JP2006299184A - Active energy ray curable compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an active energy ray-curable compound that has high adhesion or adhesive power and solvent resistance without impairing transparency of a plastic such as polycarbonate, polyolefin, etc., having excellent processability and transparency and an ultraviolet-curable composition using the same. <P>SOLUTION: The active energy ray-curable composition is obtained by reacting a hydroxy fatty acid (A) with an epoxy compound (B) containing one or more glycidyl groups and a compound (C) containing an isocyanate group and an acryloyl group in the same molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable compound, and more specifically, in technical fields such as paints, adhesives, printing inks, coating agents, fillers, molding materials, resists, and ultraviolet curable compositions for optical disks. It relates to the compounds used.

The active energy ray-curable composition can be prepared without solvent or with low volatile content. It is used in the technical fields of paints, adhesives, printing inks, coating agents, fillers, molding materials, resists, and the like because of its fast curing and excellent productivity. In the above-mentioned technical fields such as paints, adhesives, printing inks, coating agents, fillers, molding materials and resists, the curing method using ultraviolet rays among the active energy rays has a simple irradiation device and relatively low initial cost. Widely used because it is inexpensive. In general, as an active energy ray-curable composition that is cured by ultraviolet rays, viscosity and coating film properties are adjusted in addition to oligomer components such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate. Therefore, a monofunctional to polyfunctional (meth) acrylate monomer, vinyl ether monomer, etc. are blended so as to suit the application. Furthermore, in this ultraviolet curable composition, it is necessary to prepare a combination of photopolymerization initiators that generate radicals upon irradiation with ultraviolet rays.
In addition, the conventional active energy ray-curable composition is characterized by fast curing, but since it cures instantaneously, the strain due to cure shrinkage cannot be alleviated, and the faster cure cures the strain due to cure shrinkage. There is a problem that adhesion or adhesion to a substrate such as a coating film and an object to be coated or an object to be bonded is reduced.

  In order to increase the adhesion or adhesion of paints or adhesives, first, oligomers and monomers are selected according to the polarity of the object to be coated or the object to be adhered or the chemical properties of the surface. A method for preparing chemical and physical surface properties. Secondly, the distortion that occurs at the time of coating and curing so that the adhesion or adhesion to the substrate such as the cured coating film and the object to be coated, or the object to be bonded, etc. that the paint or adhesive originally has does not decrease. There are methods for reducing or reducing strain stress.

  The first method is a method for increasing the adhesion or adhesion using a material having an affinity for the substrate to be coated or the substrate to be bonded, and the surface of the substrate to be coated or the substrate to be bonded. There is a method of increasing the adhesion or adhesion by creating chemical bonds or hydrogen bonds. In particular, when the surface of the substrate to be coated or the substrate to be bonded is plastic or the like, a method of increasing the adhesive force by adding a component such as a highly soluble solvent or monomer that dissolves the plastic surface is used. However, in such a method, irregular reflection occurs on the surface of the substrate to be coated or the substrate to be bonded and lacks transparency in many cases, so that it is not suitable for applications requiring transparency.

  The conventional active energy ray-curable composition is characterized by rapid curing that cures instantaneously, so it is difficult to relieve strain due to curing shrinkage, and strain remains, so the prepared paint and adhesive are originally There is a drawback that the adhesion or adhesion of the cured coating film and the object to be coated, or the substrate to be adhered, such as the object to be adhered, decreases. In order to solve these problems, methods for relieving stress due to strain generated during curing have been studied. An active energy ray-curable composition containing a compound (oligomer) having a flexible structure in the molecule in order to relieve strain at the time of curing is disclosed.

  A composition containing a polyurethane acrylate comprising a hydroxy fatty acid ester, a polyvalent isocyanate component, and a (meth) acrylate component capable of reacting with an isocyanate is an active energy ray-curable composition having excellent adhesion to plastics, particularly polyolefin resins. It is disclosed (see Patent Document 1). In this technology, it seems that the flexible component of fatty acid polyol is a strain-relieving role at the time of curing and the structurally close component to olefinic resin enhances adhesion to olefinic resin, but only such flexible component Has poor molecular cohesiveness and has low chemical resistance such as solvent resistance and paint toughness as a paint that protects the object to be coated. There is. Furthermore, Patent Document 1 does not describe any technology relating to an ultraviolet curable composition used for an optical disc and an optical disc using the same, and discloses an ultraviolet curable composition used for an optical disc and an optical disc using the same. Is not mentioned at all.

