JP2011012115A - Active energy ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition capable of forming a cured coating film excellent in transparency, capable of easily removing a fingerprint, being hardly injured and being also hardly invaded by an organic solvent.SOLUTION: The active energy ray-curable composition includes an active energy ray-curable urethane compound (A) formed by a 6C or more mono-alcohol (a1) having one hydroxyl group and not having an acryloyl group or a methacryloyl group, an active energy ray-curable compound (a2) having an acryloyl group or a methacryloyl group and having one hydroxyl group and an isocyanate compound (a3) having two or more of isocyanate groups, and an active energy ray-curable compound (B) different from the active energy ray-curable urethane compound (A).

Description

  The present invention relates to an active energy ray-curable composition excellent in fingerprint mark erasability and a member having a cured coating film using the composition.

  Various plastic films having a hard coat layer for preventing scratches are used on the surfaces of various displays such as LCD (Liquid Crystal Display), PDP (Plasma Display), and touch panel. However, the hard coat layer was easily attached with fingerprint marks, and the attached fingerprint marks could not be easily removed. For this reason, there has been a problem that the visibility of the image on the display is remarkably impaired or the aesthetic appearance of the display is impaired. In particular, since the surface of the touch panel is directly touched by a human hand, it is strongly desired that fingerprint traces are difficult to adhere and easily removed when attached.

  In order to solve these problems, for example, the hard coat layer contains a silicone compound or a fluorine compound, and the surface energy of the display surface is lowered to repel fingerprint marks and sebum, making it difficult to adhere. Improvement techniques have been proposed. Although this conventional technology has an antifouling effect on dust and cosmetics, it has a problem that fingerprint marks and sebum are not sufficiently prevented from sticking, and rather the attached fingerprint marks and sebum are conspicuous. Had. Furthermore, if the display surface is rubbed with a cloth or tissue paper to remove fingerprint marks or sebum stains, the fingerprint marks or sebum stains will become microdroplets, causing light reflection, and the surface will appear white and cloudy. There was also a problem that dirt was more noticeable after wiping than before wiping.

Therefore, another technique has been proposed in which fingerprint marks are less likely to adhere and the attached fingerprint marks are easily wiped off by containing a nonionic surfactant in a predetermined ratio in the hard coat layer (see Patent Document 1). ).
Furthermore, a technique for improving solvent resistance by incorporating a surfactant having a radical polymerizable functional group in a molecule at a predetermined ratio has been proposed (see Patent Document 2).
On the other hand, in the field of coating materials for optical fibers, (A) a polyurethane (meth) acrylate oligomer containing a structure having a long carbon number derived from a polyol having 14 to 40 carbon atoms, (B) an ethylenically unsaturated compound, and (C) A resin composition containing a photopolymerization initiator has been proposed (Patent Document 3).

JP 2004-114355 A JP 2005-186484 A Japanese Patent Laid-Open No. 10-95640

However, the technique described in Patent Document 1 lacks the scratch resistance (a property that is difficult to be damaged) and the solvent resistance (a property that the cured coating film is not easily affected by an organic solvent), which are the original functions of the hard coat layer. In the technique described in Patent Document 2, the hardness of the formed coating film is insufficient and does not satisfy the scratch resistance.
On the other hand, the technology described in Patent Document 3 relates to a coating material for optical fibers that has a high Young's modulus and a reduced water absorption rate and hydrogen generation amount. The coating material described in Patent Document 3 has scratch resistance, solvent resistance, and resistance to resistance. Various requirements required for the hard coat layer such as fingerprint property cannot be satisfied. In particular, no effect was observed on fingerprint resistance. Probably, the polyurethane (meth) acrylate oligomer (A) described in Patent Document 3 has a low affinity for fingerprint marks because a partial structure having a long carbon number derived from polyol is located between the urethane bond and the urethane bond. Even if such a polyurethane (meth) acrylate oligomer (A) is used, it is considered that fingerprint resistance does not appear. Alternatively, since it is “polyurethane”, it has a high molecular weight, so it is considered that when forming a cured coating film, it is difficult to orient on the surface of the coating film, and as a result, fingerprint resistance was not exhibited.

  Therefore, the present invention solves the above-mentioned problems of the prior art, and is a cured coating film having excellent transparency, making the fingerprints less noticeable, removing the fingerprints easily, being hard to be damaged, and being an organic solvent. An object of the present invention is to provide an active energy ray-curable composition that can form a cured coating film that is not easily attacked.

That is, the present invention
Mono-alcohol (a1) having 6 or more carbon atoms and having one hydroxyl group and no acryloyl group or methacryloyl group, and an active energy ray-curable compound having an acryloyl group or methacryloyl group and one hydroxyl group An active energy ray-curable urethane compound (A) formed from (a2) and an isocyanate compound (a3) having two or more isocyanate groups;
An active energy ray-curable compound (B) different from the active energy ray-curable urethane compound (A);
An active energy ray-curable composition containing

The isocyanate compound (a3) preferably has three or more isocyanate groups,
The carbon number of the monoalcohol (a1) is preferably a higher monoalcohol having 12 or more,
The active energy ray-curable urethane compound (A) preferably has two or more acryloyl groups or methacryloyl groups,
Moreover, it is preferable that the amount of the hydroxyl group of the active energy ray-curable compound (a2) having one hydroxyl group is larger than the amount of the hydroxyl group of the monoalcohol (a1),
The active energy ray-curable compound (a2) having one hydroxyl group preferably has two or more acryloyl groups or methacryloyl groups.
Moreover, it is preferable that the active energy ray-curable composition of the present invention further includes fine particles having a D50 particle diameter of 0.005 to 30 μm.

  Furthermore, the present invention provides a curable coating formed from the active energy ray-curable composition according to the present invention described above on at least a part of at least one member selected from glass, plastic, metal, wood member and paper. The present invention relates to a member with a cured coating film provided with a film.

  The active energy ray-curable urethane compound (A) of the present invention (hereinafter also simply referred to as “curable urethane composition”) has a curable property having a hydrocarbon structure having 6 or more carbon atoms and an acryloyl group or a methacryloyl group. Since the urethane compound (A) is used, it is possible to form a cured coating film that is excellent in transparency, in which fingerprints are not conspicuous, are not easily scratched, and are not easily affected by an organic solvent.

