JP2010202777A - Active energy line curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curable composition capable of forming a cured coating excellent in transparency, allowing easy removal of a fingerprint or dust, being hardly injured, and being hardly eroded even with an organic solvent. <P>SOLUTION: The active energy ray curable composition contains: an active energy ray curable quarternary ammonium salt (A) having a fatty acid ester structure containing a 6-11C aliphatic acid, a polyalkylene oxide chain, and an acryloyl group or a methacryloyl group; and an active energy ray curable compound (B) different from the active energy ray curable quarternary ammonium salt (A). <P>COPYRIGHT: (C)2010,JPO&INPIT

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, fingerprint marks and dust are easily attached to the hard coat layer, and the attached fingerprint marks and dust cannot 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.

On the other hand, another technique has been proposed in which fingerprint traces are less likely to adhere and the attached fingerprint traces can be 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).

Japanese Patent Laid-Open No. 2004-114355 Japanese Patent Application Laid-Open No. 2005-186484

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 addition, the technique described in Patent Document 2 does not satisfy the scratch resistance due to insufficient hardness of the coating film to be formed, and dust is likely to adhere to the coating film, and it is difficult to remove the adhered dust. There was a problem with.

  Therefore, the present invention solves the above-mentioned problems of the prior art, is a cured coating film having excellent transparency, makes the fingerprints less noticeable, and can easily remove fingerprints, dust, etc. An object of the present invention is to provide an active energy ray-curable composition capable of forming a cured coating film that is hardly affected by an organic solvent.

According to a first aspect of the present invention,
An active energy ray-curable quaternary ammonium salt (A) having a fatty acid ester structure comprising a fatty acid having 6 to 11 carbon atoms, a polyalkylene oxide chain, and an acryloyl group or a methacryloyl group;
An active energy ray-curable compound (B) different from the active energy ray-curable quaternary ammonium salt (A);
An active energy ray-curable composition containing is provided.

  According to the second aspect of the present invention, at least part of at least one member selected from glass, plastic, metal and paper is formed from the active energy ray-curable composition according to the first aspect of the present invention. The member with a cured coating film provided with the cured coating film to be provided is provided.

  The active energy ray-curable composition of the present invention (hereinafter also simply referred to as “curable composition”) has a fatty acid ester structure composed of a fatty acid having 6 to 11 carbon atoms, a polyalkylene oxide chain, an acryloyl group or methacryloyl. An active energy ray-curable quaternary ammonium salt (A) having a group, it is excellent in transparency, fingerprints are not conspicuous, dust and the like can be easily removed, scratches are less likely, and It is possible to form a cured coating film that is hardly affected by organic solvents.

  The active energy ray-curable quaternary ammonium salt (hereinafter also simply referred to as “curable quaternary ammonium salt”) (A) used in the present invention will be described. This curable quaternary ammonium salt (A) is a compound having a fatty acid ester structure comprising a fatty acid having 6 to 11 carbon atoms, a polyalkylene oxide chain, an acryloyl group or a methacryloyl group, and a quaternary ammonium salt structure. It functions as a component that imparts good fingerprint erasability to the cured coating film, that is, a fingerprint resistance imparting 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 this curable quaternary ammonium salt (A), the fatty acid ester structure comprising a fatty acid having 6 to 11 carbon atoms and the polyalkylene oxide chain are considered to be structural portions 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.
The fatty acid ester structure composed of fatty acids having 6 to 11 carbon atoms and the polyalkylene oxide chain are considered to have a high affinity for 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 quaternary ammonium salt (A) having both structures are easily wetted and spread on the surface of the cured coating film. Since it tends to be low, 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 is a functional group responsible for active energy ray curability. All the polymerizable functional groups of the polymerizable surfactant specifically used in the examples of Patent Document 2 listed above are vinyl groups other than acryloyl groups or methacryloyl groups (hereinafter simply referred to as vinyl groups). is there. An acryloyl group or a methacryloyl group is excellent in active energy ray curability as compared with a vinyl group. Therefore, by using an acryloyl group or a methacryloyl group as an active energy ray-curable functional group, according to the composition of the present invention, a cured coating film that is more curable, less scratched, and more solvent resistant can be obtained. Can be formed.

In the present invention, it is very important that the curable quaternary ammonium salt (A) is a cationic compound having a quaternary ammonium salt structure (hereinafter sometimes referred to as a quaternary amino group).
Initially, it was considered that if the composition for forming a coating film contains a compound having a fatty acid ester structure, fingerprint resistance can be imparted to the cured coating film. And considering that the fingerprint mark and sebum components have a carboxyl group, the anti-fingerprinting agent is a compound having a fatty acid ester structure and does not have an ionic functional group, or a carboxyl group or its It was thought that those having a so-called anionic functional group such as a derived functional group, a sulfonyl group or a functional group derived therefrom were suitable. In fact, when a compound having a fatty acid ester structure and having no ionic functional group or having an anionic functional group is used, it is easy to wipe off the attached fingerprint and there is no effect that the wiping traces are not noticeable. can get.
However, even with such a compound that has an excellent effect on fingerprint marks, it has not been possible to impart dust removability to the cured coating film.

On the other hand, so-called cationic functional groups such as quaternary ammonium salts are expected to attract fingerprint traces and components having carboxyl groups in sebum and fix the fingerprint traces and sebum to the cured coating surface. It was. However, according to the study by the present inventors, contrary to the prediction, in the case of a quaternary ammonium salt compound, it adheres in the same manner as a compound having an anionic functional group as described above or a compound having no ionic functional group. It has been found that the cured coating film has a function of facilitating wiping off the fingerprint marks. The reason and mechanism are still unknown.
Surprisingly, when this quaternary ammonium salt compound is used, dust removal can be further imparted to the cured coating film.
For the above reasons, it is very important that the curable quaternary ammonium salt (A) used in the present invention has a quaternary ammonium salt structure.

