JP5540745B2 - Active energy ray-curable composition - Google Patents

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.

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).

JP 2004-114355 A JP 2005-186484 A

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.

  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. It is an object of the present invention to provide an active energy ray-curable composition capable of forming a cured coating film that is not easily attacked.

That is, the present invention relates to an active energy ray-curable compound (A) having a fatty acid amide structure composed of a fatty acid having 6 or more carbon atoms, an alkylene oxide structure, and an acryloyl group or a methacryloyl group,
An active energy ray-curable compound (B) different from the active energy ray-curable compound (A);
An active energy ray-curable composition containing

The fatty acid amide structure of the active energy ray-curable compound (A) is formed by reacting a fatty acid (a1) having 12 to 24 carbon atoms with a primary or secondary amine (a2) having a hydroxyl group. Is preferred,
The active energy ray-curable compound (A) has an acryloyl group or a methacryloyl group introduced through a urethane bond derived from the hydroxyl group of the primary or secondary amine (a2) having the hydroxyl group. Is preferred,
In addition, the urethane bond reacts at least a part of the hydroxyl groups derived from the primary or secondary amine (a2) having a hydroxyl group with the compound (a3) having an acryloyl group or a methacryloyl group and an isocyanate group. Preferably formed by
The alkylene oxide structure is formed by a reaction between a hydroxyl group-derived primary or secondary amine (a2) -derived hydroxyl group and an isocyanate group-containing compound (a3), or a fatty acid (a1 ) And a primary or secondary amine (a2) having a hydroxyl group, an alkylene oxide chain added to the hydroxyl group derived from the primary or secondary amine (a2) having a hydroxyl group in the fatty acid amide generated by the reaction of the hydroxyl group. It is preferable that
Moreover, it is preferable that the hydroxyl group of the amine (a2) having a hydroxyl group is two,
The active energy ray-curable compound (A) preferably has more than one acryloyl group or methacryloyl group in one molecule on average,
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 composition (A) of the present invention is an active energy ray-curable compound (A) having a fatty acid amide structure, an alkylene oxide chain (including a polyalkylene oxide chain), and an acryloyl group or a methacryloyl group. Therefore, it is possible to form a cured coating film that is excellent in transparency, fingerprints are not conspicuous, are not easily scratched, and are not easily affected by organic solvents.

  The active energy ray-curable compound (hereinafter simply referred to as “curable compound”) (A) used in the present invention will be described. This curable compound (A) is a compound having a fatty acid amide structure having 6 or more carbon atoms, an alkylene oxide chain, and an acryloyl group or a methacryloyl group, and imparts good fingerprint erasability to a cured coating film. That is, it functions as an anti-fingerprinting 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 compound (A), the fatty acid amide structure having 6 or more carbon atoms and the alkylene 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 inventor considered that 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. Obtaining the above knowledge, the inventor further studied a means for making the boundary line with the surrounding cured coating film inconspicuous by reducing the height of the attached fingerprint trace as much as possible, and realizing the effect of the present invention. It came to.
The fatty acid amide structure having 6 or more carbon atoms and the alkylene 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 compound (A) having both structures tend to wet and spread on the cured coating film surface, and the height tends to be low. Therefore, it is considered that there is an effect that the attached fingerprint marks are not noticeable. 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.

Such a curable compound (A) has a predetermined structure or a functional group, is excellent in transparency, is hard to notice fingerprints, is not easily damaged, and is not easily damaged by an organic solvent. There is no particular limitation as long as a film can be formed, and examples of the fatty acid amide structure having 6 or more carbon atoms include the following.
For example, a fatty acid amide formed from a primary amine having one hydroxyl group and a fatty acid, a fatty acid amide formed from a secondary amine having two hydroxyl groups and a fatty acid, a secondary amine having one hydroxyl group, and It is a fatty acid amide formed from fatty acids.
Examples of these fatty acid amides having a hydroxyl group include alkylene oxide adducts obtained by further adding an alkylene oxide chain to the hydroxyl group of a fatty acid amide having a hydroxyl group (for example, C _2-4 alkylene such as ethylene oxide adduct, propylene oxide adduct, etc.). Oxide adducts) are also included.