The active energy ray-curable urethane compound (A) (hereinafter also simply referred to as “curable urethane compound”) (A) used in the present invention will be described.
This curable urethane compound (A) is a compound having a hydrocarbon structure having 6 or more carbon atoms and an acryloyl group or a methacryloyl group, and is a curable component that imparts good fingerprint erasability to a cured coating film, that is, cured. Functions as an anti-fingerprint agent. In this specification, the fact that the attached fingerprint trace is not noticeable and the attached fingerprint trace is easy to wipe off may be collectively referred to as “fingerprint resistance” in some cases.

In the curable compound (A), the hydrocarbon structure having 6 or more carbon atoms is considered to be a structural portion mainly imparting fingerprint resistance.
At the beginning of development, the issue was to prevent fingerprints from sticking. However, it is virtually impossible to prevent the adhesion itself. Therefore, the present inventors considered whether the attached fingerprint trace could be made inconspicuous by approximating the refractive index of the cured coating film to the refractive index of the component of the fingerprint trace. However, even if the refractive indexes of both were made equal, the presence of the attached fingerprint marks was clearly visible without being integrated with the surrounding cured coating film. Based on the above knowledge, the inventors further studied the means to make the boundary line with the surrounding cured coating inconspicuous by reducing the height of the attached fingerprint trace as much as possible, and realized the effect of the present invention. It came to do.
A hydrocarbon structure having 6 or more carbon atoms is considered to have a high affinity with fingerprint marks, sebum and the like. Therefore, fingerprint marks and the like attached to the surface of the cured coating film formed from the curable composition containing the curable urethane compound (A) having such a partial structure are easily spread on the surface of the cured coating film. It is considered that there is an effect that the attached fingerprint mark is not conspicuous. And fingerprint marks attached to the surface of the cured coating film are partly transferred to cloth etc. by wiping with cloth or paper, but many of them are spread more widely and thinner on the surface of the cured coating film. It appears to be integrated with the cured coating. As a result, it is thought that the effect of becoming invisible and inconspicuous is exhibited. That is, the wiping property as used in the present invention means that it becomes difficult to see or becomes inconspicuous.

  The acryloyl group or methacryloyl group in the active energy ray-curable urethane compound (A) is a functional group responsible for active energy ray-curability and is different from the active energy ray-curable urethane compound (A). It is also a functional group that imparts compatibility with (B). Therefore, by using an acryloyl group or a methacryloyl group as an active energy ray-curable functional group, the composition of the present invention has excellent curability, transparency, resistance to scratches, and excellent solvent resistance. A cured coating film can be formed.

Such a curable urethane compound (A) has a predetermined structure or functional group, is excellent in transparency, is hard to notice fingerprints, is not easily damaged, and is hard to be attacked by an organic solvent. There is no particular limitation as long as a coating film can be formed, and it is a monoalcohol (a1) having 6 or more carbon atoms and an active energy ray-curable compound (a2) having an acryloyl group or a methacryloyl group and having one hydroxyl group. Other compounds having a different hydroxyl group can also be used.
The curable urethane compound (A) has an isocyanate group (a3) having two or more isocyanate groups described later, a hydroxyl group of a monoalcohol (a1) having 6 or more carbon atoms described later, and one hydroxyl group described later. By reacting the hydroxyl group of the active energy ray-curable compound (a2), a hydrocarbon moiety having 6 or more carbon atoms responsible for the anti-fingerprinting function derived from the monoalcohol (a1) and an acryloyl group or methacryloyl responsible for the curable function. Groups can be introduced.

In the present invention, by using a monoalcohol and introducing a hydrocarbon part having 6 or more carbon atoms, unlike the case of using a diol as in the invention described in Patent Document 3, the hydrocarbon part is sandwiched between urethane bonds. Without being able to achieve a higher degree of freedom. As a result, the curable urethane compound (A) has a high affinity for fingerprint marks, and the active energy ray-curable composition of the present invention containing the curable urethane compound (A) exhibits remarkable fingerprint resistance.
Incidentally, from the viewpoint of fingerprint resistance, it is preferable that the curable urethane compound (A) contains as many hydrocarbon moieties having 6 or more carbon atoms as possible. However, on the other hand, if the hydrocarbon portion having 6 or more carbon atoms in the curable urethane compound (A) is too much, the compatibility with the active energy ray-curable compound (B) described later is lowered, and a uniform composition is obtained. May not be obtained, or the cured coating film formed may become white. Therefore, the ratio of the site of the long-chain hydrocarbon portion in the curable urethane compound (A) is preferably 5 to 50 (wt%), more preferably 10 to 40 (wt%), particularly Preferably it is 15-35 (weight%).
Moreover, when the molecular weight of a curable urethane compound (A) is too large, when forming a cured coating film, it will become difficult to orient on the coating-film surface, and fingerprint resistance may fall as a result. Therefore, the weight average molecular weight of the curable urethane compound (A) is preferably about 50000 or less, more preferably 30000 or less, and further preferably 10,000 or less.

The monoalcohol (a1) having one hydroxyl group and not having an acryloyl group or a methacryloyl group is a monovalent alcohol of a hydrocarbon having 6 or more carbon atoms, and a chain monoalcohol is preferable as described later. The monoalcohol (a1) is sometimes referred to as a long-chain hydrocarbon monoalcohol.
In the present invention, it is important for the long-chain hydrocarbon monoalcohol (a1) to have 6 or more carbon atoms, and the number of carbon atoms from the viewpoint of ease of compatibility with fingerprints, ease of handling, and availability. Those having 10 to 60 are more preferable, those having 12 to 40 carbon atoms are more preferable, and those having 15 to 30 carbon atoms are particularly preferable. The monoalcohol may be saturated or unsaturated, may be linear, or may be branched. In addition, it may have an aromatic ring structure in a part of the molecule such as aliphatic part-aromatic part-aliphatic part-hydroxyl group, but the terminal is non-aromatic, in other words, chain aliphatic It preferably has a part or a cycloaliphatic part.