  In another technology, the use of urethane acrylate, which has excellent flexibility, and epoxy acrylate, which has high molecular cohesion and high chemical resistance, is an attempt to achieve both film flexibility and chemical resistance such as solvent resistance. However, there are problems with transparency and the like, and it has been difficult to apply to compact discs, optical discs, mobile phones and the like that require moldability and transparency.

JP-A-11-302347 (Claims, Examples)

  Therefore, the object of the present invention is to cure active energy rays having high adhesion or chemical resistance such as adhesive strength and solvent resistance without impairing the transparency of plastic such as polycarbonate or polyolefin having excellent processability and transparency. An object of the present invention is to provide a mold compound and an ultraviolet curable composition using the same.

  Conventionally, in order to improve the adhesion with the cured film of the ultraviolet curable composition, by reducing the shrinkage rate when the ultraviolet curable composition is cured, or by reducing the elastic modulus of the cured film, It has been found effective to reduce or mitigate cure strain. As a means for that purpose, attempts have been made to increase the use ratio of relatively high molecular weight oligomers and keep the use ratio of low molecular weight monomers low.

  In order to solve the problems of the present invention, the present inventors have widely used a bisphenol type epoxy acrylate that is widely used in the field of coating agents and adhesives, and is generally used in an ultraviolet curable composition for optical disks. The contained ultraviolet curable composition was examined. The cured coating film of the ultraviolet curable composition containing the bisphenol type epoxy acrylate has toughness and chemical resistance. However, it has been found that bisphenol A type epoxy acrylate increases the elastic modulus of the cured film and does not alleviate the strain at the time of curing, which causes a decrease in adhesive strength.

  Therefore, an ultraviolet curable composition containing a reaction product of castor oil, hydrogenated castor oil (hydrogenated castor oil) and a derivative compound thereof, an isocyanate compound, and hydroxy (meth) acrylate described in Examples of Patent Document 1 was studied. . The ultraviolet curable composition containing the reaction product has a low cohesive force of the coating film, and the chemical resistance such as solvent resistance of the cured coating film is low, which is insufficient. Moreover, it turned out that the combined use of epoxy acrylate and urethane acrylate has a problem in transparency.

  Based on the above results, the present inventors examined an oligomer having a molecular structure that has an affinity for the surfaces of a polyolefin resin and a polycarbonate resin and can alleviate strain generated during curing. As a result, it was found that urethane acrylate having an epoxy resin skeleton reacted with hydroxy fatty acid has the desired characteristics, and the present invention was completed.

That is, the present invention relates to a hydroxy fatty acid (A),
An epoxy compound (B) having one or more glycidyl groups;
The present invention provides an active energy ray-curable compound obtained by reacting a compound (C) having an isocyanate group and an acryloyl group in the same molecule.

  An active energy ray-curable compound obtained by reacting a hydroxy fatty acid (A), an epoxy compound (B) having one or more glycidyl groups, and a compound (C) having an isocyanate group and an acryloyl group in the same molecule; And the active energy ray-curable composition containing the compound has a hydroxy fatty acid (A) having a flexible structure and a rigid bisphenol-type epoxy resin skeleton (B) in the molecule, and has a flexible alkyl ester or alkyl ether structure. It is a urethane acrylate in which the hydroxy (meth) acrylate and the half urethane compound (C) of diisocyanate are connected via a urethane bond. For this reason, the coating agent which can relieve stress of hardening shrinkage distortion and is excellent in the adhesiveness with respect to a plastic is obtained. Half-urethane compound (C) Since the structure of the flexible structure can be adjusted by hydroxy (meth) acrylate in the molecule and the acryloyl group concentration can be adjusted by the added amount of the half-urethane compound (C), the surface hardness of the compound having a flexible structure is high. Any compound can be prepared. Therefore, it can be prepared from a compound for a coating agent that requires a hard coating film to a compound for an adhesive agent having a flexible structure that can relieve the strain of curing strain.

