JP2006124653A - Epoxy(meth)acrylate and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an epoxy(meth)acrylate that improves self restoration and resistance to scuffing of a cured product and its use. <P>SOLUTION: The epoxy(meth)acrylate is obtained by reacting (A) an aliphatic tricarboxylic acid or (B) a tricarboxylic acid represented by trimellitic acid with (C) an aliphatic (meth)acrylate containing a monooxirane ring or (D) a (meth)acrylate containing a monooxirane ring represented by an alicyclic (meth)acrylate containing a monooxirane ring. The epoxy(meth)acrylate is mixed with at least one kind that has active energy ray-curability and is selected from a long-chain alkyl group-containing compound, a silicone-based compound and a fluorine-based compound to constitute an active energy ray-curable composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an epoxy (meth) acrylate used as a raw material for forming, for example, an ultraviolet curable paint and the use thereof.

  Conventionally, the following ultraviolet curable composition and active energy ray curable composition are known as a composition used for a coating material, a coating agent, etc. (for example, refer patent document 1 and 2). That is, the ultraviolet curable composition is an ultraviolet curable urethane (meth) obtained by reacting an isocyanate prepolymer compound having three or more isocyanate groups in one molecule with polycaprolactone-modified hydroxyethyl (meth) acrylate. An acrylate and a photoinitiator are contained. And the coating film obtained by hardening | curing a ultraviolet curable composition can exhibit effects, such as abrasion resistance and adhesiveness.

In addition, the active energy ray-curable composition is a urethane (meta) obtained by reacting an organic isocyanate having two or more isocyanate groups in one molecule with a hydroxy-modified (meth) acrylate and a polycaprolactone-containing polyfunctional alcohol. ) It contains acrylate. And the coating film obtained by hardening | curing an active energy ray curable composition can improve abrasion resistance.
JP 2001-2744 A (pages 2 and 9) JP 2004-35599 A (2nd and 11th pages)

  However, the ultraviolet curable composition and the cured product of the active energy ray curable composition described in Patent Documents 1 and 2 are composed of soft segments made of polycaprolactone. For this reason, the cured product of the ultraviolet curable composition or the active energy ray curable composition becomes too flexible, and the self-healing property is lowered and the scratch resistance is also lowered. Furthermore, the hardened | cured material of the said ultraviolet curable composition or an active energy ray curable composition has a urethane bond by reaction of an isocyanate group and a hydroxyl group as frame | skeleton which comprises urethane (meth) acrylate. For this reason, there existed a problem that the hardened | cured material of an ultraviolet curable composition or an active energy ray curable composition became flexible, self-repairing property fell, and scratch resistance also fell.

  The present invention has been made paying attention to the problems existing in the above-described prior art. That is, the objective of this invention is providing the epoxy (meth) acrylate which can improve the self-restoration property and abrasion resistance of hardened | cured material, and its use.

  In order to achieve the above object, the epoxy (meth) acrylate of the invention described in claim 1 is represented by the following tricarboxylic acid represented by (A) or (B) and the following (C) or (D). It is characterized by reacting with a (meth) acrylate having a monooxirane ring.

  (A): Aliphatic tricarboxylic acid represented by the following general formula (1)

但し、Ｒは水素又は水酸基、ａ、ｂ及びｄは０〜８の整数、ｃは０〜９の整数で、０≦ａ＋ｂ＋ｃ＋ｄ≦９かつ〔ａ＜ｄ又は（ａ＝ｄかつｂ≦ｃ）〕である。

However, R is hydrogen or a hydroxyl group, a, b and d are integers of 0 to 8, c is an integer of 0 to 9, and 0 ≦ a + b + c + d ≦ 9 and [a <d or (a = d and b ≦ c)] It is.

(B): Trimellitic acid (C): Aliphatic (meth) acrylate having a monooxirane ring represented by the following general formula (2)

但し、Ｒは水素又はメチル基、ｎは１〜５の整数、ｍは１〜３の整数を表す。

However, R represents hydrogen or a methyl group, n represents an integer of 1 to 5, and m represents an integer of 1 to 3.

  (D): An alicyclic (meth) acrylate having a monooxirane ring represented by the following general formula (3)

但し、Ｒは水素又はメチル基、ｓは１〜１０の整数を表す。

However, R represents hydrogen or a methyl group, and s represents an integer of 1 to 10.

It is characterized by this.
The active energy ray-curable composition according to the second aspect of the invention contains the epoxy (meth) acrylate according to the first aspect.

  The active energy ray-curable composition of the invention according to claim 3 is the invention according to claim 1, further comprising at least one compound selected from a long-chain alkyl group-containing compound, a silicone compound and a fluorine compound. It contains.

  The active energy ray-curable composition of the invention according to claim 4 is the invention according to claim 3, wherein the long-chain alkyl group-containing compound, the silicone compound and the fluorine compound have an active energy ray-curable functional group. It is.

The cured product of the epoxy (meth) acrylate of the invention according to claim 5 is obtained by curing the epoxy (meth) acrylate according to claim 1.
The coating film of the invention described in claim 6 is characterized in that the epoxy (meth) acrylate according to claim 1 is applied to the surface of a substrate and cured.

  The coated article of the invention described in claim 7 is characterized in that it comprises a base material and a coating film obtained by applying the epoxy (meth) acrylate according to claim 1 to the surface and curing it. It is.