  Examples of the monoalcohol (a1) having 6 or more carbon atoms and having one hydroxyl group and no acryloyl group or methacryloyl group include aliphatic monoalcohols such as 1-hexanol, 4-methyl-2- Pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, Examples include 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, 2-decyltetradecanol, and oleyl alcohol. Examples of the alicyclic monoalcohol include cyclohexanol. Moreover, the alicyclic alcohol which has several cyclic structures like cholesterol can also be mentioned. Among these, 2-decyltetradecanol can be particularly preferably used.

Examples of the active energy ray-curable compound (a2) having an acryloyl group or methacryloyl group and having one hydroxyl group include compounds having one, two, or three or more acryloyl groups or methacryloyl groups. The curable compound (a2) can also be referred to as a curable monoalcohol (a2).
Examples of the curable monoalcohol having one acryloyl group or methacryloyl group include hydroxyalkyl esters of (meth) acrylic acid having 1 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, and the like can be mentioned.
Examples of the curable monoalcohol having two acryloyl groups or methacryloyl groups include 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin di (meth) acrylate, and the like.
Examples of the curable monoalcohol having 3 acryloyl groups or methacryloyl groups include pentaerythritol triacrylate, and examples of the monoalcohol having 5 acryloyl groups or methacryloyl groups include dipentaerythritol pentaacrylate. be able to.
In order to improve the scratch resistance and solvent resistance of the cured coating film formed from the curable composition of the present invention, the curable monoalcohol (a2) has two or more acryloyl groups or methacryloyl groups. A curable monoalcohol having 3 or more acryloyl groups or methacryloyl groups is particularly preferable. In addition, as curable monoalcohol (a2), what has an acryloyl group and what has a methacryloyl group can also be used together, and what has both in 1 molecule can also be used.

  Examples of the isocyanate compound (a3) having two or more isocyanate groups used for forming the curable urethane compound (A) include isocyanate compounds having two, three, four or more isocyanate groups. An isocyanate compound having three or more isocyanate groups is preferable in that it can easily introduce more acryloyl groups or methacryloyl groups into the curable urethane compound (A). That is, by reacting a long-chain hydrocarbon monoalcohol (a1) with one of three or more isocyanate groups and a curable monoalcohol (a2) with two or more other isocyanate groups as described later, More acryloyl groups or methacryloyl groups can be introduced into the curable urethane compound (A).

Examples of the diisocyanate compound include various known diisocyanates that are aromatic, aliphatic, or alicyclic.
For example, aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane. Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, etc.
Aliphatic diisocyanates include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diene. Isocyanate, dimerized isocyanate, etc., in which the carboxyl group of dimer acid is converted to an isocyanate group,
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and the like. It is done.

As an isocyanate compound (a3) having three isocyanate groups, for example,
Isocyanurate-modified isophorone diisocyanate (for example, Desmodur Z4470 manufactured by Sumika Bayer Urethane Co., Ltd.), isocyanurate-modified hexamethylene diisocyanate (for example, Sumidur N3300 manufactured by Sumika Bayer Urethane Co., Ltd., Duranate TPA- manufactured by Asahi Kasei Kogyo Co., Ltd. 100, MFX-90X), isocyanurate modified products such as isocyanurate modified toluylene diisocyanate (for example, Sumidur FL-2, FL-3, FL-4, HLBA manufactured by Sumika Bayer Urethane Co., Ltd.),
Biuret-modified hexamethylene diisocyanate (for example, Sumidur N75, N3200, N3290 manufactured by Sumika Bayer Urethane Co., Ltd., Duranate 24A-100, 22A-75PX, 21S-75E, 18H-70B manufactured by Asahi Kasei Kogyo Co., Ltd.) body,
Trimethylolpropane adduct hexamethylene diisocyanate (for example, Sumidur HT manufactured by Sumika Bayer Urethane Co., Ltd., Duranate P-301-75E manufactured by Asahi Kasei Kogyo Co., Ltd.), trimethylolpropane adduct toluylene diisocyanate (for example, Sumika Bayer Urethane Co., Ltd.) Examples thereof include isocyanate adducts having both ends with glycols or diamines such as Sumidu L75, L1375, L1365) manufactured by the company.

The total amount of hydroxyl groups of the long-chain hydrocarbon monoalcohol (a1) and the curable monoalcohol (a2) is approximately equal to the isocyanate group derived from the isocyanate compound (a3) having two or more isocyanate groups. A curable urethane compound (A) can be obtained by making it react.
And it is preferable to make it react so that the quantity of the hydroxyl group derived from curable monoalcohol (a2) may be larger than the quantity of the hydroxyl group derived from long-chain hydrocarbon monoalcohol (a1). More acryloyl groups or methacryloyl groups can be introduced into the curable urethane compound (A) by reacting so that the amount of the hydroxyl group derived from the curable monoalcohol (a2) is larger. The acryloyl group or methacryloyl group not only bears curability but also has a function of improving the compatibility between the curable urethane compound (A) and the active energy ray-curable compound (B) described later. Therefore, by introducing more acryloyl groups or methacryloyl groups into the curable urethane compound (A), the curability of the active energy ray curable composition of the present invention is improved, and the active energy ray curable composition of the present invention is improved. Scratch resistance, solvent resistance and transparency of a cured coating film formed from a product can be improved.

  Specifically, the active energy ray-curable urethane compound (A) preferably has 2 or more acryloyl groups or methacryloyl groups, more preferably 4 or more, still more preferably 6 or more, Those having 10 or more are particularly preferred. On the other hand, if the acryloyl group or the methacryloyl group is excessive, the compatibility with the active energy ray-curable compound (B) is improved too much, so that the curable urethane compound (A) is difficult to orient on the coating film surface. Therefore, it is preferable that the active energy ray-curable urethane compound (A) has 20 or less acryloyl groups or methacryloyl groups.