The cured film of the active energy ray-curable composition comprising the active energy ray-curable compound of the present invention has high adhesion without impairing the transparency of plastics such as polycarbonate and polyolefin having excellent processability and transparency. Alternatively, a film having adhesive strength and solvent resistance can be obtained. Further, an article such as an optical disk using the same can be provided. Therefore, the active energy ray-curable compound of the present invention comprises an ultraviolet curable composition for optical disks and a reflective film for reflecting laser light for reading information on a substrate, and further an ultraviolet curable composition on the reflective film. An optical disc provided with a protective layer made of a cured product film and two substrates provided with a reflective film for reflecting laser light for reading information on at least one optical disc substrate are cured films of an ultraviolet curable composition. It is useful as an ultraviolet curable resin composition used for bonded optical disk applications bonded together.

  Hereinafter, the present invention will be described in detail. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, and the same applies to acrylic acid or methacrylic acid derivatives.

  The active energy ray-curable compound of the present invention reacts a hydroxy fatty acid (A), an epoxy compound (B) having one or more glycidyl groups, and a compound (C) having an isocyanate group and an acryloyl group in the same molecule. Can be obtained.

  Examples of the hydroxy fatty acid (A) include compounds represented by the formula (1). Specifically, lactic acid, 12-hydroxystearic acid, 14-hydroxyeicosaic acid, ricinoleic acid (12-hydroxy- 9-octadecenoic acid), 3-hydroxy-5-dodecenoic acid, 12-hydroxy-9-hexadecenoic acid, 17-hydroxy-17-octadecenoic acid, 12-hydroxy-9,15-octadienoic acid, rescrelic acid (14-hydroxy 11-eicosenoic acid), 14-hydroxy-11,17-eicosadienoic acid and the like, and industrial raw materials include castor oil fatty acid containing about 90% of the above-mentioned ricinoleic acid, and water that is a hydrogenated equivalent of castor oil fatty acid. Examples thereof include added castor oil fatty acid (main component 12-hydroxystearic acid). Hydroxy fatty acids may be used alone or in combination of two or more.

（式中、Ｒ^１は分岐鎖を有していても良い炭素数２〜３０のアルキレン基又は分岐鎖を有していても良い炭素数２〜３０のアルケニレン基を表す。）

(Wherein R ¹ represents an alkylene group having 2 to 30 carbon atoms which may have a branched chain or an alkenylene group having 2 to 30 carbon atoms which may have a branched chain.)

As the epoxy compound (B) having one or more glycidyl groups, for example, a compound represented by the formula (2) can be used, and in particular, a bisphenol in which Y is —C (CH ₃ ) ₂ —. An A-type epoxy resin is preferable because of its excellent cost as well as performance such as adhesive durability.

（式中、Ｙは-SO₂-、-CH₂-、-CH(CH₃)-又は-C(CH₃)₂-を表し、ｎは０〜８の整数を表す。）で表されるエポキシ化合物は、

(Wherein Y represents —SO ₂ —, —CH ₂ —, —CH (CH ₃ ) — or —C (CH ₃ ) ₂ —, and n represents an integer of 0 to 8). Epoxy compounds

  As the compound (C) having an isocyanate group and a (meth) acryloyl group in the same molecule, for example, a compound represented by the formula (3) can be used.

（式中、Ｒ^２は水素原子又はメチル基、Ｒ^３は分岐鎖を有していても良い炭素数１〜８のアルキレン基、Ｒ^４は分岐鎖又は環構造を有していても良い炭素数１〜１６の炭化水素基を表し、
Ｘは単結合、式（４）

(Wherein R ² is a hydrogen atom or a methyl group, R ³ is a C 1-8 alkylene group which may have a branched chain, and R ⁴ is a carbon which may have a branched chain or a ring structure. Represents a hydrocarbon group of formulas 1 to 16,
X is a single bond, Formula (4)

（式中、Ｒ^５は分岐鎖を有していても良い炭素数１〜８のアルキレン基を表し、ｍは１〜１０の整数を表す。）又は式（５）

(Wherein R ⁵ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and m represents an integer of 1 to 10) or formula (5)

