituent monomer units. is there.

  Various compounds can be used as the fluoroethylene of (b-1). Specific examples include chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene and vinylidene fluoride, hexafluoropropylene and pentafluoropropylene. Among these, chlorotrifluoroethylene is preferable.

  As the hydroxyalkyl vinyl ether (b-2), various compounds can be used. Specifically, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol monovinyl ether And glycidyl vinyl ether. Among these, 4-hydroxybutyl vinyl ether is preferable.

As the vinyl monomer (b-3) which does not contain a hydroxyl group, various compounds can be used as long as they are copolymerizable with the above (b-1) and (b-2) and have a vinyl group.
Specific examples of (b-3) include alkyl vinyl ethers, vinyl esters, α-olefins and (meth) acrylates.
Examples of the alkyl vinyl ether include ethyl vinyl ether, t-butyl vinyl ether, N-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and the like.
Vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, vinyl isononanoate and pt-butylbenzoic acid.
Among these, pt-butyl vinyl benzoate and ethyl vinyl ether are preferable.

The molecular weight of component (B) is preferably 3,000 to 30,000 in terms of number average molecular weight.
In the present invention, the number average molecular weight means a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

  The component (B) is a copolymer having a hydroxyl group, and the hydroxyl value is preferably 40 to 89 mgKOH / g.

  As the copolymerization ratio of (b-1), (b-2), and (b-3), (b-1) :( b-2) :( b-3) = 40-60: 1-30: 10-59 (weight ratio) is preferable.

As the component (B), components (b-1) to (b-3) that are constituent monomers can be used and those obtained by polymerization according to a conventional method can be used.
Examples of the polymerization method include solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.

  Specific examples of the component (B) include Fluorate K-700, K-702, K-703, K-704, K-705, K-707, K-708, Asahi Glass Co., Ltd. manufactured by DIC Corporation. ) Made of Lumiflon series.

As a ratio of (A) and (B) component, (A) component: 90-99.9 weight part with respect to 100 weight part of total amounts of (A) and (B) component, (B) component: 0 0.1 to 10 parts by weight, more preferably (A) component: 99.5 to 95 parts by weight and (B) component: 0.5 to 5 parts by weight.
Fingerprint resistance can be imparted by setting the proportion of component (B) to 0.1 parts by weight or more, and transparency can be obtained by setting the proportion of component (B) to 10 parts by weight or less. it can.

3. (C) Component (C) A component is an organic solvent.
As the component (C), various compounds can be used as long as the components (A) and (B) can be dissolved.

Preferred specific examples of component (C) include alcohols such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, toluene and Aromatic compounds such as xylene; esters such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone.
As the component (C), only one kind of these compounds may be used, or two or more kinds may be used in combination.

(C) As a ratio of a component, 1-1000 weight part is preferable with respect to 100 weight part of total amounts of (A) and (B) component, More preferably, it is 10-500 weight part, Especially preferably, it is 50-200. Parts by weight.
(C) By making the content rate of a component into 1-1000 weight part, a composition can be made into a viscosity suitable for coating, and a composition can be apply | coated by the well-known coating method mentioned later.

4). Active energy ray-curable coating composition The composition of the present invention relates to an active energy ray-curable coating composition comprising the components (A) to (C) as essential components.
As a method for producing the composition, a conventional method may be followed, and the essential component and, if necessary, other components may be stirred and mixed.

  The cured product of the composition of the present invention has fingerprint resistance. Specifically, those having a contact angle with respect to oleic acid of 1 to 30 ° are preferred.

  The composition of the present invention essentially comprises the components (A) to (C). Depending on the purpose, a photopolymerization initiator, a compound having one ethylenically unsaturated group, a pigment, and a dye Various components such as a surface conditioner, an ultraviolet absorber, and a polymer can be blended.

  The composition of the present invention is a composition that is cured by irradiation with active energy rays. When visible light, ultraviolet light, or the like is used, a photopolymerization initiator is added to the composition. In addition, when hardening with an electron beam, a photoinitiator is not necessarily required.

  Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenone compounds such as phenyl} -2-methyl-propan-1-one; benzophenones such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyl-diphenylsulfide Α-ketoester compounds such as methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Phosphine oxide compounds such as oxides; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] Acetophenone / benzophenone hybrid photoinitiators such as 2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1 Oxime ester-based photopolymerization initiators such as 2-octanedione; and camphorquinone.

  As a photoinitiator, only 1 type of these compounds may be used, or 2 or more types may be used in combination.

As a content rate of a photoinitiator, 0.1-10 weight part is preferable with respect to 100 weight part of total amounts of (A) and (B) component, More preferably, it is 0.5-7 weight part, Especially. Preferably it is 1-5 weight part.
By setting the content ratio of the photopolymerization initiator to 0.1 to 10 parts by weight, the composition has excellent curability, and the cured film of the composition has excellent scratch resistance.