According to the present invention, the following effects can be exhibited.
The epoxy (meth) acrylate of the invention described in claim 1 is obtained by reacting a specific tricarboxylic acid with a (meth) acrylate having a specific monooxirane ring. This epoxy (meth) acrylate is composed of an addition reactant of a tricarboxylic acid and a monooxirane ring in place of the conventional soft segment and urethane bond by polycaprolactone. And since tricarboxylic acid is trifunctional, the crosslinking density after superposition | polymerization becomes a moderate thing compared with bifunctional or tetrafunctional. Therefore, the epoxy (meth) acrylate has a good balance between the soft segment and the hard segment, and can improve the self-repairing property and scratch resistance of the cured product.

  The active energy ray-curable composition according to the second aspect of the invention contains the epoxy (meth) acrylate according to the first aspect. For this reason, the active energy ray-curable composition easily cures the epoxy (meth) acrylate by irradiating the active energy ray, and the obtained cured product exhibits excellent self-repairability and scratch resistance. Can do.

  The active energy ray-curable composition of the invention described in claim 3 further contains at least one compound selected from a long-chain alkyl group-containing compound, a silicone-based compound, and a fluorine-based compound. By these compounds, since the cured product of the active energy ray-curable composition has surface lubricity, the force applied to the surface is relaxed, and the effect of the invention according to claim 2 can be improved.

  In the active energy ray-curable composition of the invention described in claim 4, the long-chain alkyl group-containing compound, the silicone compound and the fluorine compound have an active energy ray-curable functional group. Therefore, in addition to the effect of the invention according to claim 3, curability of the active energy ray-curable composition by active energy rays can be enhanced.

  A cured product of the epoxy (meth) acrylate of the invention according to claim 5 is obtained by curing the epoxy (meth) acrylate according to claim 1. Therefore, the cured product of epoxy (meth) acrylate can exert the effect of the invention according to claim 1.

  The coating film of the invention described in claim 6 is formed by applying the epoxy (meth) acrylate described in claim 1 to the surface of the base material and curing it. Therefore, this coating film can exhibit the effect of the invention according to claim 1.

  The coated article of the invention described in claim 7 is composed of a base material and a coating film formed by coating the epoxy (meth) acrylate according to claim 1 on the surface thereof and curing it. Therefore, the coated article can exert the effect of the invention according to claim 1 for the coating film.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The epoxy (meth) acrylate of this embodiment is obtained by reacting the tricarboxylic acid represented by the following (A) or (B) with the (meth) acrylate having a monooxirane ring represented by the following (C) or (D). It will be. The tricarboxylic acid represented by (A) and the tricarboxylic acid represented by (B) can be used alone or in combination. The (meth) acrylate having a monooxirane ring represented by (C) and the (meth) acrylate having a monooxirane ring represented by (D) can be used alone or in combination. Here, (meth) acrylate is a term that means both acrylate and methacrylate in the present specification.

  (A): Aliphatic tricarboxylic acid represented by the following general formula (1)

但し、Ｒは水素（Ｈ）又は水酸基（ＯＨ）、ａ、ｂ及びｄは０〜８の整数、ｃは０〜９の整数で、０≦ａ＋ｂ＋ｃ＋ｄ≦９かつ〔ａ＜ｄ又は（ａ＝ｄかつｂ≦ｃ）〕である。

Where R is hydrogen (H) or hydroxyl group (OH), a, b and d are integers of 0 to 8, c is an integer of 0 to 9, and 0 ≦ a + b + c + d ≦ 9 and [a <d or (a = d And b ≦ c)].

(B): Trimellitic acid (C): Aliphatic (meth) acrylate having a monooxirane ring represented by the following general formula (2)

但し、Ｒは水素又はメチル基、ｎは１〜５の整数、ｍは１〜３の整数を表す。

However, R represents hydrogen or a methyl group, n represents an integer of 1 to 5, and m represents an integer of 1 to 3.

  (D): An alicyclic (meth) acrylate having a monooxirane ring represented by the following general formula (3)

但し、Ｒは水素又はメチル基、ｓは１〜１０の整数を表す。

However, R represents hydrogen or a methyl group, and s represents an integer of 1 to 10.

  This epoxy (meth) acrylate has curability with respect to active energy rays such as ultraviolet rays and electron beams, and is suitably used as a raw material for paints, coating agents and the like. Therefore, the composition containing such an epoxy (meth) acrylate is an active energy ray-curable composition. Epoxy (meth) acrylate has a good balance between the soft segment and the hard segment, that is, the balance between the hardness and elasticity of the cured product, and the cured product can exhibit self-repairing and scratch resistance functions. Here, the self-repairing property means the recoverability of the scratch when the surface of the cured product is scratched, and the scratch resistance means the haze of the surface when the surface of the cured product is slid.

  The tricarboxylic acid (A) is 1,2,4-butanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 1 and d = 0), 1,3,5-hexanetricarboxylic acid. (R is hydrogen, a = 0, b = 1, c = 2 and d = 0) 1,2,4-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 1 and d = 1) 1,2,5-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 2 and d = 0), 1,3,4-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 0 and d = 1), 1,2,5-pentanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 1 and d = 0), 1,2, 6-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 3 and d = 0) 1,2,4-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 0, c = 1 and d = 2) 1,4,5-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 2, c = 0 and d = 1) 1,3,4-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 0 and d = 2) 1,3,6-hexanetricarboxylic acid (R is hydrogen, a = 0, b = 1, c = 2 and d = 0), 2,3,5- Hexanetricarboxylic acid (R is hydrogen, a = 1, b = 0, c = 1 and d = 1), 1,4,8-octanetricarboxylic acid (R is hydrogen, a = 0, b = 2, c = 3 And d = 0) 1,5,10-nonanetricarboxylic acid (R is hydrogen, a = 0, b = 3, c = 3 and d = 0), 1,6,12-dodecanetricarboxylic acid (R is hydrogen) , A = 0, b = 4, c = 5 and d = 0), citric acid (R is a hydroxyl group, a = b = c = d = 0) and the like.