Such an active energy ray-curable urethane compound (A) can be obtained, for example, by the following method.
(1) A long-chain hydrocarbon monoalcohol (a1) is reacted with an isocyanate compound (a3) having two or more isocyanate groups to obtain a urethane intermediate having a long-chain hydrocarbon moiety and an isocyanate group, and the urethane The curable monoalcohol (a2) having a hydroxyl group in an amount corresponding to the isocyanate group in the intermediate is reacted. Or
(2) A curable monoalcohol (a2) is reacted with an isocyanate compound (a3) having two or more isocyanate groups to obtain a urethane intermediate having an acryloyl group or a methacryloyl group and an isocyanate group, and the urethane intermediate A long-chain hydrocarbon monoalcohol (a1) having a hydroxyl group in an amount corresponding to the isocyanate group therein is reacted. Or
(3) The long-chain hydrocarbon monoalcohol (a1), the curable monoalcohol (a2), and the isocyanate compound (a3) having two or more isocyanate groups are reacted at a stretch.

The curable composition according to the present invention comprises at least one active energy ray-curable compound (A) and a different active energy ray-curable compound (B) (hereinafter simply referred to as “curable compound (B)”. ) ”).). Hereinafter, the curable compound (B) will be described.
The curable compound (B) has two or more ethylenically unsaturated double bonds that contribute to curing so as to form a tough cured coating film that is excellent in scratch resistance and solvent resistance. A polyfunctional compound is preferably used mainly, and a monofunctional compound can be used as an auxiliary. As the ethylenically unsaturated double bond, an acryloyl group or a methacryloyl group is preferable. The curable compound (B) may be used in combination of a plurality of compounds as exemplified below.

As a polyfunctional thing among curable compounds (B), specifically, for example,
Dimethylol tricyclodecane diacrylate, (ethoxylated) bisphenol A diacrylate, (propoxylated) bisphenol A diacrylate, cyclohexane dimethanol diacrylate, (poly) ethylene glycol diacrylate, (ethoxylated) 1,6-hexanediol Diacrylate, (propoxylated) 1,6-hexanediol diacrylate, (ethoxylated) neopentyl glycol diacrylate, (propoxylated) neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, pentaerythritol tri (meta ) Acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimer Roll propane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acryloxyethyl) isocyanurate, trimethylol ethane tri (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified Dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate DOO, ester compounds of polyhydric alcohols and (meth) acrylic acid such as 1,2,3-cyclohexane tetra (meth) acrylate;

  Polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, polyacryl poly (meth) acrylate, polyalkyd poly (meth) acrylate, polyepoxy poly (meth) acrylate, polyspiroacetal poly Polyfunctional poly (meth) acrylate compounds such as (meth) acrylate, polybutadiene poly (meth) acrylate, polythiol polyene poly (meth) acrylate, and polysilicon poly (meth) acrylate;

  Ester compounds synthesized from polyhydric alcohols, polybasic acids and (meth) acrylic acid, for example, ester compounds synthesized from trimethylolethane / succinic acid / acrylic acid = 2/4 (molar ratio) It is done.

Among the curable compounds (B), from the viewpoint of toughness and scratch resistance,
A polyfunctional acrylate having an ester compound of a polyhydric alcohol and (meth) acrylic acid and having four or more (meth) acryloyl groups in the molecule;
Polyurethane poly (meth) acrylate having 6 or more (meth) acryloyl groups,
A polyepoxy poly (meth) acrylate having 4 or more (meth) acryloyl groups can be preferably used. Of course, those having more (meth) acryloyl groups can also be used.

  Polyurethane poly (meth) acrylate having 6 or more (meth) acryloyl groups is obtained by reacting, for example, polyisocyanate and (meth) acrylate having a hydroxyl group, and polyol and polyisocyanate are excessive in isocyanate group. There are those obtained by reacting an isocyanate group-containing urethane prepolymer obtained by reaction under the above conditions with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

Examples of polyisocyanates include tolylene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hydrogenated diphenylmethane-4,4′-diisocyanate, norbornane diisocyanate methyl, isophorone diisocyanate, hexamethylene diisocyanate, and the like. Can be mentioned. Moreover, the trimethylol propane adduct body of the said diisocyanate compound, the burette body which reacted with water, the trimer which has an isocyanurate ring, etc. can be used.

  Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, and the like.

  Examples of (meth) acrylates having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, (meth) acryloyl isocyanate, and the like.

  The polyepoxy poly (meth) acrylate having 4 or more (meth) acryloyl groups is obtained by, for example, reacting a carboxyl group of (meth) acrylic acid with an epoxy group of an epoxy resin to introduce a (meth) acryloyl group. And (meth) acrylic acid adducts of novolac-type epoxy resins.

  The curable composition according to the present invention preferably contains the curable compound (A) in a range of 0.1 to 15 parts by mass in solid content with respect to 100 parts by mass of the curable compound (B). It is more preferable to contain 0.5-10 mass parts, and it is still more preferable to contain 1.0-7.0 mass parts. If the amount is less than 0.1 parts by mass, the effect of fingerprint resistance may be insufficient. If the amount exceeds 15 parts by mass, basic properties such as toughness, scratch resistance, solvent resistance, and adhesion as a cured coating film may be obtained. There is a risk of damage.

The curable composition according to the present invention can further contain fine particles as necessary. Examples of the fine particles include inorganic fine particles and organic fine particles. These may be used alone or in combination of two or more. For example, silica is preferable as the inorganic fine particles, and acrylic resin, styrene resin, acrylic-styrene resin, etc. are preferable as the organic fine particles.
The fine particles can be appropriately selected from a particle size range of D50 particle size of 0.005 to 30 μm according to required functions such as refractive index, string resistance, antireflection property, low shrinkage and low curling property. .

When fine particles having a D50 particle size of 0.1 μm to 10 μm are used, it is possible to impart antiglare properties (property to suppress glare) to the cured coating film.
When fine particles having a D50 particle size of 0.005 to 0.1 μm are used, the refractive index of the cured coating film is adjusted, and shrinkage during curing of the cured coating film is suppressed, or the cured coating film is used in a high temperature and high humidity environment. It is possible to suppress contraction when the is placed.
The D50 particle size is a particle size corresponding to 50% of the volume distribution cumulative amount of the particle size distribution curve obtained by a Microtrac ultrafine particle size analyzer (model: UPA-EX150, manufactured by Nikkiso Co., Ltd.).