（式中、Ｒ^６は分岐鎖を有していても良い炭素数１〜８のアルキレン基を表し、ｐは１〜１０の整数を表す。）で表される基である。）

(Wherein R ⁶ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and p represents an integer of 1 to 10). )

  Specific examples of the compound of formula (3) include a reaction product of 1 mol of diisocyanate (c1), 1 mol of compound (c2) having one hydroxyl group and one or more (meth) acryloyl groups in the molecule. I can do it. Examples of the diisocyanate (c1) include lysine diisocyanate, 1,6 hexamethylene diisocyanate, aliphatic diisocyanate such as 2,2,4-trimethylhexamethylene diisocyanate, or isophorone diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, hydrogenated. Tolylene diisocyanate, methylcyclohexylene diisocyanate, isopropylidenecyclohexyl-4,4-diisocyanate, alicyclic diisocyanate such as norbornene diisocyanate, or xylylene diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, o -Tolidine diisocyanate (3,3'-dimethylbiphenyl-4,4'-diisocyanate ), Araliphatic diisocyanates such as 1,5-naphthalene diisocyanate, or isocyanate compounds having a carbodiimide group such as Carbodilite V-05 (Nisshinbo Co., Ltd .: terminal aliphatic isocyanate compound having a polycarbodiimide group). These two or more types of diisocyanate compounds can be mixed and used. Of these, diisocyanates such as isophorone diisocyanate and 2,4-tolylene diisocyanate having a difference in reactivity of isocyanate groups in the molecule are preferable.

  The compound (c2) having one hydroxyl group and one or more (meth) acryloyl groups in the molecule includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth). Acrylates, hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc., and ε-caprolactone, β-methyl-δ-valerolactone, etc. to the hydroxyalkyl (meth) acrylate The compound obtained by adding the lactones can be mentioned. Furthermore, the radical polymerizable unsaturated double such as the hydroxyalkyl (meth) acrylate, or (meth) acrylic acid, acrylic acid dimer, half ester compound obtained from hydroxyalkyl (meth) acrylate and dibasic acid anhydride. A compound in which an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, tetrahydrofuran, or the like is added to a compound having a bond and one carboxyl group. Among these, a compound obtained by adding 1 to 8 mol of ε-caprolactone to hydroxyalkyl (meth) acrylate is preferable, and a compound obtained by adding 2 to 5 mol of ε-caprolactone is more preferable.

  The structure of the active energy ray-curable compound of the present invention includes a structure obtained by reacting the above-mentioned various compounds, and among them, the compound represented by the formula (6) is preferable.

（式中、Ｒ^１は分岐鎖を有していても良い炭素数２〜３０のアルキレン基又は分岐鎖を有していても良い炭素数２〜３０のアルケニレン基を表し、Ｙは-SO₂-、-CH₂-、-CH(CH₃)-又は-C(CH₃)₂-を表し、Ｚは-OH又は式（７）

(In the formula, R ¹ represents an alkylene group having 2 to 30 carbon atoms which may have a branched chain or an alkenylene group having 2 to 30 carbon atoms which may have a branched chain, and Y represents —SO _2. -, -CH _2- , -CH (CH ₃ )-or -C (CH ₃ ) ₂ -is represented, and Z is -OH or formula (7)

（式中、Ｒ^２は水素原子又はメチル基、Ｒ^３は分岐鎖を有していても良い炭素数１〜８のアルキレン基、Ｒ^４は分岐鎖又は環構造を有していても良い炭素数１〜１６の炭化水素基、Ｘは単結合、式（４）

(Wherein R ² is a hydrogen atom or a methyl group, R ³ is a C 1-8 alkylene group which may have a branched chain, and R ⁴ is a carbon which may have a branched chain or a ring structure. A hydrocarbon group of formulas 1 to 16, X is a single bond, formula (4)

（式中、Ｒ^５は分岐鎖を有していても良い炭素数１〜８のアルキレン基を表し、ｍは１〜１０の整数を表す。）又は式（５）

(Wherein R ⁵ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and m represents an integer of 1 to 10) or formula (5)