Such a curable quaternary ammonium salt (A) is not particularly limited as long as it has a predetermined structure or functional group. For example, a fatty acid ester structure comprising a fatty acid having 6 to 11 carbon atoms and a polyalkylene. With respect to the oxide chain, compounds having the following structure can be exemplified.
(S1) A fatty acid ester formed from at least part of a hydroxyl group of a polyhydric alcohol having no polyalkylene oxide chain (hereinafter also simply referred to as “polyhydric alcohol”) and a fatty acid comprising a fatty acid having 6 to 11 carbon atoms. Construction.
(S2) A structure in which, in (S1) above, the fatty acid having 6 to 11 carbon atoms is a hydroxy acid (hydroxy fatty acid), and at least a part of the polyalkylene oxide chain is ether-bonded to the hydroxyl group of the hydroxy acid.
(S3) A structure in which a polyalkylene oxide chain is ether-bonded to a part of hydroxyl groups of the polyhydric alcohol in the above (S1) (so-called polyether polyol structure).
(S4) A structure in which a polyalkylene oxide chain (polyalkylene glycol) is bonded to at least a part of hydroxyl groups of a polyhydric alcohol having no polyalkylene oxide chain.
(S5) A fatty acid ester structure formed from at least a part of the terminal hydroxyl groups of the polyalkylene oxide chain and a fatty acid having 6 to 11 carbon atoms in (S4) above.
A polyalkylene oxide chain (polyalkylene glycol) is formed from a polyhydric alcohol not having a polyalkylene oxide chain and at least part of a terminal hydroxyl group and a fatty acid having 6 to 11 carbon atoms having a hydroxyl group. Alkylene oxide addition fatty acid ester can also be used like (a3) mentioned later.

The acryloyl group or methacryloyl group and the quaternary ammonium salt structure are not particularly limited. For example, when using a polyhydric alcohol, a hydroxyl group thereof, a terminal hydroxyl group of a polyalkylene oxide chain, and / or a hydroxy fatty acid is used. From the viewpoint of the production method, a structure in which these are introduced via a urethane bond derived from the hydroxyl group thereof can be given as a preferred example.
That is, depending on the type of synthesis raw material and the synthesis method, there are a plurality of different hydroxyl groups derived from a hydroxyl group of a polyhydric alcohol, a terminal hydroxyl group of a polyalkylene oxide chain, and a hydroxyl group derived from a hydroxy fatty acid, and the ester bond of the hydroxyl group By using an ether bond or a urethane bond, curable quaternary ammonium salts (A) having various structures can be obtained.

More specifically, such a curable quaternary ammonium salt (A) can be obtained, for example, by the following method.
In the case of the curable quaternary ammonium salt (A1) having the structure (S1) (and (S2), (S3)), first, a polyvalent oxide having no fatty acid having 6 to 11 carbon atoms and no polyalkylene oxide chain. A fatty acid ester (a1) composed of a fatty acid having 6 to 11 carbon atoms having a hydroxyl group is formed from the alcohol.

  A fatty acid having 6 to 11 carbon atoms is a monovalent carboxylic acid of a long chain hydrocarbon. Furthermore, those having 6 to 11 carbon atoms are preferable from the viewpoint of easy compatibility with fingerprints, ease of handling, and availability. The fatty acid having 6 to 11 carbon atoms may be either saturated or unsaturated, may be linear or branched, and is preferably a hydroxy acid having a hydroxyl group (hydroxy fatty acid). Examples of the fatty acid having 6 to 11 carbon atoms include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, leucine acid, pantoic acid and the like.

  Examples of the polyhydric alcohol used when obtaining a fatty acid ester comprising a fatty acid having a prime number of 6 to 11 include polyhydric alcohols having two hydroxyl groups such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, and triethylene glycol, glycerin, Polyhydric alcohols having 3 hydroxyl groups such as trimethylolpropane, polyhydric alcohols having 4 hydroxyl groups such as pentaerythritol, diglycerin, xylose, sorbitan, etc. Polyhydric alcohol having 6 hydroxyl groups such as monohydric alcohol, sorbitol, malbitol, tetraglycerin, polyglycerin having more than 6 hydroxyl groups, sucrose, trehalol, lactose and other disaccharides, maltoto It can be exemplified 3 saccharides of Orth. These can be used singly or as a mixture of two or more. Among these, glycerin is preferable.

The obtained fatty acid ester (a1) comprising a fatty acid having 6 to 11 carbon atoms preferably has two or more hydroxyl groups in one molecule. The hydroxyl group of the fatty acid ester (a1) comprising a fatty acid having 6 to 11 carbon atoms means both a hydroxyl group derived from a polyhydric alcohol and a hydroxyl group derived from a hydroxy acid when the fatty acid is a hydroxy acid.
If the reaction product of a fatty acid having 6 to 11 carbon atoms and a polyhydric alcohol and having a hydroxyl group is available as a natural product or an industrial product, they can be used as appropriate.

For example, as the fatty acid ester (a1) comprising a fatty acid having 6 to 11 carbon atoms having a hydroxyl group, which is obtained by esterifying a fatty acid having 6 to 11 carbon atoms and glycerin, all three hydroxyl groups of glycerin are esterified. In addition to the glycerin (so-called triglyceride), a part of the hydroxyl group of glycerin is esterified.
When a hydroxy acid is used and reacted with all three hydroxyl groups of glycerin, a fatty acid triglyceride having three or more hydroxyl groups derived from a hydroxy acid is used as the fatty acid ester (a1) composed of the fatty acid having 6 to 11 carbon atoms. Obtainable. Moreover, the fatty acid ester (a1) which consists of a C6-C11 fatty acid which has a hydroxyl group derived from glycerol and a hydroxyl group derived from a hydroxy acid by esterifying a part of three hydroxyl groups of glycerol using a hydroxy acid. Can be obtained. Furthermore, as a fatty acid having 6 to 11 carbon atoms, a fatty acid having no hydroxyl group is used, and one of the three hydroxyl groups of glycerin is esterified with a fatty acid, whereby 6 to 11 carbon atoms having two hydroxyl groups derived from glycerin. It is also possible to obtain a fatty acid ester (a1) comprising the above fatty acid.