  When blending the fine particles, considering the hardness and refractive index of the cured coating film and further considering the shrinkage inhibiting effect, the total of 100% by mass of the curable compound (A), the curable compound (B), and the fine particles. It is preferable that 0.1-70 mass% is contained in 20 to 60 mass%. If the amount is less than 0.1% by mass, the desired performance may not be achieved. If the amount exceeds 70% by mass, formation of a coat layer may be difficult and the hardness may decrease.

The curable composition according to the present invention is cured by irradiating active energy rays such as ultraviolet rays and electron beams. In the case of curing by ultraviolet irradiation, the curable composition contains a photopolymerization initiator.
Examples of the photopolymerization initiator used include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2, 4,6-trimethylbenzoindiphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like, and these photopolymerization initiators are used alone. Two or more types may be used in combination.

  These photoinitiators are the sum total of the said active energy ray-curable compound (A), active energy ray-curable compound (B), and a photoinitiator from a viewpoint of ensuring appropriate crosslinking density and hard-coat property. It is preferable that 0.1-20 mass% is contained in 100 mass%, and 1-10 mass% is more preferable.

The curable composition concerning this invention can contain a solvent in view of the convenience of coating. That is, the solvent is used to adjust the viscosity and leveling properties of the curable composition (also referred to as a coating solution or a coating composition), or the drying property at the time of coating, and the coating method of the curable composition. If necessary, an appropriate amount may be blended. Therefore, the solid content of the curable composition is not particularly limited, but may be, for example, 20% by mass to 100% by mass.
Specific examples of the solvent include the following. These can be used alone or in combination of two or more.

  Examples of the ether solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, and phenetole.

  Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, 1,2 -Diacetoxyacetone and the like.

  Examples of the ester solvents include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-ptyrolactone, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, 2- Examples include ethyl ethoxy acetate, ethyl 2-ethoxypropionate, isobutyl acetate, methyl acetoacetate, ethyl acetoacetate and the like.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexyl alcohol, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, diacetone alcohol and the like.

Examples of the saturated hydrocarbon solvent include hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
Examples of the aromatic solvent include benzene, toluene, xylene and the like.
Examples of glycol solvents include ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, and butyl carbitol.

  If necessary, the curable composition further includes a photosensitizer, a light stabilizer, an ultraviolet absorber, a catalyst, a colorant, a lubricant, a leveling agent, an antifoaming agent, a polymerization accelerator, an antioxidant, a difficult agent. One or more of a flame retardant, an infrared absorber, a surfactant, a surface modifier, a thixotropic agent, and the like can be appropriately added within a range that does not impair the effects of the present invention.

When the curable composition according to the present invention is applied to various members and contains an organic solvent, it is dried and then irradiated with active energy rays to form a cured coating film.
The thickness of the cured coating film is preferably 4 to 20 μm from the viewpoint of ensuring pencil hardness and wear resistance, and avoiding a decrease in adhesion to the member or occurrence of cracks in the cured coating film. More preferably, it is -15 micrometers, and it is still more preferable that it is 5-10 micrometers.

The member for providing the cured coating film can be appropriately selected from the group consisting of glass, plastic, metal, wood member and paper. Furthermore, a composite member composed of a plurality of members can also be selected. These members may have a flat shape such as a plate, film, or paper, or may have a three-dimensional shape.
The plastic film is preferably transparent.

Examples of the plastic material include transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and acrylic polymers.
Examples of the polyester polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulose polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the acrylic polymer include polymethyl methacrylate.

Examples of the plastic material include transparent polymers such as a styrene polymer, an olefin polymer, a vinyl chloride polymer, and an amide polymer.
Examples of the styrene polymer include polystyrene and acrylonitrile / styrene copolymer. Examples of the olefin polymer include polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and an ethylene / propylene copolymer. Examples of the amide polymer include nylon and aromatic polyamide.

  Furthermore, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ketone polymer, polyphenyl sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene Examples thereof include transparent polymers such as polymer-based polymers, epoxy-based polymers, and blends of the aforementioned polymers. In particular, those having a low birefringence are preferably used.

  When a plastic film is used as a member, the surface on which a cured coating film is formed is selected from the group of acrylic resins, copolymer polyester resins, polyurethane resins, styrene-maleic acid graft polyester resins, acrylic graft polyester resins, and the like. A so-called easy adhesion type film provided with a resin layer can also be used.

  Among the members, the thickness of the flat member can be determined as appropriate, but in the case of a plastic film, it is generally about 10 to 500 μm from the viewpoints of workability such as strength and handling, and thin layer properties. It is preferable. 20-300 micrometers is especially preferable, and 30-200 micrometers is more preferable. When the member has a three-dimensional shape, the thickness is not limited.

The wood member may be a single plate made of natural wood or a so-called plywood made by laminating a plurality of members. Prior to the formation of the cured coating film, a coating layer, a coating film for imparting color or design, a coating film for glazing, a coating film for matting, and the like may be provided.
Among the wooden members, the thickness of the flat member may be determined as appropriate, and may be a thin plate of less than 1 mm or a thick plate of several tens of mm. When the member has a three-dimensional shape, the thickness is not limited.

  The curable composition may be applied by a conventional method, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. When a solvent is included, it is preferable to dry the coating film at about 50 to 150 ° C. after applying the curable composition.

As described above, the curable composition after application can be cured by irradiation with active energy rays. Examples of active energy rays include ultraviolet rays and electron beams. When ultraviolet rays are used, a light source such as a high-pressure mercury lamp, an electrodeless lamp, or a xenon lamp is used, and the ultraviolet irradiation amount is preferably about 100 to 2000 mJ / cm ² , for example. The obtained cured coating film is excellent in fingerprint mark erasability.

  Hereinafter, the present invention will be specifically described by way of examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively. The NCO equivalent and the hydroxyl equivalent mean the molecular weight per NCO group or hydroxyl group in the molecule.