  The introduction of the acryloyl group or methacryloyl group is not particularly limited. For example, an acryloyl group or a methacryloyl group can be introduced via an ester bond, an ether bond, or a urethane bond using a hydroxyl group derived from an amine having a hydroxyl group or a terminal hydroxyl group of a polyalkylene oxide chain. It is convenient and preferable to introduce an acryloyl group or a methacryloyl group via a urethane bond.

More specifically, such a curable compound (A) can be obtained, for example, by the following method.
First, by using an amidation reaction between a fatty acid (a1) and a primary or secondary amine (a2) having a hydroxyl group, a fatty acid amide having a hydroxyl group and a hydrocarbon moiety having 6 or more carbon atoms introduced is formed.

  Here, the fatty acid is a monovalent carboxylic acid of a long-chain hydrocarbon. In the present invention, the fatty acid preferably has 6 or more carbon atoms. Furthermore, those having 10 to 24 carbon atoms are more preferable, those having 12 to 24 carbon atoms are more preferable, and those having 14 to 18 carbon atoms are particularly preferable from the viewpoints of ease of compatibility with fingerprints, ease of handling, and availability. Those are preferred. The fatty acid may be saturated or unsaturated, may be linear, or may be branched.

Examples of fatty acids having 6 or more carbon atoms include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, Saturated fatty acids such as nonadecanoic acid, arachidic acid, behenic acid, Linderic acid, Tuzu acid, myristoleic acid, palmitoleic acid, undecylic acid, oleic acid, elaidic acid, gadrenic acid, gondolic acid, cetreic acid, erucic acid, brassic acid And unsaturated fatty acids such as sorbic acid, linoleic acid, linoelaidic acid, linolenic acid, eleostearic acid, arachidonic acid, sardine acid, and nisic acid. Examples of natural fats and oils obtained as a mixture of these include linseed oil, olive oil, mustard oil, cacao butter, tung oil, sesame oil, rice bran oil, safflower oil, soybean oil, tall oil, corn oil, rapeseed oil, palm Examples include natural oils and fats such as oil, castor oil, sunflower oil, cottonseed oil, coconut oil, peanut oil, sardine oil, beef tallow, whale oil, shark liver oil, pork fat and butter.
Among these, oleic acid can be particularly preferably used. These saturated or unsaturated fatty acids can be used singly or in combination in any quantity ratio.

The amine (a2) having a hydroxyl group is also referred to as an alkanolamine.
Among the alkanolamines, primary amines having one hydroxyl group (ie, N-monosubstituted amine) include monoalkanolamines such as ethanolamine, isopropanolamine, butanolamine (C _1-6 alkanolamines, particularly C _2-4 alkanolamines).
Among alkanolamines, secondary amines having two hydroxyl groups (ie, N, N-disubstituted amines) include dialkanolamines such as diethanolamine and diisopropanolamine (diC _1-6 alkanolamines, particularly Di _C2-4 alkanolamines) and the like.
Among the alkanolamines, secondary amines having one hydroxyl group (that is, N, N-disubstituted amine) include alkylalkanolamines (C _1-6 alkyl C ₁ -1) such as methylethanolamine and ethylethanolamine. ₆ alkanolamines, especially C _1-4 alkyl C _2-4 alkanolamines) and the like.
Among these, dialkanolamine which is an amine having two hydroxyl groups is preferable, and diethanolamine is particularly preferable.

A fatty acid mono- or dialkanol amide having a hydroxyl group can be obtained by an amidation reaction of these fatty acid and an amine having a hydroxyl group.
Next, an alkanolamine-derived alkylene oxide structure and a urethane bond are generated by reacting a hydroxyl group in the fatty acid amide with a compound (a3) having an acryloyl group or methacryloyl group and an isocyanate group, which will be described later.
Alternatively, a urethane bond is obtained by reacting an alkylene oxide adduct of a fatty acid amide, which is obtained by adding an alkylene oxide chain to a hydroxyl group in the fatty acid amide, and a compound (a3) having an acryloyl group or a methacryloyl group and an isocyanate group. Can be generated.
The fatty acid amide to which no alkylene oxide is added and the fatty acid amide to which an alkylene oxide is added can be used alone or in combination of two or more.