Examples of trimellitic acid (B) include 1,2,4-trimellitic acid and 1,3,5-trimellitic acid and 1,2,3-trimellitic acid.
As the aliphatic (meth) acrylate having a monooxirane ring of (C), 4-hydroxybutyl acrylate monoglycidyl ether [4-HBAGE, a compound in which n = 4 and m = 1 in the general formula (2)], 2- Hydroxyethyl acrylate monoglycidyl ether [2-HEAGE, compound of general formula (2) where n = 2, m = 1] and the like.

Examples of the alicyclic (meth) acrylate having a monooxirane ring represented by the general formula (3) in (D) include alicyclic epoxy group-containing acrylate (s = 6).
It is desirable that the active energy ray-curable composition further contains at least one compound selected from a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound. With these compounds (slip agents), the cured product of the active energy ray-curable composition can exhibit surface lubricity, and as a result, a part of the force applied to the surface of the cured product is converted to a sliding force and relaxed. In addition, the function of improving self-repairability and scratch resistance can be exhibited. When these slip agents have an active energy ray-curable functional group, curability of the active energy ray-curable composition by active energy rays can be increased. Accordingly, it is possible to cope with the low viscosity and high solidification of the active energy ray curable composition, and it is possible to improve the adhesion and solvent resistance of the cured product.

  In the long-chain alkyl group-containing compound, the long-chain alkyl group preferably has 13 to 25 carbon atoms. Specific examples of the long-chain alkyl group-containing compound include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene cetyl alcohol, polyoxyethylene stearyl alcohol, glycerol monostearate and the like; tridecyl (meta ) Acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, and the like.

  Specific examples of the silicone compound include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethyl. Examples thereof include siloxane.

  Specific examples of the fluorine-based compound include compounds having a fluoroalkyl group such as a fluoroalkyl carboxylate, a fluoroalkyl quaternary ammonium salt, and a fluoroalkylethylene oxide adduct; a perfluoroalkyl carboxylate and a perfluoroalkyl quaternary ammonium salt. A compound having a perfluoroalkyl group, such as a perfluoroalkylethylene oxide adduct; a compound having a fluorocarbon group; a tetrafluoroethylene polymer; a copolymer of vinylidene fluoride and tetrafluoroethylene; a copolymer of vinylidene fluoride and hexafluoropropylene Fluorine-containing (meth) acrylic acid ester; Fluorine-containing (meth) acrylic acid ester polymer; Fluorine-containing (meth) acrylic acid alkyl ester polymer; Fluorine-containing (meth) acrylic acid A copolymer of ester and other monomers.

  The epoxy (meth) acrylate or the active energy ray-curable composition containing the epoxy (meth) acrylate may be applied to the surface of the substrate and cured by a curing means to form a coating film on the substrate. A coated article is obtained from this substrate and a coating film formed thereon. As described above, the coating film constituting the coated article can exhibit self-repairing and scratch resistance functions.

  Specific examples of base materials include electric and electronic devices such as mobile phones, watches, compact discs, audio devices, and OA devices; electronic material components such as touch panels and antireflection plates for cathode ray tubes; home appliances such as refrigerators, vacuum cleaners, and microwave ovens. Products: Automotive interiors such as meter panels and dashboards; Pre-coated metal steel plates; Automotive bodies, bumpers, spoilers, door knobs, handles, headlamps, motorcycle gasoline tanks, plated, evaporated or sputtered aluminum wheels and door mirrors Automotive parts such as: Carport roofs, daylighting roofs; Plastic molded products such as polyvinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate, ABS resin; woodwork products such as stairs, floors, desks, chairs, chiffons, and other furniture A cloth, paper or the like.

  The coating method may be in accordance with a conventional method, and examples thereof include an air spray method, an airless spray method, an electrostatic coating method, a roll coater method, a flow coater method, and a spin coat method. The thickness of the coating film is preferably about 1 to 100 μm. When the thickness of the coating film is less than 1 μm, the function of the coating film such as protecting the substrate surface cannot be sufficiently exhibited. On the other hand, if the thickness exceeds 100 μm, the coating film becomes too thick and the properties of the substrate cannot be fully exhibited.

Further, as a curing means, in addition to a method of irradiating active energy rays such as ultraviolet rays and electron beams, a heating method or the like is employed. In the case of the method of irradiating with ultraviolet rays, it is preferable to use a mercury lamp, a metal halide lamp or the like, and it is preferable to irradiate ultraviolet rays with an integrated light quantity of 100 to 1000 mJ / cm ² . On the other hand, when curing by irradiating an electron beam, it is preferable to irradiate an electron beam of 1 to 5 Mrad at an acceleration voltage of 150 to 250 keV.