（式中、Ｒ^６は分岐鎖を有していても良い炭素数２〜８のアルキレン基を表し、ｐは１〜１０の整数を表す。）で表される基であるが、すべてのＺが-OHとなることはなく、ｎは０〜８の整数を表す。）で表される基である。）

(Wherein R ⁶ represents an alkylene group having 2 to 8 carbon atoms which may have a branched chain, and p represents an integer of 1 to 10). Does not become —OH, and n represents an integer of 0 to 8. ). )

In the active energy ray-curable compound of the present invention, the molar ratio of the carboxyl group of the hydroxy fatty acid (A) to the glycidyl group of the epoxy compound is 0.9 to 1.1, preferably equimolar, as the first step reaction. To obtain a compound obtained by reaction.
As the second stage reaction, separately in the same molecule represented by the formula (3) obtained by reacting a compound (c2) having a hydroxyl group and a (meth) acryloyl group in the same molecule as diisocyanate (c1) in advance. The half urethane compound (C) having an isocyanate group and an acryloyl group and the compound obtained by reacting the above (A) and (B) are reacted at a molar ratio of 0.9 to 1.1, preferably equimolar.

  The first stage reaction of the carboxyl group of the hydroxy fatty acid (A) and the glycidyl group of the epoxy compound (B) is desirably performed at a reaction temperature of 60 to 150 ° C, preferably 90 to 130 ° C. Any known catalyst can be used as the ring-opening catalyst for the glycidyl group. Representative examples include tertiary amines such as triethylenediamine and tri-n-butylamine, phosphines such as triphenyl phosphite, phosphite, and triphenylphosphine. Compound (C) having an isocyanate group and an acryloyl group in the same molecule represented by formula (3) is (half urethane compound), and in the presence of an inhibitor, a hydroxyl group and (meth) in the same molecule as diisocyanate (c1). It can be obtained by reacting the compound (c2) having an acryloyl group, and the reaction temperature can be reacted at 30 ° C. to 100 ° C., but diisocyanate is an isophorone diisocyanate having a difference in reactivity between two isocyanate groups, 2,4-tri In the case of a diisocyanate, a difference in reactivity at a low temperature is increased, so that 40 to 70 ° C. is particularly preferable. When preparing this half urethane compound, a reaction catalyst is not particularly required, but a small amount of a known urethane reaction catalyst can be used.

  The reaction between the reaction product of the hydroxy fatty acid (A) and the epoxy compound (B) and the compound (C) can be performed at a reaction temperature of 30 ° C to 100 ° C. The reaction time becomes longer at 60 ° C. or lower, and the polymerization of unsaturated double bonds of hydroxyalkyl (meth) acrylate (a1) is likely to occur at 90 ° C. or higher. Therefore, the reaction is carried out at a reaction temperature of 65 to 75 ° C. in the presence of an inhibitor. It is desirable to do. In this reaction, a known urethane reaction catalyst can be used.

  In the ultraviolet curable composition, the active energy ray-curable compound of the present invention is preferably contained in an amount of 10 to 90% by mass, preferably 20 to 60% by mass, based on the entire ultraviolet curable composition. . Further, known radical polymerizable monomers, oligomers, photopolymerization initiators, thermal polymerization initiators, and the like can be used in the ultraviolet curable composition.

  As a known radical polymerizable monomer, for example, as monofunctional (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate , Hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, etc. Is mentioned.

  Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, ethylene glycol di (meth) Polyoxyalkyl ether (meth) polyacrylates such as acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; Lunan dimethanol diacrylate, norbornane diethanol di (meth) acrylate, di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to norbornane dimethanol, tricyclodecane dimethanol di (meth) acrylate, tri Cyclodecanediethanol di (meth) acrylate, di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to tricyclodecanedimethanol, pentacyclopentadecanedimethanol di (meth) acrylate, pentacyclopentadecanediethanol Di (meth) acrylate and pentacyclopentadecane dimethanol are added with 2 moles of ethylene oxide or propylene oxide. ) Monomers having an alicyclic structure such as di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to acrylate, pentacyclopentadecane diethanol; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-acryloyloxybutyl) hydroxybutyl isocyanurate, bis (2-methacryloyloxy) Ethyl) hydroxyethyl isocyanurate, bis (2-methacryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-methacryloyloxy) Butyl) hydroxybutyl isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, tris (2-acryloyloxybutyl) isocyanurate, tris (2-methacryloyloxyethyl) isocyanurate , Monomers having an isocyanurate structure such as tris (2-methacryloyloxypropyl) isocyanurate, tris (2-methacryloyloxybutyl) isocyanurate, poly (meth) acrylates of dipentaerythritol, ethylene oxide-modified phosphoric acid (meth) ) Acrylate, ethylene oxide modified alkylated phosphoric acid (meth) acrylate, diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcapro A lactam, a vinyl ether monomer, etc. can be mentioned, The 1 type (s) or 2 or more types of the said radically polymerizable unsaturated monomer can be used.