  As the fatty acid ester (a1) composed of a fatty acid having 6 to 11 carbon atoms, a fatty acid ester having two or more hydroxyl groups (the hydroxyl group is derived from a polyhydric alcohol and / or a hydroxy acid) is used. To a polyalkylene oxide-added fatty acid ester (a3-1) having a terminal hydroxyl group derived from two or more polyalkylene oxides, for example, by adding an alkylene oxide to all the hydroxyl groups in the fatty acid ester consisting of 11 to 11 fatty acids. Can be synthesized.

  Alternatively, a terminal hydroxyl group derived from polyalkylene oxide and a fatty acid having 6 to 11 carbon atoms can be obtained by adding alkylene oxide to a part of the hydroxyl group of a fatty acid ester (a1) comprising a fatty acid having 6 to 11 carbon atoms having a plurality of hydroxyl groups. It is also possible to synthesize a polyalkylene oxide-added fatty acid ester (a3-1) having a hydroxyl group derived from the fatty acid ester (a1).

Specific structural examples of these polyalkylene oxide-added fatty acid esters (a3-1) are shown as image diagrams below.
Formula 1 below is an example in which glycerin is used as the polyhydric alcohol and hydroxy acid is used as the fatty acid having 6 to 11 carbon atoms (R ¹ represents a portion obtained by removing COOH and OH from the hydroxy acid. , B and c represent the number of moles of alkylene oxide chain added.)

Formula 2 below is an example in which glycerin is used as the polyhydric alcohol and a fatty acid having 6 to 11 carbon atoms having no hydroxyl group is used as the fatty acid (R ³ represents a portion obtained by removing COOH from a fatty acid having no hydroxyl group. B and c represent the number of added moles of the alkylene oxide chain).

  Furthermore, an alkylene oxide is added to a fatty acid ester (a1) composed of a fatty acid having 6 to 11 carbon atoms having only one hydroxyl group, and a polyalkylene oxide-added fatty acid ester containing a terminal hydroxyl group derived from one polyalkylene oxide ( a3-1) can also be synthesized. However, from the viewpoint of imparting a further functional group such as a polymerizable functional group, the fatty acid ester (a3-1) composed of a fatty acid having 6 to 11 carbon atoms has a plurality of hydroxyl groups (regardless of origin). It is preferable that it contains.

  As the alkylene oxide, those having 2 to 4 carbon atoms are preferable, and ethylene oxide is particularly preferable. It is also preferable to use a combination of a plurality of types of alkylene oxides such as ethylene oxide and propylene oxide for the synthesis.

  Instead of alkylene oxide, a compound having a hydroxyl group and a polyalkylene oxide chain, for example, polyalkylene glycol may be reacted. In this case, the alkylene chain preferably has 2 to 4 carbon atoms. Examples thereof include a diol having a polyethylene oxide chain, a diol having a polypropylene oxide chain, and a diol having an ethylene oxide chain and a propylene oxide chain. A diol having a polyethylene oxide chain and a diol having a polypropylene oxide chain can be used in combination. Further, the compound having a hydroxyl group and a polyalkylene oxide chain may have one hydroxyl group, and examples thereof include a structure in which one hydroxyl group of the diol as described above is sealed with a monoalkyl alcohol. be able to.

  The number of moles of alkylene oxide added in the polyalkylene oxide-added fatty acid ester (a3-1) is preferably 2 to 30 per one hydroxyl group of the fatty acid ester (a1) comprising a fatty acid having 6 to 11 carbon atoms, More preferably, it is 5-20. When the added mole number of the alkylene oxide chain is small, the transparency of the cured coating film tends to be lowered. On the other hand, if the number of added moles of the alkylene oxide chain is too large, the hydrophilicity becomes strong and the fingerprint mark erasing performance may be lowered.

  The number of moles of alkylene oxide added in the polyalkylene oxide-added fatty acid ester (a3-1) having two or more hydroxyl groups is preferably 6 to 90 in total per molecule, and more preferably 15 to 60. Preferably, it is 20-50. If the added mole number of the alkylene oxide chain is small, the transparency of the cured coating film tends to be lowered. If the added mole number of the alkylene oxide chain is too large, the fingerprint mark erasing performance may be lowered.

Next, an example of a synthesis method when the curable quaternary ammonium salt (A) is the curable quaternary ammonium salt (A2) having the structures (S4) and (S5) will be described. Here, the description which overlaps with the case of the said curable quaternary ammonium salt (A1), such as an illustration of a specific compound, shall be omitted.
For example, an alkylene oxide is added to a hydroxyl group of a polyhydric alcohol not having a polyalkylene oxide chain to synthesize a polyol (a2) to which a polyalkylene oxide is added. A polyalkylene oxide-added fatty acid ester having a hydroxyl group by reacting at least a part of the hydroxyl group of the polyalkylene oxide-added polyol (a2) (a hydroxyl group derived from a polyhydric alcohol and / or a terminal hydroxyl group of a polyalkylene glycol) with a fatty acid ( a3-2) is synthesized. The hydroxyl group of the polyalkylene oxide-added fatty acid ester (a3-2) may be any of a hydroxyl group derived from a polyhydric alcohol, a hydroxyl group derived from a polyalkylene oxide, or a hydroxyl group derived from a hydroxy acid.

A specific structural example of this polyalkylene oxide-added fatty acid ester (a3-2) is shown as an image diagram below.
Formula 3 below is an example in which glycerin is used as the polyhydric alcohol and hydroxy acid is used as the fatty acid (R ² represents a portion obtained by removing COOH and OH from the hydroxy acid. A, b, and c are Indicates the number of added moles of alkylene oxide chain.)