(Synthesis Example 1)
<Synthesis process of active energy ray-curable compound>
In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube, 192 parts of propyl acetate, isocyanurate-modified hexamethylene diisocyanate (NCO group: 3, NCO equivalent: 193, trade name: “Sumidule N −”) 3300 "(manufactured by Sumitomo Bayer Urethane Co., Ltd.), 193 parts, 4 parts of N, N-dimethylbenzylamine were charged, and at a temperature of 90 ° C., while blowing nitrogen, 2-decyltetradecanol (hydroxyl group: 1, hydroxyl group equivalent: 355, Product name: “Risonol 24SP” (manufactured by Higher Alcohol Industry Co., Ltd.) 118 parts was added dropwise, reacted for 3 hours after completion of the addition, and urethane intermediate having a long chain hydrocarbon moiety of C ₁₂ H ₂₅ (C ₁₀ H ₂₁ ) CHCH ₂ Got the body.
Next, after thoroughly mixing 456 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl equivalent: 684, trade name: “Aronix M403” manufactured by Toagosei Co., Ltd.) and 138 parts of propyl acetate, air was blown into the mixture. Then, after dropping into the urethane intermediate and reacting for 5 hours after the completion of dropping, the disappearance of the isocyanate group was confirmed by infrared absorption spectrum, and then cooled to room temperature to obtain a compound (A-1) solution (solid content 50 wt%). Got.
In addition, the molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from 2-decyltetradecanol and the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from 2-decyltetradecanol): Hydroxyl group (derived from dipentaerythritol pentaacrylate) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (A-1) of Synthesis Example 1 is 10.

(Synthesis Example 2)
Instead of 118 parts of 2-decyltetradecanol used in Synthesis Example 1, 1-octanol having 8 carbon atoms (hydroxyl group: 1, hydroxyl group equivalent: 129, trade name: “Calcoal 0898”, manufactured by Kao Corporation) The same operation as in Synthesis Example 1 was performed except that 43 parts were used to obtain a compound (A-2).
In addition, the molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from 1-octanol and the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from 1-octanol): hydroxyl group (dipentaerythritol pentane). Acrylate origin) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (A-2) of Synthesis Example 2 is 10.

(Synthesis Example 3)
Instead of 118 parts of 2-decyltetradecanol used in Synthesis Example 1, 12-carbon 1-dodecanol (hydroxyl group: 1, hydroxyl group equivalent: 186, trade name: “CALCOL 2098”, manufactured by Kao Corporation) Was used in the same manner as in Synthesis Example 1 except that 62 parts of Compound (A-3) were used.
In addition, the molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from 1-dodecanol and the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from 1-dodecanol): hydroxyl group (dipentaerythritol pentane). Acrylate origin) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (A-3) of Synthesis Example 3 is 10.

(Synthesis Example 4)
Instead of 118 parts of 2-decyltetradecanol used in Synthesis Example 1, carbon number 18 isostearyl alcohol (hydroxyl group: 1, hydroxyl group equivalent: 271, trade name: “Lisonol 18SP”, manufactured by Higher Alcohol Industry Co., Ltd. ) Was used in the same manner as in Synthesis Example 1 except that 90 parts were used to obtain compound (A-4).
The molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from isostearyl alcohol and the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from isostearyl alcohol): hydroxyl group (dipentaerythritol). Derived from pentaacrylate) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (A-4) of Synthesis Example 4 is 10.

(Synthesis Example 5)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, which was 456 parts in Synthesis Example 1, was converted to polyethylene glycol monoacrylate (hydroxyl group: 1, hydroxyl group equivalent: 621, trade name: “Blemmer AE-400”, NOF Corporation. The compound (A-5) was obtained in the same manner as in Synthesis Example 1 except for changing to 414 parts.
In addition, the molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from 2-decyltetradecanol and the hydroxyl group derived from polyethylene glycol monoacrylate is isocyanate group: hydroxyl group (derived from 2-decyltetradecanol): hydroxyl group (Derived from polyethylene glycol monoacrylate) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (A-5) of Synthesis Example 5 is two.

(Synthesis Example 6)
Instead of 193 parts of isocyanurate-modified hexamethylene diisocyanate used in Synthesis Example 1, 111 parts of isophorone diisocyanate (NCO group: 2, NCO equivalent: 111) was used, and further, 2-decyltetradecanol 118 having 24 carbon atoms. The same operation as in Synthesis Example 1 was carried out except that the content was changed to 178 parts and 456 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were changed to 342 parts to obtain compound (A-6).
The molar ratio of the isocyanate group derived from isophorone diisocyanate, the hydroxyl group derived from 2-decyltetradecanol and the hydroxyl group derived from dipentaerythritol pentaacrylate is: isocyanate group: hydroxyl group (derived from 2-decyltetradecanol): hydroxyl group (dipenta Derived from erythritol pentaacrylate) = 2 mol: 1 mol: 1 mol, and the average number of acryloyl groups in the compound (A-6) of Synthesis Example 6 is 5.

(Synthesis Example 7)
Instead of 193 parts of isocyanurate-modified hexamethylene diisocyanate used in Synthesis Example 1, 48 parts of 2-acryloyloxyethyl isocyanate (NCO group: 1, product name: “Karenz AOI”, Showa Denko KK) was used, and dipenta Except not using the mixture of erythritol pentaacrylate and dipentaerythritol hexaacrylate, operation similar to the synthesis example 1 was performed, and the compound (X-1) was obtained.
The molar ratio of the isocyanate group derived from 2-acryloyloxyethyl isocyanate and the hydroxyl group derived from decyltetradecanol is isocyanate group: hydroxyl group (derived from decyltetradecanol): = 1 mol: 1 mol. The average number of acryloyl groups in compound (X-1) is one.