The alkylene oxide adduct of the fatty acid amide may have a polyalkylene oxide unit (such as a poly C _2-4 alkylene oxide unit), and is a compound in which an alkylene oxide is added to the fatty acid amide.
Examples of the alkylene oxide adduct of fatty acid amide include polyoxyethylene capric acid ethanolamide, polyoxyethylene lauric acid ethanolamide, polyoxypropylene lauric acid ethanolamide, polyoxyethylene lauric acid isopropanolamide, and polyoxyethylene myristic acid ethanolamide. PolyoxyC _2-4 alkylene N- (hydroxy C _1-4 alkyl) -C _6-24 alkanecarboxylic acid amide, such as polyoxyethylene coconut oil fatty acid ethanolamide, polyoxyethylene oleic acid ethanolamide; polyoxyethylene lauric acid Di-C _1-4 alkanol such as diethanolamide, polyoxyethylene coconut fatty acid diethanolamide, polyoxyethylene oleic acid diethanolamide Examples include amide C _2-4 alkylene oxide adducts of ruamine and C _6-24 alkanecarboxylic acid.

  The addition mole number (or average addition mole number) of alkylene oxide in the alkylene oxide adduct is not particularly limited and is, for example, 1 to 50 moles, preferably 1 to 30 moles, more preferably 1 mole relative to 1 mole of fatty acid amide. Is preferably about 1 to 10 moles. If the added mole number of the alkylene oxide chain is too large, the hydrophilicity becomes strong and the fingerprint mark erasing performance may be deteriorated.

Next, an example of introduction of an acryloyl group or a methacryloyl group will be described.
A compound having a hydroxyl group and not having an alkylene oxide chain, or a fatty acid amide having a hydroxyl group and an alkylene oxide chain, and having at least a part of these hydroxyl groups having an acryloyl group or a methacryloyl group and an isocyanate group (a3 ) Can be synthesized to synthesize a compound having an acryloyl group or a methacryloyl group. It is preferable to react all the hydroxyl groups of the fatty acid amide with the compound (a3) having the isocyanate group. Thereby, these functional groups can be introduced into the curable compound (A) via a urethane bond.
The compound obtained at this time has an alkylene oxide structure between the fatty acid amide structure and the urethane structure.

  When a compound having one acryloyl group or one methacryloyl group and one isocyanate group is used as the compound (a3) having an acryloyl group or methacryloyl group and an isocyanate group, for example, a compound in which the fatty acid amide has two hydroxyl groups In this case, an average of more than one (meth) acryloyl group per molecule is caused by reacting more than 1/2 of the total amount of hydroxyl groups with an isocyanate group in the compound (a3). Can be obtained.

Further, when a compound having one isocyanate group and two or more acryloyl groups or methacryloyl groups is used as the compound (a3) having an acryloyl group or methacryloyl group and an isocyanate group, for example, the fatty acid amide has two hydroxyl groups. In the case of a compound having at least one acryloyl group or methacryloyl group in one molecule on average, by reacting at least 1/2 of the total amount of hydroxyl groups with an isocyanate group in the compound (a3). Can be introduced.
By using a curable compound (A) obtained from a fatty acid amide having an average of more than one acryloyl group or methacryloyl group, the scratch resistance of the cured coating film formed from the curable composition of the present invention, Solvent resistance can be improved.

  The compound (a3) having an acryloyl group or methacryloyl group and an isocyanate group preferably has one isocyanate group. As such a compound (a3), for example, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloylmethyl) ethyl isocyanate and the like can be used. The compound (a3) to be used is not particularly limited as long as it is a compound having an acryloyl group or a methacryloyl group and an isocyanate group. A urethane acrylate having one isocyanate group obtained by reacting with a compound having a hydroxyl group may be used.