That is, when a polyhydric alcohol having no polyalkylene oxide chain (hereinafter referred to as glycerin as a representative compound) is reacted with alkylene oxide (or polyalkylene glycol), when all the hydroxyl groups of glycerin are reacted, Certain ether compounds may have terminal hydroxyl groups derived from polyalkylene oxide.
When all the hydroxyl groups in such an ether compound are reacted with a fatty acid as described above, a structure in which alkylene oxide is added to a hydroxyl group derived from glycerin (S4), an ester structure of a terminal hydroxyl group derived from polyalkylene oxide and a fatty acid ( A compound having S5) is obtained.
Alternatively, when a part of the hydroxyl group in the ether compound as described above having the structure (S4) is reacted with a fatty acid to leave a part, a structure (S4) in which an alkylene oxide is added to the hydroxyl group derived from glycerin, A compound having an ester structure (S5) of a terminal hydroxyl group derived from polyalkylene oxide and a fatty acid and a terminal hydroxyl group derived from polyalkylene oxide is obtained.

Alternatively, when a polyhydric alcohol having no polyalkylene oxide chain (hereinafter, glycerin as a representative compound) is reacted with alkylene oxide (or polyalkylene glycol), a part of the hydroxyl group of glycerin is reacted to leave a part. In this case, the ether compound as a reaction product may have a hydroxyl group derived from glycerin and a terminal hydroxyl group derived from polyalkylene oxide.
When a hydroxyl group in such an ether compound is reacted with a fatty acid as described above, a structure in which an alkylene oxide is added to a hydroxyl group derived from glycerin (S4), an ester structure of a terminal hydroxyl group derived from a polyalkylene oxide and a fatty acid (S5) In addition, it may have an ester structure (the same structure as (S1) above) of a hydroxyl group derived from glycerin and a fatty acid.

Another specific structural example of the polyalkylene oxide-added fatty acid ester (a3-2) is shown as an image diagram below.
Formula 4 below is an example in which glycerin is used as the polyhydric alcohol and a fatty acid having no hydroxyl group is used as the fatty acid (R ⁴ represents a portion obtained by removing COOH from a fatty acid having no hydroxyl group. A, b , C represents the number of moles of alkylene oxide chain added).

Next, an example of introduction of a tertiary amino group for forming a quaternary ammonium salt structure with an acryloyl group or a methacryloyl group will be described.
Compound (a4) having a acryloyl group or a methacryloyl group and an isocyanate group, and a tertiary amino group, using the polyalkylene oxide-added fatty acid ester (a3-1) or (a3-2) and at least a part of the hydroxyl groups. By reacting with an isocyanate group of the compound (a5) having an isocyanate group, a polyalkylene oxide addition compound (a6) having an acryloyl group or a methacryloyl group and having a tertiary amino group can be synthesized. . It is preferable to react all the hydroxyl groups of the polyalkylene oxide-added fatty acid ester (a3-1) or (a3-2) with the compounds (a4) and (a5) having the isocyanate group. Thereby, these functional groups can be introduced into the curable quaternary ammonium salt (A) via the urethane bond.

  Any one of the isocyanate group-containing compounds (a4) and (a5) may be reacted first with the polyalkylene oxide-added fatty acid ester (a3-1) or (a3-2), or both may be reacted simultaneously. You can also. Among them, the compound (a5) having a tertiary amino group and an isocyanate group is reacted with a part of the hydroxyl groups of the polyalkylene oxide-added fatty acid ester (a3-1) or (a3-2), and at least the remaining hydroxyl groups are reacted. It is preferable to react the compound (a4) partially having the acryloyl group or methacryloyl group and an isocyanate group.

  When a compound having one acryloyl group or one methacryloyl group and one isocyanate group is used as the compound (a4) having an acryloyl group or methacryloyl group and an isocyanate group, for example, the polyalkylene oxide-added fatty acid ester (a3 -1) or (a3-2) is a compound having three hydroxyl groups, the average number of hydroxyl groups by reacting more than 1/3 of the total number of hydroxyl groups with an isocyanate group in the compound (a4) The above polyalkylene oxide addition compound (a6) having more than one (meth) acryloyl group in one molecule can be obtained.

When the compound (a4) having an acryloyl group or methacryloyl group and an isocyanate group is one having one isocyanate group and two or more acryloyl groups or methacryloyl groups, for example, the above polyalkylene oxide-added fatty acid ester In the case where (a3-1) or (a3-2) is a compound having three hydroxyl groups, the hydroxyl group of at least 1/3 of the total amount of the hydroxyl groups is reacted with an isocyanate group in the compound (a4) to obtain an average. Thus, more than one acryloyl group or methacryloyl group can be introduced in one molecule.
Formed from the curable composition of the present invention by using the curable quaternary ammonium salt (A) obtained from the polyalkylene oxide addition compound (a6) having an average of more than one acryloyl group or methacryloyl group. It is possible to improve the scratch resistance and solvent resistance of the cured coating film.

  The compound (a4) having an acryloyl group or methacryloyl group and an isocyanate group does not have a tertiary amino group, and preferably has one isocyanate group. As such compound (a4), for example, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloylmethyl) ethyl isocyanate and the like can be used.

  As the compound (a5) having a tertiary amino group and an isocyanate group, those having one isocyanate group are preferable. Such a compound (a5) is, for example, a compound having one tertiary amino group and one hydroxyl group, a compound having two isocyanate groups, and the condition that the amount of isocyanate groups is twice the amount of hydroxyl groups. It can be obtained by reacting below.

  Examples of the compound having one tertiary amino group and one hydroxyl group include 2-dimethylaminoethanol, 2-dimethylamino-1-propanol, 3-dimethylamino-1-propanol, 1-dimethylamino-2-propanol, N -Methyl-N-ethylethanolamine, 2-diethylaminoethanol, 3-dimethylamino-1-butanol, 3-dimethylamino-2-butanol, N-methyl-N-isopropylethanolamine, N-methyl-N-ethyl- 3-amino-1-propanol, 4-dimethylamino-1-butanol, 4-dimethylamino-1-butanol, 3-dimethylamino-2-methyl-1-propanol, 1-dimethylamino-2-methyl-2- Propanol, 2-dimethylamino-1-butanol and 2-dimethyla Roh-2-methyl-1-propanol, and the like. These can be used alone or in admixture of two or more.