(Synthesis Example 8)
In place of 193 parts of isocyanurate-modified hexamethylene diisocyanate used in Synthesis Example 1, 111 parts of isophorone diisocyanate (NCO groups: 2, NCO equivalent: 111) were used, and hydroxyl group was substituted for 118 parts of 2-decyltetradecanol. A diol having 36 carbon atoms and a 11 carbon atom portion having a hydroxyl group (hydroxyl group: 2, hydroxyl group equivalent: 271, "trade name: SVERMOL908", manufactured by Cognis Japan) 180 In the same manner as in Synthesis Example 1, except that 456 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate was changed to 228 parts, compound (X-2) was obtained.
In addition, the molar ratio of the isocyanate group derived from isophorone diisocyanate, the hydroxyl group derived from diol, and the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from diol): hydroxyl group (derived from dipentaerythritol pentaacrylate) = 8 mol: 6 Mole: 2 mol, and the average number of acryloyl groups in the compound (X-2) of Synthesis Example 8 is 10.

(Synthesis Example 9)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: “Aronix M403” manufactured by Toagosei Co., Ltd.), which was 456 parts in Synthesis Example 1, was polyethylene glycol monomethyl ether (hydroxyl group: 1, hydroxyl group equivalent: 400). , Trade name: “Uniox M-400” (manufactured by NOF Corporation), except for changing to 267 parts, Compound (X-3) was obtained in the same manner as in Synthesis Example 1.
The molar ratio of the isocyanate group derived from isocyanurate-modified hexamethylene diisocyanate, the hydroxyl group derived from 2-decyltetradecanol and the hydroxyl group derived from polyethylene glycol monomethyl ether is: isocyanate group: hydroxyl group (derived from 2-decyltetradecanol): hydroxyl group (Derived from polyethylene glycol monomethyl ether) = 3 mol: 1 mol: 2 mol, and the average number of acryloyl groups in the compound (X-3) of Synthesis Example 9 is 0.

Example 1
For 100 parts of pentaerythritol tetraacrylate (trade name: “Aronix M450” manufactured by Toa Gosei Co., Ltd.) as the compound (B), 5 parts of the compound (A-1) synthesized in Synthesis Example 1 in a solid content and photopolymerization started. As the agent, 5 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals) and 110 parts of propylene glycol methyl ether were mixed to obtain a curable composition (also referred to as a coating composition or a coating liquid).
This composition was applied to the surface of an easily adhesive-treated polyethylene terephthalate film (trade name: “Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) having a thickness of about 100 μm using a bar coater, and the solvent was removed with a hot air oven. After that, ultraviolet rays were irradiated with a high-pressure mercury lamp with an output of 80 w / cm to polymerize and cure the coating film to obtain a substrate with a cured coating film having a coating layer having a dry film thickness of about 6 μm.

(Examples 2 to 6)
Curing was conducted in the same manner as in Example 1 except that instead of the compound (A-1) synthesized in Synthesis Example 1, the compounds (A-2) to (A-6) synthesized in Synthesis Examples 2-8 were changed. A substrate with a coating film was obtained.

Example 9
Except that the coating resin composition was prepared by adding 4 parts of silica having a D50 particle diameter of 4 μm (trade name: “Nipsil SS50-B” manufactured by Tosoh Silica Co., Ltd.) as fine particles to the coating resin composition of Example 1. In the same manner as in Example 1, a substrate with a cured coating film was obtained.

(Comparative Example 1)
A substrate with a cured coating film was obtained in the same manner as in Example 1 except that the compound (A-1) synthesized in Synthesis Example 1 was not used.

(Comparative Example 2)
Instead of the compound (A-1) synthesized in Synthesis Example 1, except that 5 parts of 2-decyltetradecanol (hydroxyl group: 1, trade name: “Lisonol 24SP”, manufactured by Higher Alcohol Industry Co., Ltd.) was used, Although it was going to obtain the base material with a cured coating film like Example 1, the coating-film surface did not harden | cured but it did not have to evaluate various physical properties.

(Comparative Example 3)
A base material with a cured coating film was obtained in the same manner as in Example 1 except that the compound (X-1) synthesized in Synthesis Example 7 was used instead of the compound (A-1) synthesized in Synthesis Example 1. .

(Comparative Example 4)
A substrate with a cured coating film was obtained in the same manner as in Example 1 except that the compound (X-2) synthesized in Synthesis Example 8 was used instead of the compound (A-1) synthesized in Synthesis Example 1. .

(Comparative Example 5)
A substrate with a cured coating film was obtained in the same manner as in Example 1 except that the compound (X-3) synthesized in Synthesis Example 9 was used instead of the compound (A-1) synthesized in Synthesis Example 1. .

(Comparative Example 6)
Example 1 except that 5 parts of a leveling agent (trade name: “BYK-UV3500” manufactured by Big Chemie Japan) containing a dimethylsiloxane skeleton was used instead of the compound (A-1) synthesized in Synthesis Example 1. In the same manner, a substrate with a cured coating film was obtained.

(Comparative Example 7)
Instead of compound (A-1) synthesized in Synthesis Example 1, polyoxyethylene hydrogenated castor oil (hydroxyl group: 3, ethylene oxide unit number 30, product name: “EMALEX HC-30”, manufactured by Nippon Emulsion Co., Ltd. ) Was used in the same manner as in Example 1 to obtain a substrate with a cured coating film.

(Comparative Example 8)
Instead of compound (A-1) synthesized in Synthesis Example 1, changed to 5 parts polyoxyethylene alkylphenyl ether containing 1 vinyl group (trade name: “AQUALON RN-10”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Except having done, it carried out similarly to Example 1, and obtained the base material with a cured coating film.

  About the base material with a cured coating film of Examples 1-9 and Comparative Examples 1-8 (except comparative example 2), the following physical-property evaluation was performed and the result was put together in Table 1 and Table 2.

(Pencil hardness)
Based on JISK5400, it measured with the load of 750g with respect to the cured coating film surface of a base material with a cured coating film using the Clemens type scratch hardness tester (model | form: product made from HA-301 tester industry company).

(Abrasion resistance)
Place a square pad of 1 centimeter centimeter equipped with # 0000 steel wool on the cured coating surface of the substrate with the cured coating, and after reciprocating 10 times with a load of 500 g, visually evaluate the appearance and determine the number of scratches. It was measured.