Through the above steps, a curable compound (A) using a fatty acid amide having a hydroxyl group can be obtained.
That is, the active energy ray-curable compound (A) has, for example, at least a fatty acid amide structure formed from a fatty acid having 6 or more carbon atoms and a primary or secondary amine having a hydroxyl group, and an alkylene oxide chain. And a compound having a urethane bond and an acryloyl group or a methacryloyl group.

A preferred method of the curable compound (A) in the present invention includes the following steps.
(1) a step of synthesizing a fatty acid amide having a hydroxyl group by subjecting a fatty acid (a1) having 6 or more carbon atoms and a primary or secondary amine (a2) having a hydroxyl group to an amidation reaction;
(2) synthesizing a fatty acid amide having an acryloyl group or a methacryloyl group by reacting at least a part of the hydroxyl group of the fatty acid amide with a compound (a3) having an acryloyl group or a methacryloyl group and an isocyanate group;
It is provided by the manufacturing method of the active energy ray-curable compound (A) having a fatty acid amide structure, an alkylene oxide chain, and an acryloyl group or a methacryloyl group.

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. 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 the polyisocyanate 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 curable composition according to the present invention preferably contains the curable compound (A) in a range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the curable compound (B). 10 to 10 parts by mass is more preferable, and 1.0 to 7.0 parts by mass is further preferable. 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. 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 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.

(Synthesis Example 1)
<Synthesis process of active energy ray-curable compound>
A flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube was charged with 28.7 parts of lauric acid diethanolamide (hydroxyl group: 2, product name: “Amizole LDE”, manufactured by Kawaken Fine Chemical Co., Ltd.) While blowing air at a temperature of 70 ° C., 28.2 parts of 2-acryloyloxyethyl isocyanate (isocyanate group: 1, product name: “Karenz AOI”, manufactured by Showa Denko KK) was added dropwise, and the mixture was stirred for 3 hours after the completion of the addition. Maintained. After completion of the reaction, the mixture was cooled to room temperature to obtain compound (A-1).
In addition, the molar ratio of the hydroxyl group derived from lauric acid diethanolamide and the isocyanate group derived from 2-acryloyloxyethyl isocyanate is hydroxyl group: isocyanate group = 2 mol: 2 mol, and acryloyl of the compound (A-1) of Synthesis Example 1 The average number of groups is two.

(Synthesis Example 2)
Instead of 28.7 parts of lauric acid diethanolamide used in Synthesis Example 1, 31.6 parts of myristic acid diethanolamide (2 hydroxyl groups, trade name: “Amizole MDE”, manufactured by Kawaken Fine Chemical Co., Ltd.) was used. Were the same as in Synthesis Example 1 to obtain compound (A-2).
In addition, the molar ratio of the hydroxyl group derived from myristic acid diethanolamide and the isocyanate group derived from 2-acryloyloxyethyl isocyanate is hydroxyl group: isocyanate group = 2 mol: 2 mol, and acryloyl of the compound (A-2) of Synthesis Example 2 The average number of groups is two.

(Synthesis Example 3)
Instead of 28.7 parts of lauric acid diethanolamide used in Synthesis Example 1, 37.2 parts of stearic acid diethanolamide (hydroxyl group: 2, product name: “Amizole SDE”, manufactured by Kawaken Fine Chemical Co., Ltd.) was used. Were the same as in Synthesis Example 1 to obtain compound (A-3).
In addition, the molar ratio of the hydroxyl group derived from stearic acid diethanolamide and the isocyanate group derived from 2-acryloyloxyethyl isocyanate is hydroxyl group: isocyanate group = 2 mol: 2 mol, and acryloyl of the compound (A-3) of Synthesis Example 3 The average number of groups is two.

(Synthesis Example 4)
Instead of 28.7 parts of lauric acid diethanolamide used in Synthesis Example 1, 37.0 parts of oleic acid diethanolamide (hydroxyl group: 2, product name: “Amizole ODHE”, manufactured by Kawaken Fine Chemical Co., Ltd.) was used. Were the same as in Synthesis Example 1 to obtain compound (A-3).
In addition, the molar ratio of the hydroxyl group derived from oleic acid diethanolamide and the isocyanate group derived from 2-acryloyloxyethyl isocyanate is hydroxyl group: isocyanate group = 2 mol: 2 mol, and acryloyl of the compound (A-4) of Synthesis Example 4 The average number of groups is two.