Moreover, the compound which has one ethylenically unsaturated group can also be used for the purpose of viscosity adjustment and hardness adjustment of a composition.
Specific examples of the compound having one ethylenically unsaturated group include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl phthalate ( (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, and an alkylene oxide adduct of phenol ( (Meth) acrylate, (meth) acrylate of alkylene oxide adduct of alkylphenol, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of paracumylphenol alkylene oxide adduct, orthophenylphenol (meth) acrylate, (meth) of orthophenylphenol alkylene oxide adduct Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) Hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone , N-vinylcaprolactam and the like.

5). Coating Method The substrate to which the composition of the present invention can be applied can be applied to various materials, and examples thereof include metals, glass and plastics.
Specific examples of the plastic include, but are not limited to, polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, polycarbonate resin, epoxy resin, and polyurethane resin.
The composition of the present invention can be preferably applied particularly to a plastic substrate, and can be used as a hard coat agent imparted with so-called fingerprint resistance.

What is necessary is just to follow a conventional method as a coating method of the composition of this invention.
Specifically, a method of applying a coating composition to a substrate, drying it if necessary, and irradiating active energy rays can be used.
Examples of the method for applying the coating composition of the present invention to the substrate include bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, knife coating, die coating, cap coating, and spray coating. It is not limited to.

What is necessary is just to set the coating method of the composition with respect to a base material, and the film thickness after drying suitably according to the objective.
The drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, a UV electrodeless lamp, and an LED lamp.
Examples of the electron beam irradiation apparatus include an eyelight beam manufactured by Iwasaki Electric Co., Ltd., Mini-EB manufactured by Ushio Electric Co., and a curetron manufactured by NHV Corporation.
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. For example, when UV irradiation is performed with a high-pressure mercury lamp, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm. ² is preferable, and 200 to 1,000 mJ / cm ² is more preferable.
When irradiating an electron beam, 30-300 kV and 10-300 kGy are preferable.

The cured film of the composition of the present invention is excellent in fingerprint resistance, hard coat property and transparency, and the material having the cured film of the composition of the present invention is used for various applications by taking advantage of this property. be able to.
For example, a display panel front panel, a touch panel, a display or casing of a mobile phone, a front panel such as a liquid crystal television, a casing of home appliances, a lighting fixture, and various lenses such as glasses.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, “part” means part by weight, and “%” means% by weight.

(Example 1 to Example 5)
The components shown in Table 1 were stirred and mixed according to a conventional method to produce an active energy ray-curable coating composition.
In addition, the numerical value of Table 1 represents a weight part number. Abbreviations in the table mean the following.

○ Abbreviation
(A) Component M-305: A mixture of pentaerythritol triacrylate and tetraacrylate, trade name Aronix M-400 manufactured by Toagosei Co., Ltd.
UA: Urethane adduct that is a reaction product of M-305 and hexamethylene diisocyanate
(B) component * K-703: fluorine resin, DIC Corporation product name Fluoronate K-703, active ingredient 60%, hydroxyl value 68 mgKOH / g, (b-1): (b-2): (b −3) = 51: 15: 34 (estimated from NMR measurement, integral intensity ratio (JNM-JNM-ECA400 manufactured by JEOL)). Number average molecular weight: 12000 (SEC measurement (HLC-8120 manufactured by Tosoh Corporation), PSt conversion).
(C) Component · MEK: Methyl ethyl ketone
Other components Irg-184: 1-hydroxy-cyclohexyl-phenyl-ketone, photo radical polymerization initiator manufactured by Ciba Japan Co., Ltd., trade name Irgacure 184;

(Comparative Examples 1 to 5)
The components shown in Table 2 were stirred and mixed according to a conventional method to produce a photocurable coating composition.
In addition, the numerical value of Table 2 represents a weight part number. Abbreviations in the table mean the following, except for those defined above.

○ Abbreviation
(B) 'component * RS-72K: Fluorine-type additive, DIC Corporation brand name Mega-Fac RS-72K.
DAC-HP: Fluorine-based additive, trade name OPTOOL DAC-HP manufactured by Daikin Industries, Ltd.

The composition shown in Table 1 and Table 2 was applied to a polyethylene terephthalate film (trade name Lumirror U35, 125 μm thickness, manufactured by Toray Industries, Inc.) with a bar coater so that the coating thickness after drying was about 5 μm. After drying with a hot air dryer at 70 ° C. for 5 minutes, a cured film was formed by ultraviolet irradiation or electron beam irradiation.
For ultraviolet (UV) irradiation, an ultraviolet irradiation machine (high pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. was used, and irradiation was performed for 3 passes at a lamp height of 24 cm and a conveyor speed of 8.8 m / min. The irradiation energy per pass was 200 mJ / cm ² in the UV-A region of UV POWER PUCK manufactured by EIT (total 600 mJ / cm ² ). The peak illuminance was 220 mW / cm ² in the UV-A region.
Electron beam (EB) irradiation uses an electron beam irradiator manufactured by Iwasaki Electric Co., Ltd., with an acceleration voltage of 200 kV, a beam current of 5.1 mA, a conveyor speed of 5.0 m / min, a dose of 100 kGy, and an oxygen concentration of 100 ppm or less. It was.
About the obtained cured film, fingerprint resistance, hard coat properties (abrasion resistance, pencil hardness), transparency and contact angle (water, oleic acid) were evaluated by the methods shown below. The evaluation results are shown in Table 3.