  Epoxy (meth) acrylate or an active energy ray-curable composition containing the same is used for the light-reflective film, anti-reflective film, polarizing film, light diffusion film, and retardation film in addition to the use as the paint or coating agent described above , Viewing angle adjustment films, lens sheets (for example, prism sheets used in backlight units such as liquid crystal display devices, Fresnel lens sheets and lenticular lens sheets used in projection televisions), heat ray reflective films, ultraviolet shielding films, It can also be suitably used as a constituent material for functional members such as electromagnetic shielding films and touch sensor films. That is, the functional member is configured by curing the epoxy (meth) acrylate or the active energy ray-curable composition of the present embodiment into a predetermined shape, or by applying it to the surface of the base material and curing it. Is also possible. In the latter case, the case where the cured product of the epoxy (meth) acrylate or the active energy ray-curable composition itself functions as a functional member, and the substrate plays the role of the functional member, and the epoxy (meth) acrylate or the active energy ray There are cases where the cured product of the curable composition plays a role of protecting the substrate, and any of them may be used.

  Among the functional members, the epoxy (meth) acrylate or active energy ray-curable composition of the present embodiment is a light reflection film, an antireflection film, a polarizing film, a light diffusion film, a retardation film, a viewing angle adjustment film, a lens. More preferably, it is used as a constituent material of an optical functional member such as a sheet. In these optical functional members, if the surface is scratched, it causes an optical defect, so that particularly scratch resistance is required, and a cured product capable of exhibiting scratch resistance can be formed. It is because the request | requirement can be met if an optical functional member is comprised with the epoxy (meth) acrylate or active energy ray curable composition of a form.

A reactive diluent, a photopolymerization initiator, a solvent and the like can be added to the active energy ray-curable composition.
Examples of reactive diluents include monofunctional or polyfunctional monomers or oligomers having a (meth) acryloyl group. Specifically, monohydroxyethyl (meth) acrylate phthalate, 2-ethoxyhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl (meth) Monofunctional monomers such as acrylate, vinyl acetate, styrene; neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanedio Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Dipropylene glycol di (meth) acrylate, bisphenol F diglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct, bisphenol F ethylene oxide modified diacrylate, bisphenol A ethylene oxide modified diacrylate, etc. Monomers of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane Tri (meth) acrylate of lenoxide adduct, 6 mol ethylene oxide adduct of trimethylolpropane tri (meth) acrylate, glycerin propoxy tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone of dipentaerythritol Polyfunctional monomers such as hexa (meth) acrylate as an adduct; unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate And the like.

  Examples of photopolymerization initiators include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, p-dimethylaminobenzoic acid Isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane 1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenz Formate, and the like.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol and isobutanol, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Examples of the solvent include ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.

  When preparing an epoxy (meth) acrylate, the (A) or (B) specific tricarboxylic acid and the (C) or (D) specific monooxirane ring (meth) acrylate and Are mixed and heated to cause addition reaction. This reaction proceeds easily by heating at about 100 ° C. The obtained epoxy (meth) acrylate is formed of an addition reactant of a tricarboxylic acid and a monooxirane ring. This addition reactant can express moderate hardness and elasticity compared to the conventional polycaprolactone bond or urethane bond. In addition, the soft segment and the hard segment of epoxy (meth) acrylate, that is, mainly the methylene chain and the (meth) acryloyl group can be improved in balance to have appropriate hardness and elasticity.

  When using the obtained epoxy (meth) acrylate, for example, a slip agent such as a long-chain alkyl group-containing compound, a photopolymerization initiator, and the like are added to prepare an active energy ray-curable composition. The active energy ray-curable composition is applied to the surface of a substrate, for example, and cured by irradiation with ultraviolet rays, whereby a coating film is formed and a coated article is obtained. Since the epoxy (meth) acrylate is formed from an addition reaction product of a tricarboxylic acid and a monooxirane ring and is trifunctional with a tricarboxylic acid, the polymer has an appropriate crosslinking density. Therefore, the coating film has good hardness and moderate elasticity. As a result, when the coating film is damaged, it can be repaired, and the surface can be prevented from becoming clouded when a force sliding on the coating film surface is applied.

The effects exhibited by the above embodiment will be described below.
-Epoxy (meth) acrylate of this embodiment reacts the specific tricarboxylic acid of the said (A) or (B), and the (meth) acrylate which has the specific monooxirane ring of the said (C) or (D). It is something to be made. This epoxy (meth) acrylate is composed of an addition reactant of a tricarboxylic acid and a monooxirane ring in place of the conventional soft segment and urethane bond by polycaprolactone. Therefore, the epoxy (meth) acrylate can exhibit appropriate hardness and elasticity of the cured product, and can improve the self-repairability and scratch resistance of the cured product.

  Moreover, this epoxy (meth) acrylate has active energy ray curable, and the composition containing epoxy (meth) acrylate is an active energy ray curable composition. Therefore, in this active energy ray-curable composition, the epoxy (meth) acrylate is easily cured by irradiating active energy rays, and the obtained cured product exhibits excellent self-repairability and scratch resistance. Can do.

  The active energy ray-curable composition preferably further contains at least one compound (slip agent) selected from a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound. With these slip agents, the cured product of the active energy ray-curable composition has surface lubricity, so that the force applied to the surface is reduced, and self-repairability and scratch resistance can be improved. Moreover, when the slip agent has an active energy ray-curable functional group, the curability of the active energy ray-curable composition by the active energy rays can be increased.