(Synthesis Example 5)
Instead of 28.7 parts of lauric acid diethanolamide used in Synthesis Example 1, 37.0 parts of oleic acid diethanolamide (hydroxyl group: 2, product name: “Amizole ODHE”, manufactured by Kawaken Fine Chemical Co., Ltd.) were used. . Instead of 2-acryloyloxyethyl isocyanate used in 2 parts, 17.8 bis (acryloylmethyl) ethyl isocyanate (isocyanate group: 1, product name: “Karenz BEI”, Showa Denko) 47.8 A compound (A-5) was obtained in the same manner as in Synthesis Example 1 except that a part of the compound was used.
In addition, the molar ratio of the hydroxyl group derived from oleic acid diethanolamide and the isocyanate group derived from 1,1-bis (acryloylmethyl) ethyl isocyanate is hydroxyl group: isocyanate group = 2 mol: 2 mol, and the compound (A The average number of acryloyl groups in -5) is 4.

(Synthesis Example 6)
Instead of 28.7 parts of lauric acid diethanolamide used in Synthesis Example 1, polyoxyethylene coconut oil fatty acid monoethanolamide (hydroxyl group: 1, ethylene oxide number of 10, trade name: “Amidette 10C”, Kawaken Fine Chemical 69.7 parts, and instead of 2-acryloyloxyethyl isocyanate using 28.2 parts, 1,1-bis (acryloylmethyl) ethyl isocyanate (isocyanate group: 1, trade name: “Karenz BEI”) The compound (A-6) was obtained in the same manner as in Synthesis Example 1 except that 23.9 parts of “made by Showa Denko KK” were used.
In addition, the molar ratio of the hydroxyl group derived from polyoxyethylene coconut oil fatty acid and the isocyanate group derived from 1,1-bis (acryloylmethyl) ethyl isocyanate is hydroxyl group: isocyanate group (derived from 1,1-bis (acryloylmethyl) ethyl isocyanate). = 1 mol: 1 mol, and the average number of acryloyl groups in the compound (A-6) of Synthesis Example 6 is two.

(Synthesis Example 7)
A flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube was charged with 35.5 parts of decyltetradecanol (hydroxyl group: 1, product name: “Lisonol 24SP”, manufactured by Higher Alcohol Industry Co., Ltd.) While blowing air at a temperature of 70 ° C., 14.1 parts of 2-acryloyloxyethyl isocyanate (trade name: “Karenz AOI”, manufactured by Showa Denko KK) was added dropwise, and stirring was maintained for 3 hours after completion of the dropwise addition. After completion of the reaction, the mixture was cooled to room temperature to obtain compound (X-2).
The molar ratio between the hydroxyl group derived from decyltetradecanol and the isocyanate group derived from 2-acryloyloxyethyl isocyanate is hydroxyl group (derived from decyltetradecanol): isocyanate group (derived from 2-acryloyloxyethyl isocyanate) = 1 mol: 1 The average number of acryloyl groups in the compound (X-1) of Synthesis Example 7 is 1.

Example 1
For 100 parts of pentaerythritol triacrylate (trade name: “Aronix M305” manufactured by Toa Gosei Co., Ltd.) as compound (B), 5 parts of compound (A-1) synthesized in Synthesis Example 1 were used as a photopolymerization initiator. 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 to 6)
Curing was carried out in the same manner as in Example 1 except that the compounds (A-2) to (A-6) synthesized in Synthesis Examples 2 to 6 were used instead of the compound (A-1) synthesized in Synthesis Example 1. A substrate with a coating film was obtained.

(Example 7)
Except that 4 parts of silica having a D50 particle diameter of 4 μm (trade name: “Nipsil SS50-B” manufactured by Tosoh Silica Co., Ltd.) was added to the coating resin composition of Example 4 as fine particles, and the coating liquid was prepared. 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)
Example 1 was used except that instead of the compound (A-1) synthesized in Synthesis Example 1, oleic acid diethanolamide (hydroxyl group: 2, product name: “Amizole ODHE”, manufactured by Kawaken Fine Chemical Co., Ltd.) was used. Similarly, a substrate with a cured coating film was obtained.