  Examples of the oligomer include a polyurethane (meth) acrylate such as a urethane (meth) acrylate having a polyether skeleton, a urethane (meth) acrylate having a polyester skeleton, a urethane (meth) acrylate having a polycarbonate skeleton, or a polyol having a polyester skeleton (meth). One or more active energy ray-curable oligomers such as polyester (meth) acrylate esterified with acrylic acid, polyether (meth) acrylate esterified with (meth) acrylic acid into a polyether skeleton polyol Can be used.

  As the photopolymerization initiator, any known and commonly used photopolymerization initiators can be used, but those of molecular cleavage type or hydrogen abstraction type are suitable as the photopolymerization initiator used in the present invention. Examples of the photopolymerization initiator used in the present invention include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyldimethyl ketal, 2-hydroxy 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2 -Use a molecular cleavage type such as morpholinopropan-1-one, or a hydrogen abstraction type photopolymerization initiator such as benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenyl sulfide. Can do.

  Examples of sensitizers include trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone or the like can be used, and further, an amine that does not cause an addition reaction with the photopolymerizable compound can be used in combination. Of course, it is preferable to select and use those which are excellent in solubility in the ultraviolet curable compound and do not inhibit the ultraviolet transmittance. In addition, in the ultraviolet curable resin composition, as necessary, surfactants, leveling agents, thermal polymerization inhibitors, antioxidants such as hindered phenols and phosphites, and light stabilizers such as hindered amines are added as necessary. Can also be used

  When the ultraviolet curable composition is used for an optical disk, it is preferable to add a compound represented by the formula (4) to the ultraviolet curable composition. By adding the compound represented by the formula (8), the initial adhesive force of the cured film of the ultraviolet curable composition can be further increased, and further, after the optical disk is left in a high temperature and high humidity environment for a long time. It is possible to prevent a considerable decrease in the adhesive strength, the change in the appearance of the reflective film, and the increase in signal reading errors.

(８)
（式中、Ｒ^１、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵はそれぞれ独立的に、(i)水素原子、(ii)ハロゲン原子、(iii)水酸基、(iv)炭素数１〜８のアルコキシル基、(v)カルボキシル基、(vi)式(９)

(8)
(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently (i) a hydrogen atom, (ii) a halogen atom, (iii) a hydroxyl group, (iv) having 1 to 8 carbon atoms) Alkoxyl group, (v) carboxyl group, (vi) formula (9)

（９）
（式中、Ｒ^６は、ハロゲン原子で置換されていても良い炭素数１〜２０のアルキル基又はハロゲン原子で置換されていても良い炭素数１〜２０のアルケニル基を表す。）で表される基、或いは(vii)置換基としてカルボキシル基、アルコキシカルボニル基、アシルオキシル基又はアルコキシル基を有していても良い炭素数１〜２４のアルキル基若しくはアルケニル基を表すが、Ｒ^１、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵の中の少なくともひとつは水酸基である。）

(9)
(In the formula, R ⁶ represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an alkenyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom). Or (vii) a C1-C24 alkyl group or alkenyl group which may have a carboxyl group, an alkoxycarbonyl group, an acyloxyl group or an alkoxyl group as a substituent, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are hydroxyl groups. )

  The compound represented by the formula (8) includes compounds having various structures, and among them, compounds represented by the following formula (10), formula (11), formula (12) and formula (13) are preferable.