  Examples of the compound having two isocyanate groups include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-naphthalene diisocyanate, lysine diisocyanate, water. Examples include 4,4′-diphenylmethane diisocyanate and hydrogenated tolylene diisocyanate. These may be used alone or in admixture of two or more.

  Finally, an acryloyl group or methacryloyl group and a tertiary amino group obtained by reacting the polyalkylene oxide-added fatty acid ester (a3-1) or (a3-2) with the compounds (a4) and (a5) Is reacted with a compound (a7) capable of reacting with a tertiary amino group to form a salt.

  Examples of the compound (a7) used for quaternizing the tertiary amino group in the polyalkylene oxide addition compound (a6) include various halides such as alkylbenzyl chloride, benzyl chloride, alkyl chloride, and alkyl bromide, Examples thereof include alkyl sulfates such as dimethyl sulfate, diethyl sulfate and dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate and methyl benzenesulfonate, and alkyl phosphates such as trimethyl phosphite.

Through the above steps, a curable quaternary ammonium salt (A1) using the polyalkylene oxide-added fatty acid ester (a3-1) and a curable quaternary ammonium salt using the polyalkylene oxide-added fatty acid ester (a3-2) ( A2) can be obtained.
That is, the active energy ray-curable quaternary ammonium salt (A1) has the above structure (S1), and has, for example, a fatty acid ester structure formed from a fatty acid composed of 6 to 11 fatty acids and a polyhydric alcohol. It is a quaternary ammonium salt having at least (which may further have other fatty acid ester structure), a polyalkylene oxide chain, a urethane bond, and an acryloyl group or a methacryloyl group.

  The active energy ray-curable quaternary ammonium salt (A2) has the above structures (S4) and (S5). For example, a polyalkylene oxide chain bonded to at least a part of hydroxyl groups of a polyhydric alcohol, At least a fatty acid ester structure formed from a terminal hydroxyl group of at least a part of the polyalkylene oxide chain and a fatty acid composed of 6 to 11 fatty acids (may further have other fatty acid ester structures), urethane It is a quaternary ammonium salt having a bond and an acryloyl group or a methacryloyl group.

A preferred method for producing the curable quaternary ammonium salt (A1) includes the following steps.
(1) A step of synthesizing a fatty acid ester (a1) having a hydroxyl group by esterifying a fatty acid comprising 6 to 11 fatty acids and a polyhydric alcohol;
(2) a step of synthesizing a polyalkylene oxide-added fatty acid ester (a3-1) having a hydroxyl group by adding an alkylene oxide to the hydroxyl group of the fatty acid ester (a1) comprising the fatty acids 6 to 11;
(3) The compound (a4) having an acryloyl group or a methacryloyl group and an isocyanate group and a tertiary amino group and an isocyanate group at least part of the hydroxyl groups in the polyalkylene oxide-added fatty acid ester (a3-1) A step of reacting each with compound (a5) to synthesize a polyalkylene oxide addition compound (a6) having an acryloyl group or a methacryloyl group and a tertiary amino group; and (4) the polyalkylene oxide addition compound (a6) Reacting with a compound (a7) capable of reacting with a tertiary amino group to form a salt to form a quaternary ammonium salt of the polyalkylene oxide addition compound (a6).

A preferred method for producing the curable quaternary ammonium salt (A2) includes the following steps.
(1) A step of synthesizing a polyalkylene oxide-added polyol (a2) by adding an alkylene oxide to a polyhydric alcohol;
(2) The hydroxyl group of the polyalkylene oxide-added polyol (a2) and a fatty acid composed of a fatty acid having 6 to 11 carbon atoms are esterified to synthesize a polyalkylene oxide-added fatty acid ester (a3-2) having a hydroxyl group. Process;
(3) At least part of the hydroxyl group in the polyalkylene oxide-added fatty acid ester (a3-2) has a compound (a4) having an acryloyl group or a methacryloyl group and an isocyanate group, and a tertiary amino group and an isocyanate group. A step of reacting each with compound (a5) to synthesize a polyalkylene oxide addition compound (a6) having an acryloyl group or a methacryloyl group and a tertiary amino group; and (4) the polyalkylene oxide addition compound (a6) Reacting with a compound (a7) capable of reacting with a tertiary amino group to form a salt to form a quaternary ammonium salt of the polyalkylene oxide addition compound (a6).

The curable composition according to the present invention comprises at least one active energy ray-curable quaternary ammonium salt (A) and a different active energy ray-curable compound (B) (hereinafter simply referred to as “curability”). 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. The curable compound (B) may be used in combination of a plurality of compounds as exemplified below.

Among the curable compounds (B), specific examples of polyfunctional compounds include dimethylol tricyclodecane diacrylate, (ethoxylated) bisphenol A diacrylate, (propoxylated) bisphenol A diacrylate, and cyclohexane di. Methanol diacrylate, (poly) ethylene glycol diacrylate, (ethoxylated) 1,6-hexanediol diacrylate, (propoxylated) 1,6-hexanediol diacrylate, (ethoxylated) neopentyl glycol diacrylate, (propoxy) ) Neopentyl glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethy Propanetri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acryloxyethyl) isocyanurate, Trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified di Pentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate DOO, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 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, poly (meth) acrylates such as polyurethane poly (meth) acrylate having 6 or more functional groups and polyepoxy poly (meth) acrylate, In addition, polyfunctional acrylates having 4 or more acryloyl groups in the molecule can be preferably used.

  Polyepoxy poly (meth) acrylate is, for example, a (meth) acryloyl group introduced by reacting an epoxy group of an epoxy resin with a carboxyl group of (meth) acrylic acid, and (meth) acrylic acid of a novolac type epoxy resin. Additives can be mentioned.