  -A cured product of epoxy (meth) acrylate is obtained by curing the epoxy (meth) acrylate by a curing means, and the cured product is excellent in self-repairability and scratch resistance.

  -A coating film is formed by applying and curing epoxy (meth) acrylate on the surface of the substrate, and the coating film can exhibit self-repairing properties and scratch resistance. A coated article is constituted by such a substrate and a coating film formed on the surface thereof. The coated article has an excellent self-repairing property and scratch resistance. Therefore, it is useful as a paint, a coating agent, an optical film or the like.

Hereinafter, the embodiment will be described more specifically with reference to synthesis examples, examples, and comparative examples. In addition, unless otherwise indicated, the part and% in each example show a mass part and mass%.
(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, thermometer and condenser, 415.8 parts of toluene, 100 parts of 1,2,4-butanetricarboxylic acid (acid value: 886), 4-hydroxybutyl acrylate monoglycidyl ether [Nippon Kasei Co., Ltd. Made, 4-HBAGE] 315.8 parts and hydroquinone monomethyl ether 0.1 parts were charged and heated to 100 ° C. Thereafter, it was confirmed that 1,2,4-tricarboxylic acid was completely dissolved, 2 parts of TPP (triphenylphosphine) was charged, and the reaction was terminated by maintaining at the same temperature for 24 hours. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 4.2 mgKOH / g (in terms of solid content) was obtained. The yield was 96.1%.

About the obtained epoxy acrylate, the infrared (IR) absorption spectrum was taken and the structure was confirmed. The infrared absorption spectrum is shown in FIG. As shown in FIG. 1, the absorption spectrum derived from the epoxy ring of 900 to 950 cm ⁻¹ based on the raw material 4-hydroxybutyl acrylate monoglycidyl ether disappeared, and the epoxy ring was opened from 3500 to 3600 cm ^−1. The absorption spectrum derived from the hydroxyl group produced | generated by this was confirmed.
(Synthesis Example 2)
In a four-necked flask equipped with a stirrer, thermometer and condenser, 310.5 parts of toluene, 100 parts of 1,2,4-butanetricarboxylic acid (acid value: 886), 210.5 parts of 4-hydroxybutyl acrylate monoglycidyl ether, hydroquinone monomethyl ether 0.1 part was charged and the temperature was raised to 100 ° C. Thereafter, it was confirmed that 1,2,4-tricarboxylic acid was completely dissolved, 2 parts of TPP (triphenylphosphine) was charged, and the reaction was terminated by maintaining at the same temperature for 24 hours. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 95.1 mg KOH / g (in terms of solid content) was obtained.
(Synthesis Example 3)
The reaction was performed in the same manner as in Synthesis Example 1 except that 354.4 parts of 2-hydroxyethyl acrylate monoglycidyl ether (2-HEAGE) as an epoxy compound and 454.4 parts of toluene as a solvent were used. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.
(Synthesis Example 4)
The reaction was conducted in the same manner as in Synthesis Example 1 except that 100 parts of 1,3,6-hexanetricarboxylic acid was used as the tricarboxylic acid, 265.6 parts of 4-hydroxybutyl acrylate monoglycidyl ether as the epoxy compound, and 365.6 parts of toluene as the solvent. . As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.
(Synthesis Example 5)
The reaction was conducted in the same manner as in Synthesis Example 1 except that 100 parts of 1,3,5-pentanetricarboxylic acid was used as the tricarboxylic acid, 294.1 parts of 4-hydroxybutyl acrylate monoglycidyl ether as the epoxy compound, and 394.1 parts of toluene as the solvent. . As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.
(Synthesis Example 6)
The reaction was conducted in the same manner as in Synthesis Example 1 except that 100 parts of 1,3,6-hexanetricarboxylic acid was used as the tricarboxylic acid, 271.6 parts of 2-hydroxyethyl acrylate monoglycidyl ether as the epoxy compound, and 371.6 parts of toluene as the solvent. . As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.
(Synthesis Example 7)
100 parts of 1,3,6-hexanetricarboxylic acid as tricarboxylic acid, alicyclic epoxy group-containing acrylate as an epoxy compound [A-200, manufactured by Daicel Chemical Industries, Ltd., compound of s = 6 in the above general formula (3) The reaction was conducted in the same manner as in Synthesis Example 1 except that 265.6 parts and 365.6 parts of toluene were used as the solvent. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.
(Synthesis Example 8)
Other than using 100 parts of 1,2,4-trimellitic acid as tricarboxylic acid, 279.7 parts of alicyclic epoxy group-containing acrylate [Daicel Chemical Industries, A-200] as epoxy compound and 379.7 parts of toluene as solvent The reaction was carried out in the same manner as in Synthesis Example 1. As a result, an epoxy acrylate having a solid content of 50% by mass and an acid value of 5 mgKOH / g (in terms of solid content) or less was obtained.