○ Fingerprint resistance (difficult to stand out)
Press the finger pad with nasal grease on the surface of the coating for 3 seconds under a load of 500 g, ○ which is less noticeable than the fingerprint attached to the coating prepared in Comparative Example 1, ○ X.

○ Fingerprint resistance (fingerprint wiping)
The fingerprint adhered as described above was wiped off three times by applying a load of 500 g to tissue paper (manufactured by Daio Paper Co., Ltd.). In the case of wiping within 3 reciprocations, ◯, in the case of wiping within 6 reciprocations, and in the case where 7 reciprocations or more are required, the evaluation was cross.
Fingerprint resistance was determined to be good when the fingerprint was not easily noticeable and easy to wipe off.

Scratch resistance Scratch resistance was determined by the number of scratches when a load of 500 g was applied to Bonster # 0000 manufactured by Nippon Steel Wool Co., Ltd. and rubbed 50 times. Scratch was 0 for scratch, 1 for 3 or less, ◯ for 4-10, Δ for 11 or more, and 3 or less for good.

○ Pencil hardness It evaluated according to JIS-K5600-5-4.

○ Transparency The appearance of the coating film was checked for visual defects such as cloudiness. The case where there was no defect such as cloudiness was marked as ◯, and the case where there was a defect was marked as x.

○ Contact angle measurement Using a Dataphysics OCA system (manufactured by Eihiro Seiki Co., Ltd.), 10 μl of water and oleic acid were dropped on the surface of the coating film, and the contact angle after 30 seconds was measured at room temperature.

In the compositions of Examples 1 to 5, the cured product surface is oleophilic, and the fingerprints are less noticeable by spreading and spreading the fingerprint fat and suppressing light scattering. At the same time, it was excellent in hard coat properties and transparency.
On the other hand, the composition of Comparative Example 1 that does not contain the component (B) has a poor fingerprint wiping property of the cured product. In the compositions of Comparative Examples 2 and 3 containing the water- and oil-repellent fluorine-based additive (B) ′ in place of the component (B), fingerprints attached to the surface of the cured product were easily noticeable. In Comparative Example 4 in which the amount of component (B) added was increased to 15 parts, the scratch resistance and transparency deteriorated.

  The active energy ray-curable coating composition of the present invention can be suitably used for coating various substrates such as metal, glass and plastic, and in particular, it is a hard material for plastic substrates to which fingerprint resistance is imparted. Useful as a coating material.

Claims (10)

  A compound (A) having two or more (meth) acrylic groups, fluoroethylene (b-1), a hydroxyl group-containing vinyl ether (b-2), and a vinyl monomer not containing a hydroxyl group (b-3) are used as constituent monomer units. An active energy ray-curable coating composition containing a copolymer (B) and an organic solvent (C). The active energy ray-curable coating composition according to claim 1, comprising the components (A) to (C) in the following ratio with respect to 100 parts by weight of the total amount of the components (A) and (B).
(A) Component: 90-99.9 parts by weight (B) Component: 0.1-10 parts by weight (C) Component: 1-1000 parts by weight   The active energy ray-curable coating composition according to claim 1 or 2, wherein the component (A) contains a compound having 3 or more (meth) acryl groups.   The active energy ray-curable coating composition according to claim 1, wherein the component (B) has a hydroxyl value of 40 to 89 mg KOH / g.   The number average molecular weight of the said (B) component is 3,000-30,000, The active energy ray hardening-type coating composition of any one of Claims 1-4.   The active energy ray-curable coating composition according to any one of claims 1 to 5, wherein the (B) component fluoroethylene is chlorotrifluoroethylene.   When the component (B) is a copolymerization ratio of fluoroethylene (b-1), a hydroxyl group-containing vinyl ether (b-2), and a vinyl monomer (b-3) not containing a hydroxyl group, the weight ratio is (b-1) :( The active energy ray-curable coating material according to any one of claims 1 to 6, wherein b-2): (b-3) is a copolymer of 40 to 60: 1 to 30:10 to 59. Composition.   The cured film of the composition of any one of Claims 1-7.   The cured film according to claim 8, wherein a contact angle of the cured product with respect to oleic acid is 1 to 30 °.   An article having the cured film according to claim 7 or 8.