  Polyurethane poly (meth) acrylate is obtained, for example, by reacting polyisocyanate with (meth) acrylate having a hydroxyl group, containing an isocyanate group obtained by reacting polyol and polyisocyanate under the condition of excess isocyanate group. Some are obtained by reacting a urethane prepolymer 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 the (meth) acrylates having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, (meth) acryloyl isocyanate, and the like.

  The curable composition according to the present invention preferably contains the curable quaternary ammonium salt (A) in a range of 0.1 to 15 parts by mass 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 effects of fingerprint resistance and dust removal may be insufficient. If the amount exceeds 15 parts by mass, the toughness, scratch resistance, solvent resistance, adhesion, etc. as a cured coating film may be reduced. The basic performance may be impaired.

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. 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 of the curable quaternary ammonium salt (A), the curable compound (B) and the fine particles is 100. It is preferable that 0.1-70 mass% is contained in the mass%, and 20-60 mass% is more preferable. 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-trimethylbenzoin diphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like. These photopolymerization initiators can be used alone. Two or more types may be used in combination.

  These photoinitiators are the above-mentioned active energy ray-curable quaternary ammonium salt (A), active energy ray-curable compound (B), and photopolymerization initiator from the viewpoint of ensuring an appropriate crosslinking density and hard coat property. It is preferable that 0.1-20 mass% is contained in 100 mass% in total, 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 solvent 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 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, a 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 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 and dust removability.

  The member with a cured coating film according to the present invention obtained as described above can be suitably used for a surface member for display of a touch panel. As a touch panel method, a resistive film type touch panel is generally used. A touch-side transparent plastic substrate in which a transparent conductive thin film such as a tin-doped indium oxide (ITO) film is laminated on one side of a transparent plastic substrate, and glass or the like. A typical structure is a display-side transparent substrate in which a transparent conductive thin film such as an ITO film is laminated on one side of a transparent base material, and is opposed to each other so that the transparent conductive thin films face each other via an insulating spacer. Input is performed by pressing the touch input surface of the touch-side transparent plastic substrate with a pen or a finger, and bringing the transparent conductive thin film on the touch-panel side transparent plastic substrate into contact with the transparent conductive thin film on the display-side transparent substrate. The member with a cured coating film according to the present invention is preferably used on the touch input surface side as a display surface member.

  Specific examples of other touch panel methods include an ultrasonic method, a capacitance method, an electric strain method, a magnetostriction method, an infrared method, an electromagnetic induction method, and the like. The member with a film can be used for any system and is not particularly limited.

  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.

<Synthesis of isocyanate group-added amine>
(Synthesis Example 1)
A flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube was charged with 111.1 parts of isophorone diisocyanate, and 44.6 of N, N-dimethylaminoethanol was stirred while stirring at a temperature of 90 ° C. under a nitrogen stream. Part (isocyanate group: hydroxyl group = 2 mol: 1 mol) was added dropwise, and reacted at a temperature of 90 ° C. for 5 hours after completion of the addition. After completion of the reaction, an isocyanate group-added amine compound was obtained by cooling to room temperature.

<Synthesis of polyalkylene oxide-added fatty acid ester>
(Synthesis Example 2)
A flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube was charged with 185 parts of glycerin, 345 parts of capric acid, and 2.6 parts of sodium hydroxide, and the reaction system was sufficiently nitrogenized under a nitrogen stream. Substitution and heating were carried out for 5 hours while distilling off water at a temperature of 220 ° C. After the reaction, the catalyst was removed by filtration to synthesize capric acid monoglyceride. 480 parts of the resulting capric acid monoglyceride and 0.45 part of potassium hydroxide were charged into an autoclave, dehydrated under reduced pressure at 110 ° C. and 30 torr for 1 hour, and then added for 2.5 hours while injecting 885 parts of ethylene oxide at 155 ° C. Reaction was performed, and the mixture was cooled to 110 to 120 ° C., neutralized with a 50% aqueous citric acid solution, and precoated with diatomaceous earth. It exhibits the structure of Formula 2 above).

(Synthesis Example 3)
A flask similar to Synthesis Example 1 was charged with 185 parts of glycerin, 235 parts of caproic acid, and 2.6 parts of sodium hydroxide. The reaction system was sufficiently purged with nitrogen under a nitrogen stream, heated and heated to a temperature of 220 ° C. An ester reaction was carried out for 5 hours while distilling off water, and after the reaction, the catalyst was removed by filtration to synthesize caproic acid monoglyceride. 380 parts of the obtained caproic acid monoglyceride and 0.45 part of potassium hydroxide were charged into an autoclave, dehydrated under reduced pressure at 110 ° C. and 30 torr for 1 hour, and then added for 2.5 hours while injecting 885 parts of ethylene oxide at 155 ° C. The reaction was performed, and the mixture was cooled to 110 to 120 ° C., neutralized with a 50% aqueous citric acid solution, and precoated through diatomaceous earth, and an average addition of 10 mol of polyoxyethylenecaproic acid monoglyceride compound (C-2) was obtained. It exhibits the structure of Formula 2 above).