About the obtained epoxy acrylate, the infrared (IR) absorption spectrum was taken and the structure was confirmed. The infrared absorption spectrum is shown in FIG. As shown in FIG. 2, the absorption spectrum derived from the epoxy ring of 900 to 950 cm ⁻¹ based on the alicyclic epoxy group-containing acrylate as the raw material disappeared, and by opening of the epoxy ring of 3500 to 3600 cm ⁻¹ An absorption spectrum derived from the generated hydroxyl group was confirmed.
Example 1
As shown in Table 1, with respect to 831.6 parts of the epoxy acrylate obtained in Synthesis Example 1, 3 parts of active energy ray-curable silicone compound [BYK-3500, manufactured by BYK Chemie Co., Ltd.], photopolymerization initiator ( 17 parts of Irgacure 184) manufactured by Ciba Specialty Chemicals was mixed to obtain an active energy ray-curable composition.
(Example 2)
As shown in Table 1, an active energy ray-curable composition was prepared in the same manner as in Example 1 except that the active energy ray-curable silicone compound [BYK-3500, manufactured by BYK Chemie Co., Ltd.] was not used. Obtained.
(Example 3)
As shown in Table 1, instead of active energy ray-curable silicone compound [BYK-3500, manufactured by BYK Chemie Co., Ltd.], polyoxyethylene monostearate [Nippon Yushi Co., Ltd., Nonion S-4 An active energy ray-curable composition was obtained in the same manner as in Example 1 except that 3 parts were used.
Example 4
As shown in Table 1, instead of the active energy ray-curable silicone compound [BYK-3500, manufactured by BYK Chemie Co., Ltd.], 3 parts of a fluorine-based compound [manufactured by Daikin Industries, Ltd., NS-2103] An active energy ray-curable composition was obtained in the same manner as in Example 1 except that it was used.
(Example 5)
As shown in Table 1, instead of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 621.0 parts of the epoxy acrylate of Synthesis Example 2 and 12 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 6)
As shown in Table 1, in place of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 908.8 parts of the epoxy acrylate of Synthesis Example 3 and 18 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 7)
As shown in Table 1, in place of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 731.2 parts of the epoxy acrylate of Synthesis Example 4 and 15 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 8)
As shown in Table 1, using 788.2 parts of the epoxy acrylate of Synthesis Example 5 instead of 831.6 parts of the epoxy acrylate of Synthesis Example 1, the active energy ray-curable silicone compound [BYK-3500, manufactured by BYK Chemie Corp.] was used. Instead, an active energy ray-curable composition was obtained in the same manner as in Example 1, except that 3 parts of a fluorine compound [NS-2103, manufactured by Daikin Industries, Ltd.] was used.
Example 9
As shown in Table 1, instead of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 743.2 parts of the epoxy acrylate of Synthesis Example 6 was used and 15 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemical Co., Ltd.) was used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 10)
As shown in Table 1, instead of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 731.2 parts of the epoxy acrylate of Synthesis Example 7 and 15 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 11)
As shown in Table 1, instead of 831.6 parts of the epoxy acrylate of Synthesis Example 1, 759.4 parts of the epoxy acrylate of Synthesis Example 8 and 15 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) were used. The active energy ray-curable composition was obtained in the same manner as in Example 1.
(Example 12)
In a four-necked flask equipped with a stirrer, a thermometer and a condenser, 385.6 parts of toluene, 100 parts of citric acid monohydrate (acid value: 267), 285.6 parts of 4-hydroxyethyl acrylate monoglycidyl ether (4-HEAGE), 0.1 part of hydroquinone monomethyl ether was charged, and the temperature was raised to 100 ° C. Thereafter, it was confirmed that citric acid monohydrate was completely dissolved, 2 parts of TPP (triphenylphosphine) was added, and the reaction was terminated by maintaining at the same temperature for 24 hours. An energy beam curable composition was obtained.

100 parts of this composition was mixed with 2 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) to prepare an active energy ray-curable composition.
Citric acid is represented by the general formula (1) in which R is a hydroxyl group (OH) and a = b = c = d = 0.

（比較例１）
表２に示したように、ジペンタエリスリトールヘキサアクリレート〔東亞合成（株）製、M-402〕84部、N-ビニルピロリドン〔東亞合成（株）製、M-150〕14部、トルエン100部及び光重合開始剤（チバスペシャリティーケミカル社製、イルガキュア184）4部を混合して活性エネルギー線硬化性組成物を調製した。
（比較例２）
攪拌機、温度計及びコンデンサーを備えた四ツ口フラスコに、トルエン120部、キシリレンジイソシアネートのトリメチロールプロパンアダクト変性タイプ（三井タケダケミカル社製、D-110N）100部、ポリカプロラクトン変性ヒドロキシエチルアクリレート〔ダイセル化学工業（株）製、プラクセルFA-1〕70部、ジブチル錫ジラウレート0.02部及びハイドロキノンモノメチルエーテル0.2部を仕込んだ。そして、７０℃まで昇温して３時間保持することで、固形分５０質量％の変性ウレタンアクリレート（ＵＡ1）を得た。

(Comparative Example 1)
As shown in Table 2, dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., M-402) 84 parts, N-vinylpyrrolidone [manufactured by Toagosei Co., Ltd., M-150] 14 parts, toluene 100 parts And 4 parts of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 184) were mixed to prepare an active energy ray-curable composition.
(Comparative Example 2)
In a four-necked flask equipped with a stirrer, thermometer and condenser, 120 parts of toluene, 100 parts of xylylene diisocyanate trimethylolpropane adduct modified type (D-110N, Mitsui Takeda Chemical Co., Ltd.), polycaprolactone modified hydroxyethyl acrylate [ Daicel Chemical Industries, Plaxel FA-1] 70 parts, dibutyltin dilaurate 0.02 part and hydroquinone monomethyl ether 0.2 part were charged. And it heated up to 70 degreeC and hold | maintained for 3 hours, and the modified | denatured urethane acrylate (UA1) of 50 mass% of solid content was obtained.