(Fingerprint wiping property)
For the front side evaluation of the solvent treatment, the index finger was pressed against the tester's cheek for 1 second, and then the index finger was pressed onto the cured coating surface of the substrate with the cured coating film of each Example and Comparative Example for 2 seconds. Then, it wiped lightly 10 times with another finger | toe, and wiped off property (unprocessed surface) was evaluated by the following references | standards by visual observation. In addition, evaluation A and evaluation B have the performance which does not have trouble in practical use.
A: No wiping trace remains.
B: A trace of wiping remains.
C: A wipe mark remains.
Moreover, as a post-solvent treatment evaluation, absorbent cotton moistened with isopropanol was placed on the coating layer surface of the substrate with the coating layer, and after 50 reciprocations, evaluation was performed in the same manner as the untreated surface evaluation.

(Solvent resistance)
The cured coating film surface of the substrate with a cured coating film was rubbed 50 times with absorbent cotton moistened with isopropanol, and then the coating film appearance was evaluated with the naked eye.

(Haze value / total light transmittance)
The haze value (Hz) and total light transmittance (T.t.) of the substrate with a cured coating film were measured using a Haze Meter (model: NDH2000, manufactured by Nippon Denshoku).

From the results in Table 1, the substrate with a cured coating film using the curable compositions of Examples 1 to 8 is excellent in balance of fingerprint wiping property, scratch resistance, pencil hardness, solvent resistance, and the like. found. Accordingly, these cured and film-coated substrates can be suitably used for applications requiring hard coat properties, transparency and antifouling properties such as displays, touch panels, and building materials.
Furthermore, the base material with a cured coating film of Example 9 using the curable composition containing fine particles was able to obtain a relatively large haze value of 5% without significantly reducing the total light transmittance. . Therefore, such a substrate with a cured coating film also has the effect of softening reflected light entering the eyes and reducing glare by irregularly reflecting light incident from the cured coating film side on the surface of the cured coating film. .

On the other hand, as shown in Table 2, in Comparative Example 1 containing no curable compound (A), the hard coat property of the cured coating film was good, but the fingerprint wiping property was not expressed at all.
In Comparative Example 3 containing Compound (X-1) obtained by reacting a compound having one isocyanate group and one acryloyl group with a higher alcohol, the entire coating film was cloudy white. Further, there were many scratches in the scratch resistance test, and the hard coat property was insufficient.

  Comparative Example 4 containing a polyurethane structure compound (X-2) using diol instead of monool had good transparency and hard coat properties of the coating film, but lacked fingerprint wiping properties.

  Comparative Example 5 had better fingerprint wiping properties than Comparative Example 1, but the urethane compound (X-3) used did not have an acryloyl group responsible for the active energy ray curing function. The solvent resistance of the film was insufficient, and after wiping the cured coating film with the solvent, the wiping property of the fingerprint was lowered, and there were many scratches in the scratch resistance test, and the hard coat property was insufficient.

  Comparative Example 6 is an example containing a compound having a plurality of (meth) acryloyl groups and a dimethylsiloxane skeleton but not having a fatty acid ester structure. In the comparative example 4, when the fingerprint wiping test of the cured coating film was performed, the wiping traces appeared cloudy and became noticeable rather than before wiping.

  In Comparative Example 7 containing a fatty acid ester, the fingerprint wiping property was better than in Comparative Example 1, but the fatty acid ester used does not have any functional group responsible for the active energy ray curing function. , The solvent resistance of the cured coating film is insufficient, and after wiping the cured coating film with a solvent, the fingerprint wiping property decreases, and there are many scratches in the scratch resistance test, resulting in insufficient hard coat properties. It was.

  Comparative Example 8 is an example using a compound having a vinyl group and a fatty acid ester structure, not a (meth) acryloyl group, and has a functional group responsible for an active energy ray curing function, and thus has no curable functional group at all. The solvent resistance of the cured coating film was better than Comparative Example 5, and the fingerprint wiping performance after the solvent treatment was maintained. However, the vinyl group is less reactive than the (meth) acryloyl group, and the number of functional groups in one molecule is small. Therefore, the (meth) acryloyl group is a functional group responsible for the active energy ray curing function. The fingerprint wiping property was inferior to those of the examples having the scratches, scratches in the scratch resistance test, and hard coat properties were insufficient.

  The active energy ray-curable composition according to the present invention can be suitably used for imparting fingerprint resistance to a display surface member of a touch panel, as well as various plastic molded products, lenses on the outermost surface portion of a camera, and glasses. It can also be used to impart the same function to the surface of each lens, window glass for buildings and vehicles, various printed materials, and wooden member products such as building materials and furniture.

Claims (9)

Mono-alcohol (a1) having 6 or more carbon atoms and having one hydroxyl group and no acryloyl group or methacryloyl group, and an active energy ray-curable compound having an acryloyl group or methacryloyl group and one hydroxyl group An active energy ray-curable urethane compound (A) formed from (a2) and an isocyanate compound (a3) having two or more isocyanate groups;
An active energy ray-curable compound (B) different from the active energy ray-curable urethane compound (A);
An active energy ray-curable composition containing   The active energy ray-curable composition according to claim 1, wherein the monoalcohol (a1) is a higher monoalcohol having 12 or more carbon atoms.   The active energy ray-curable composition according to claim 1 or 2, wherein the isocyanate compound (a3) has three or more isocyanate groups.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the active energy ray-curable urethane compound (A) has two or more acryloyl groups or methacryloyl groups.   The active energy ray-curable property according to any one of claims 1 to 4, wherein the amount of the hydroxyl group of the active energy ray-curable compound (a2) having one hydroxyl group is larger than the amount of the hydroxyl group of the monoalcohol (a1). Composition.   The active energy ray-curable composition according to any one of claims 1 to 5, wherein the active energy ray-curable compound (a2) having one hydroxyl group has two or more acryloyl groups or methacryloyl groups.   The active energy ray-curable composition according to any one of claims 1 to 6, further comprising fine particles having a D50 particle diameter of 0.005 to 30 µm.   The active energy ray-curable composition according to any one of claims 1 to 7, which is used for forming a fingerprint-resistant cured coating film.   A cured coating film formed from the active energy ray-curable composition according to any one of claims 1 to 8 is formed on at least a part of at least one member selected from glass, plastic, metal, wood member, and paper. A member with a cured coating film provided.