<Synthesis of active energy ray-curable quaternary ammonium salt>
(Synthesis Example 4)
In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube, the polyoxyethylene capric acid monoglyceride compound (C-1) obtained in Synthesis Example 2 (hydroxyl group: 2; average addition of ethylene oxide 10) Mol) 68.8 parts were charged, and 31.1 parts of the isocyanate group-added amine obtained in Synthesis 1 was added dropwise while blowing air at a temperature of 70 ° C., and stirring was maintained at 70 ° C. for 2 hours after completion of the addition. did. Thereafter, 23.9 parts of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: “Karenz BEI”, manufactured by Showa Denko KK) was added dropwise, and stirring was maintained for 3 hours after the completion of the dropwise addition. Next, after cooling the system to a temperature of 60 ° C., 10.9 parts of methyl chloroacetate was added dropwise, and stirring was maintained at a temperature of 60 ° C. for 3 hours after completion of the dropwise addition. After completion of the reaction, the mixture was cooled to room temperature to obtain compound (A-1).
The molar ratio of the hydroxyl group of the polyoxyethylene capric acid monoglyceride compound (C-1), the isocyanate group derived from the isocyanate-added amine and the isocyanate group of 1,1-bis (acryloyloxymethyl) ethyl isocyanate is hydroxyl group: isocyanate group. (Derived from amine): Isocyanate group (derived from 1,1-bis (acryloyloxymethyl) ethyl isocyanate) = 2 mol: 1 mol: 1 mol, and the average number of acryloyl groups in compound (A-1) of Synthesis Example 4 Is two.

(Synthesis Example 5)
The polyoxyethylene caproic acid monoglyceride compound (C-1) used in Synthesis Example 4 was used in place of the polyoxyethylene caproic acid monoglyceride compound (C-2) obtained in Synthesis Example 3 except that 63.2 parts were used. The same operation as in Synthesis Example 1 was performed to obtain compound (A-2).
In addition, the molar ratio of the hydroxyl group derived from the polyoxyethylene caproic acid monoglyceride compound (C-2), the isocyanate group derived from the isocyanate group-added amine and the isocyanate group derived from 1,1-bis (acryloyloxymethyl) ethyl isocyanate is a hydroxyl group: Isocyanate group (derived from amine): Isocyanate group (derived from 1,1-bis (acryloyloxymethyl) ethyl isocyanate) = 2 mol: 1 mol: 1 mol of the acryloyl group of compound (A-2) of Synthesis Example 5 The average number is two.

(Synthesis Example 6)
A compound (A-3) was obtained in the same manner as in Synthesis Example 1, except that 12.7 parts of benzyl chloride was used instead of methyl chloroacetate used in Synthesis Example 1.

(Synthesis Example 7)
In the same manner as in Synthesis Example 1, without using the isocyanate group-added amine obtained in Synthesis 1, the polyoxyethylene capric acid monoglyceride compound (C-1) obtained in Synthesis Example 2 (hydroxyl group: 2) In addition, 13.8 parts of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: “Karenz BEI”, manufactured by Showa Denko KK) was added dropwise to 68.8 parts of ethylene oxide with an average addition of 10 mol). A compound (A-4) containing no quaternary ammonium salt was obtained.
The molar ratio of the hydroxyl group of the polyoxyethylene capric acid monoglyceride compound (C-1), the isocyanate group derived from the isocyanate-added amine and the isocyanate group of 1,1-bis (acryloyloxymethyl) ethyl isocyanate is hydroxyl group: isocyanate group. (Derived from amine): Isocyanate group (derived from 1,1-bis (acryloyloxymethyl) ethyl isocyanate) = 2 mol: 0 mol: 1 mol, and the average number of acryloyl groups in compound (A-4) of Synthesis Example 7 Is two.

Example 1
5 parts of compound (A-1) synthesized in Synthesis Example 1 for 100 parts of pentaerythritol triacrylate (trade name: “Aronix M305” manufactured by Toagosei Co., Ltd.) as the active energy ray-curable compound (B) As a polymerization initiator, 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 having a nonvolatile content of 50% (also referred to as a coating composition or a coating solution).
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 2-3)
Curing was carried out in the same manner as in Example 1 except that instead of the compound (A-1) synthesized in Synthesis Example 4, the compounds (A-2) to (A-3) synthesized in Synthesis Examples 4 to 5 were changed. A substrate with a coating film was obtained.

Example 4
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 4 was not used.

(Comparative Example 2)
Example 1 except that the polyoxyethylene capric acid monoglyceride compound (C-1) having an average addition of 10 moles of ethylene oxide synthesized in Synthesis Example 2 was used instead of the compound (A-1) synthesized in Synthesis Example 4. In the same manner, a substrate with a cured coating film was obtained.

(Comparative Example 3)
A substrate with a cured coating film was obtained in the same manner as in Example 1 except that the compound (A-4) synthesized in Synthesis Example 7 was used instead of the compound (A-1) synthesized in Synthesis Example 4. .

(Comparative Example 4)
Instead of the compound (A-1) synthesized in Synthesis Example 4, a leveling agent containing a dimethylsiloxane skeleton (trade name: “BYK-UV3500” manufactured by Big Chemie Japan) was used, as in Example 1. Thus, a substrate with a cured coating film was obtained.

(Comparative Example 5)
In place of the compound (A-1) synthesized in Synthesis Example 4 except that it is changed to polyoxyethylene alkylphenyl ether containing one vinyl group (trade name: “AQUALON RN-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Obtained a base material with a cured coating film in the same manner as in Example 1.

(Comparative Example 6)
Example 1 was used except that polyoxypropylenemethyldiethylammonium chloride (trade name: “ADEKA COAL CC-36” manufactured by Asahi Denka Kogyo Co., Ltd.) was used instead of the compound (A-1) synthesized in Synthesis Example 4. Similarly, a substrate with a cured coating film was obtained.

  About the base material with a cured coating film of Examples 1-4 and Comparative Examples 1-6, the following physical-property evaluation was performed and the result was put together in Table 1.

(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.

(Dust wipeability)
Tissue paper (trade name: Kleenextesh, manufactured by Crecia Co., Ltd.) is folded in pairs, and the cured coating surface of the cured coating of the substrate with a cured coating is rubbed 10 times with this four-fold tissue paper, and then On the cured coating film, the four-fold tissue paper was torn 5 times in a non-contact state, and pseudo dust was dropped on the cured coating film surface. Next, a new tissue paper (of the same type as described above) is folded in four, and the pseudo dust on the cured coating surface is wiped with the four-fold tissue paper, and the degree of removal of the pseudo dust is visually determined. In addition, evaluation A and evaluation B have the performance which does not have trouble in practical use.
A: Simulated dust can be wiped off with quadruped tissue paper.
B: The pseudo dust can be almost wiped off with the four-fold tissue paper, but remains slightly.
C: Pseudo dust cannot be wiped off with quadruped tissue paper and remains almost.