As shown in Table 2, an active energy ray-curable composition was prepared by mixing 100 parts of this modified urethane acrylate with 4 parts of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals).
(Comparative Example 3)
As shown in Table 2, 100 parts of adipic acid as a dicarboxylic acid, 264.4 parts of an alicyclic epoxy group-containing acrylate (Daicel Chemical Industries, A-200) as an epoxy compound, 364.4 parts of toluene as a solvent, and light 15 parts of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) was mixed to obtain an active energy ray-curable composition.
(Comparative Example 4)
As shown in Table 2, 100 parts of butanetetracarboxylic acid as a tetracarboxylic acid, 341.9 parts of 4-hydroxybutyl acrylate monoglycidyl ether [manufactured by Nippon Kasei Co., Ltd., 4-HBAGE] as an epoxy compound, and 441.9 parts of toluene as a solvent Further, 18 parts of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemical Co., Ltd.) was mixed to obtain an active energy ray-curable composition.

  The compositions of each Example and Comparative Example were coated and cured on a 100 μm thick polyethylene terephthalate film that had been subjected to an easy adhesion treatment so as to have a dry film thickness of 10 to 15 μm. Curing was performed by drying in an oven at 80 ° C. for 1 minute to volatilize the solvent, and then irradiated with ultraviolet rays at a conveyor speed of 3 m / min in an ultraviolet (UV) drying oven with a lamp output of 80 W / cm.

以上の実施例１〜１２及び比較例１〜４の活性エネルギー線硬化性組成物の硬化物について、自己修復性及び耐擦傷性をはじめ、加工性、カール性、全光線透過率、ヘイズ値、密着性、耐溶剤性、耐酸性及び耐アルカリ性を以下に示す方法により評価した。それらの結果を表３〜５に示した。
<全光線透過率>
東京電色社製TC-H3DPKを使って全光線透過率（％）を測定した。
<ヘイズ値>
東京電色社製TC-H3DPKを使ってヘイズ（Haze）値を測定した。

About hardened | cured material of the active energy ray curable composition of the above Examples 1-12 and Comparative Examples 1-4, including self-restorability and scratch resistance, workability, curl property, total light transmittance, haze value, Adhesion, solvent resistance, acid resistance and alkali resistance were evaluated by the following methods. The results are shown in Tables 3-5.
<Total light transmittance>
Total light transmittance (%) was measured using TC-H3DPK manufactured by Tokyo Denshoku.
<Haze value>
Haze value was measured using TC-H3DPK manufactured by Tokyo Denshoku.

Haze value (%) = scattered light / total light transmitted light × 100
<Adhesion>
When a cross-cut peel test is performed in accordance with JIS K5400, the remaining rate is 100%, ◯ is 96-100%, ○ is 91-95%, □ is 81-90%. Δ, 80% or less was evaluated as ×.
<Solvent resistance>
Toluene was subjected to a spot test at 20 ° C. for 4 hours, and evaluated as ○ when no change was observed after the test, Δ when whitening / swelling was slightly observed, and × when whitening / swelling was remarkably observed.
<Abrasion resistance>
A 50-round rubbing test was performed using # 0000 steel wool under a load of 500 g. When the Haze value before and after the test is measured, the value obtained by subtracting the Haze value before the test from the Haze value after the test is 0, 0.1 to 0.5 is ○, 0.5 to 1.0 is □, 1.0 to 2.0 was evaluated as Δ, and 2.1 or more was evaluated as ×.
<Self-healing>
A scratch that has been recovered within 1 minute at 20 ° C after scratching the coating film with a nail, ○, a scratch that has been recovered within 2 to 10 minutes, and a scratch within 11 to 60 minutes Was evaluated as □, a case where the scratches were recovered within 1 day, and a case where the scratches were not recovered as ×.
<Processability>
When the cut surface was cut, the case where no burrs were generated on the cut surface was evaluated as ◯, and the case where burrs were observed was evaluated as ×.
<Curl properties>
When the test plate is cut into a 10cm square and a 2cm wide crosscut is placed in the center, the one with a curl depth of 0mm is ◎, the one with 0-0.5mm is ○, the one with 0.5-1.0mm is △ , 1.0 mm or more was evaluated as x.
<Acid resistance>
A spot test of 0.1 normal sulfuric acid at 20 ° C for 24 hours was conducted. Evaluation was as follows: ◯ for which no change was observed after the test, △ for whitening / swelling a little, and x for whitening / swelling markedly. did.
<Alkali resistance>
Perform a spot test of 0.1 normal sodium hydroxide at 20 ° C for 24 hours. ○ shows no change after the test, △ shows a little whitening / swelling, x shows a marked whitening / swelling It was evaluated.

表３及び表４に示したように、実施例１〜１２では全て自己修復性が認められ、耐擦傷性も良好であった。そのほか、加工性、カール性等の特性にも優れていた。また、実施例１と７及び実施例４と８を比較すると、ブタントリカルボン酸を用いた実施例１及び４がヘキサントリカルボン酸を用いた実施例７及びペンタントリカルボン酸を用いた実施例８に比べて耐擦傷性に優れる結果が得られた。

As shown in Table 3 and Table 4, in Examples 1 to 12, self-healing properties were all recognized, and scratch resistance was also good. In addition, it was excellent in properties such as processability and curling properties. Moreover, when Examples 1 and 7 and Examples 4 and 8 are compared, Examples 1 and 4 using butanetricarboxylic acid are compared with Example 7 using hexanetricarboxylic acid and Example 8 using pentanetricarboxylic acid. As a result, excellent scratch resistance was obtained.