(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)
Instead of the compound (A-1) synthesized in Synthesis Example 1, a leveling agent containing a dimethylsiloxane skeleton (trade name: “BYK-UV3500” manufactured by Big Chemie Japan Co., Ltd.) 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 1 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.

  About the base material with a cured coating film of Examples 1-7 and Comparative Examples 1-5, the following physical-property evaluation was performed and the result was put together in Table 1 and Table 2. FIG.

(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 shown in Table 1, the substrate with a cured coating film using the curable compositions of Examples 1 to 6 has excellent 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 7 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 not containing the curable compound (A), the hard coat property of the cured coating film was good, but the fingerprint wiping property was not exhibited at all.
In Comparative Example 2 containing a fatty acid amide, the fingerprint wiping property was better than in Comparative Example 1, but the fatty acid amide 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.

  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 is an example containing a compound having a plurality of (meth) acryloyl groups and a dimethylsiloxane skeleton but not having a fatty acid amide 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.

  Comparative Example 5 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 the 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 that of Comparative Example 2 containing a fatty acid amide, 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. As compared with the examples containing the fatty acid amide, the fingerprint wiping property was inferior, there was a scratch in the scratch resistance test, and the hard coat property was 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 similar functions to the surfaces of lenses, window glass of buildings and vehicles, and various printed materials.

Claims (11)

An active energy ray-curable compound (A) having a fatty acid amide structure comprising a fatty acid having 6 or more carbon atoms, an alkylene oxide structure, and an acryloyl group or a methacryloyl group;
An active energy ray-curable compound (B) different from the active energy ray-curable compound (A);
An active energy ray-curable composition containing   The fatty acid amide structure of the active energy ray-curable compound (A) is formed by reacting a fatty acid (a1) having 6 or more carbon atoms with a primary or secondary amine (a2) having a hydroxyl group. The active energy ray-curable composition according to claim 1.   The fatty acid amide structure of the active energy ray-curable compound (A) is formed by reacting a fatty acid (a1) having 12 or more carbon atoms with a primary or secondary amine (a2) having a hydroxyl group. The active energy ray-curable composition according to claim 2, wherein   The fatty acid amide structure of the active energy ray-curable compound (A) was formed by reacting a fatty acid (a1) having 12 to 24 carbon atoms with a primary or secondary amine (a2) having a hydroxyl group. The active energy ray-curable composition according to claim 3, wherein In the active energy ray-curable compound (A), an acryloyl group or a methacryloyl group is introduced through a urethane bond derived from the hydroxyl group of the primary or secondary amine (a2) having the hydroxyl group. Item 5. The active energy ray-curable composition according to any one of Items 2 to 4 .   The urethane bond is formed by reacting at least a part of hydroxyl groups derived from a primary or secondary amine (a2) having a hydroxyl group with a compound (a3) having an acryloyl group or a methacryloyl group and an isocyanate group. The active energy ray-curable composition according to claim 5, which has been prepared.   The alkylene oxide structure is formed by a reaction between a hydroxyl group-derived primary or secondary amine (a2) -derived hydroxyl group and an isocyanate group-containing compound (a3), or a fatty acid (a1) and It is an alkylene oxide chain added to a hydroxyl group derived from a primary or secondary amine (a2) having a hydroxyl group in a fatty acid amide generated by a reaction with a primary or secondary amine (a2) having a hydroxyl group. The active energy ray-curable composition according to claim 6.   The active energy ray-curable composition according to any one of claims 2 to 7, wherein the amine (a2) having a hydroxyl group has two hydroxyl groups.   The active energy ray according to any one of claims 1 to 8, wherein the active energy ray-curable compound (A) has an average of more than one acryloyl group or methacryloyl group in one molecule. Curable composition. The active energy ray-curable composition according to any one of claims 1 to 9 , which is used for forming a fingerprint-resistant cured coating film. The curable coating formed from the active energy ray-curable composition according to any one of claims 1 to 10 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 with a film.