(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 of Table 1, the substrate with a cured coating film using the curable compositions of Examples 1 to 3 is excellent in good balance of fingerprint wiping property, dust wiping property, scratch resistance, pencil hardness, solvent resistance, and the like. Turned out to be. 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 4 using a curable composition containing fine particles can obtain a relatively large haze value of 6.5% without significantly reducing the total light transmittance. did it. 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, in Comparative Example 1 containing no curable quaternary ammonium salt (A), the hard coat property of the cured coating film was good, but neither fingerprint wiping property nor dust wiping property was exhibited.
In Comparative Example 2 containing a fatty acid ester, the fingerprint wiping property was better than that 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. Furthermore, since the fatty acid ester used was not a quaternary ammonium salt, the dust wiping property was also poor.

  Comparative Example 3 is an example in which a compound having a fatty acid ester structure and an acryloyl group but not a quaternary ammonium salt is used, and the cured film has good fingerprint wiping property, solvent resistance, and scratch resistance, Since it is not a quaternary ammonium salt, the dust wiping property was insufficient.

  Comparative Example 4 is an example containing a compound which has a plurality of (meth) acryloyl groups and a dimethylsiloxane skeleton but does not have a fatty acid ester structure and is not a quaternary ammonium salt. In Comparative Example 4, when the fingerprint wiping test of the cured coating film was performed, the wiping marks looked cloudy and became more noticeable than before wiping, and the dust wiping property was insufficient.

  Comparative Example 5 is an example using a compound having a vinyl group instead of a (meth) acryloyl group, and contains a fatty acid ester having no curable functional group since it has a functional group responsible for the active energy ray curing function. Compared to Comparative Example 2, the solvent resistance of the cured coating film was better, and the fingerprint wiping performance after solvent treatment was maintained. However, since the vinyl group is less reactive than the (meth) acryloyl group, the vinyl group has scratches in the scratch resistance test, and the hard coat property is insufficient.

  Comparative Example 6 was an example using polyoxypropylene methyldiethylammonium chloride which is a quaternary ammonium salt, and the dust wiping property of the cured coating film was good. However, since it does not have a fatty acid ester structure, it does not exhibit a fingerprint wiping function, and since it does not have a functional group responsible for the active energy ray curing function, there are scratches in the scratch resistance test, and the hard coat property is insufficient. The solvent resistance was not satisfactory.

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

Claims (12)

An active energy ray-curable quaternary ammonium salt (A) having a fatty acid ester structure comprising a fatty acid having 6 to 11 carbon atoms, a polyalkylene oxide chain, and an acryloyl group or a methacryloyl group;
An active energy ray-curable compound (B) different from the active energy ray-curable quaternary ammonium salt (A);
An active energy ray-curable composition containing   The fatty acid ester structure consisting of a fatty acid having 6 to 11 carbon atoms of the active energy ray-curable quaternary ammonium salt (A) and the polyalkylene oxide chain are composed of a polyhydric alcohol having no polyalkylene oxide chain and a carbon atom having 6 to 11 carbon atoms. The active energy ray-curable composition according to claim 1, which is present as a polyalkylene oxide-added fatty acid ester (a3) having a hydroxyl group, which is composed of a fatty acid composed of a fatty acid and an alkylene oxide.   The active energy ray-curable composition according to claim 2, wherein the polyhydric alcohol having no polyalkylene oxide chain is glycerin.   The active energy ray-curable quaternary ammonium salt (A) has an acryloyl group or a methacryloyl group and a quaternary ammonium salt structure via a urethane bond derived from the hydroxyl group of the polyalkylene oxide-added fatty acid ester (a3) having the hydroxyl group. The active energy ray-curable composition according to claim 2 or 3, wherein   The urethane bond comprises at least part of the hydroxyl group of the polyalkylene oxide-added fatty acid ester (a3) having a hydroxyl group, a compound (a4) having an acryloyl group or a methacryloyl group and an isocyanate group, and a tertiary amino group and an isocyanate group. The active energy ray-curable composition according to claim 4, wherein the active energy ray-curable composition is formed by reacting with the compound (a5).   The polyalkylene oxide-added fatty acid ester (a3) having a hydroxyl group is a hydroxyl group formed from at least a part of a hydroxyl group of a polyhydric alcohol not having a polyalkylene oxide chain and a fatty acid composed of a fatty acid having 6 to 11 carbon atoms. The active energy ray-curable composition according to any one of claims 2 to 5, which is a polyalkylene oxide-added fatty acid ester (a3-1) having a hydroxyl group, wherein an alkylene oxide is added to the hydroxyl group of the fatty acid ester. object.   The active energy ray-curable composition according to claim 6, wherein the fatty acid comprising the fatty acid having 6 to 11 carbon atoms is a hydroxy acid, and at least a part of the polyalkylene oxide chain is bonded to a hydroxyl group of the hydroxy acid.   The polyalkylene oxide-added fatty acid ester (a3) having a hydroxyl group is a fatty acid comprising a polyalkylene oxide-added polyol (a2) obtained by adding an alkylene oxide to a polyhydric alcohol not having a polyalkylene oxide chain and a fatty acid having 6 to 11 carbon atoms. The active energy ray-curable composition according to any one of claims 2 to 5, which is a polyalkylene oxide-added fatty acid ester (a3-2) having a hydroxyl group, formed from   The active energy ray-curable quaternary ammonium salt (A) has an average of more than one acryloyl group or methacryloyl group in one molecule, according to any one of claims 1 to 8. An active energy ray-curable composition.   The active energy ray-curable composition according to any one of claims 1 to 9, 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 10, 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 11 is provided on at least a part of at least one member selected from glass, plastic, metal, and paper. A member with a cured coating film.