表５に示したように、ハードコート系のコーティング剤の場合（比較例１）には、自己修復性が全く認められなかった。ポリカプロラクトン系のコーティング剤の場合（比較例２）には、自己修復性及び耐擦傷性共に不良であった。カルボン酸としてジカルボン酸を用いた場合（比較例３）及びテトラカルボン酸を用いた場合（比較例４）には、共に自己修復性は認められず、耐擦傷性も不良であった。従って、カルボン酸としてトリカルボン酸を使用したときのみが特異的に、自己修復性及び耐擦傷性をはじめとする特性に優れていることが明らかとなった。

As shown in Table 5, in the case of the hard coat type coating agent (Comparative Example 1), no self-repairing property was observed. In the case of the polycaprolactone-based coating agent (Comparative Example 2), both the self-healing property and the scratch resistance were poor. When dicarboxylic acid was used as the carboxylic acid (Comparative Example 3) and when tetracarboxylic acid was used (Comparative Example 4), no self-healing property was observed and the scratch resistance was poor. Accordingly, it was revealed that only when tricarboxylic acid was used as the carboxylic acid, the properties including the self-repairing property and the scratch resistance were excellent.

It should be noted that the present embodiment can be modified as follows.
A tricarboxylic acid other than the tricarboxylic acid represented by (A) or (B) can be used in combination.

  -In addition to the tricarboxylic acid shown by said (A) or (B), epoxy (meth) acrylate can also be obtained by adding dicarboxylic acid, tetracarboxylic acid, etc. In this case, the crosslinking density of the cured product of epoxy (meth) acrylate can be adjusted.

A (meth) acrylate other than the (meth) acrylate having a monooxirane ring represented by (c) or (D) can be used in combination.
A cured product of epoxy (meth) acrylate obtained by curing epoxy (meth) acrylate can be used as a filler in addition to molded products such as films and sheets.

Further, the technical idea that can be grasped from the embodiment will be described below.
An optical functional member obtained by curing the epoxy (meth) acrylate according to claim 1 into a film shape or a sheet shape. When comprised in this way, it can suppress that the surface of an optical function member is damaged.

  An optical functional member obtained by curing the active energy ray-curable composition according to any one of claims 2 to 4 into a film shape or a sheet shape. When comprised in this way, an optical function member can be obtained easily by irradiation of an active energy ray, and it can suppress that the surface of the optical function member is damaged.

  The active energy ray-curable composition according to any one of claims 2 to 4, further comprising a photopolymerization initiator. When comprised in this way, the sclerosis | hardenability by irradiation of an active energy ray can be improved.

  A cured product of the active energy ray-curable composition obtained by curing the active energy ray-curable composition according to any one of claims 2 to 4. When comprised in this way, the hardened | cured material of an active energy ray curable composition can exhibit the effect of the invention which concerns on any one of Claims 2-4.

  A coating film, wherein the active energy ray-curable composition according to any one of claims 2 to 4 is applied to a surface of a substrate and cured. When comprised in this way, a coating film can exhibit the effect of the invention which concerns on any one of Claims 2-4.

  A coating comprising: a base material; and a coating film formed by applying and curing the active energy ray-curable composition according to any one of claims 2 to 4 on the surface of the base material. Goods. When comprised in this way, the coated article can exhibit the effect of the invention which concerns on any one of Claims 2-4.

The infrared absorption spectrum figure for identifying the epoxy acrylate of the synthesis example 1. FIG. The infrared absorption spectrum figure for identifying the epoxy acrylate of the synthesis example 8. FIG.

Claims (7)

An epoxy (meth) obtained by reacting a tricarboxylic acid represented by the following (A) or (B) with a (meth) acrylate having a monooxirane ring represented by the following (c) or (D): Acrylate.
(A): Aliphatic tricarboxylic acid represented by the following general formula (1)

However, R is hydrogen or a hydroxyl group, a, b and d are integers of 0 to 8, c is an integer of 0 to 9, and 0 ≦ a + b + c + d ≦ 9 and [a <d or (a = d and b ≦ c)] It is.
(B): Trimellitic acid (C): Aliphatic (meth) acrylate having a monooxirane ring represented by the following general formula (2)

However, R represents hydrogen or a methyl group, n represents an integer of 1 to 5, and m represents an integer of 1 to 3.
(D): An alicyclic (meth) acrylate having a monooxirane ring represented by the following general formula (3)

However, R represents hydrogen or a methyl group, and s represents an integer of 1 to 10. An active energy ray-curable composition comprising the epoxy (meth) acrylate according to claim 1. The active energy ray-curable composition according to claim 2, further comprising at least one compound selected from a long-chain alkyl group-containing compound, a silicone-based compound, and a fluorine-based compound. The active energy ray-curable composition according to claim 3, wherein the long-chain alkyl group-containing compound, the silicone compound and the fluorine compound have an active energy ray-curable functional group. A cured product of the epoxy (meth) acrylate obtained by curing the epoxy (meth) acrylate according to claim 1. A coating film obtained by coating the epoxy (meth) acrylate according to claim 1 on the surface of a base material and curing it. A coated article comprising: a base material; and a coating film formed by applying the epoxy (meth) acrylate according to claim 1 to the surface and curing the base material.

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