（１０）
（式中、Ｒ^７は、水素原子、ハロゲン原子で置換されていても良い炭素数１〜２０のアルキル基又はハロゲン原子で置換されていても良い炭素数１〜２０のアルケニル基を表す。）

(10)
(Wherein R ⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or an alkenyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom.)

（１１）
（式中、Ｒ^８、Ｒ⁹、Ｒ¹⁰及びＲ¹¹はそれぞれ独立的に、水素原子、ハロゲン原子、炭素数１〜８のアルコキシル基、置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルキル基、或いは置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルケニル基を表す（式中、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立的に、炭素数１〜８のアルキル基又は炭素数１〜８のアルケニル基を表す。）。）

(11)
(Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, or —COOH, —COOR ¹² , —OCOR ¹³ or An alkyl group having 1 to 24 carbon atoms which may have —OR ¹⁴ ; or a substituent having 1 to 24 carbon atoms which may have —COOH, —COOR ¹² , —OCOR ¹³ or —OR ¹⁴ as a substituent. Represents an alkenyl group (wherein R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms).

（１２）
（式中、Ｒ^１５、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸はそれぞれ独立的に、水素原子、ハロゲン原子、炭素数１〜８のアルコキシル基、置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルキル基、或いは置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルケニル基を表す（式中、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立的に、炭素数１〜８のアルキル基又は炭素数１〜８のアルケニル基を表す。）。）

(12)
(Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, or —COOH, —COOR ¹² , —OCOR ¹³ or An alkyl group having 1 to 24 carbon atoms which may have —OR ¹⁴ ; or a substituent having 1 to 24 carbon atoms which may have —COOH, —COOR ¹² , —OCOR ¹³ or —OR ¹⁴ as a substituent. Represents an alkenyl group (wherein R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms).

（１３）
（式中、Ｒ^１９、Ｒ²⁰、Ｒ²¹及びＲ²²はそれぞれ独立的に、水素原子、ハロゲン原子、炭素数１〜８のアルコキシル基、置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルキル基、或いは置換基として-COOH、-COOR^１２、-OCOR^１３又は-OR^１４を有していても良い炭素数１〜２４のアルケニル基を表す（式中、Ｒ^１２、Ｒ^１３、及びＲ^１４はそれぞれ独立的に、炭素数１〜８のアルキル基又は炭素数１〜８のアルケニル基を表す。）。）

(13)
(Wherein R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, or —COOH, —COOR ¹² , —OCOR ¹³ or An alkyl group having 1 to 24 carbon atoms which may have —OR ¹⁴ ; or a substituent having 1 to 24 carbon atoms which may have —COOH, —COOR ¹² , —OCOR ¹³ or —OR ¹⁴ as a substituent. Represents an alkenyl group (wherein R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms).

The alkyl group and alkenyl group in the above formula (10) may be branched or linear, and the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among them, R ⁸ is preferably a hydrogen atom or an alkyl group which may have an unsubstituted branched chain having 1 to 20 carbon atoms, and a hydrogen atom or an unsubstituted branched chain having 1 to 8 carbon atoms. It is more preferable that it is the alkyl group which may have. Furthermore, a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms is particularly preferable.

  Specific examples of the gallic acid ester represented by the above formula (10) include methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, isopentyl gallate, octyl gallate, dodecyl gallate, and gallic acid. Tetradecyl, hexadecyl gallate, octadecyl gallate and the like. As the compound represented by the formula (10), gallic acid is preferably used. Gallic acid is readily available as a commercial product, for example, manufactured by Dainippon Pharmaceutical Co., Ltd.

In formula (11), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are specifically: (i) a hydrogen atom, (ii) a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; iii) alkoxyl groups such as methoxy, ethoxy, butoxy and octyloxy; (iv) alkyl groups such as methyl, butyl, hexyl, octyl, lauryl and octadecyl; (v) alkenyl groups such as ethenyl, propenyl and 2-butenyl; ) 4-carboxybutyl, 2-methoxycarbonylethyl, methoxymethyl, ethoxymethyl and the like.

  Among the compounds represented by the formula (11), preferred are catechol, 3-sec-butylcatechol, 3-tert-butylcatechol, 4-sec-butylcatechol, 4-tert-butylcatechol, 3,5-di- -Tert-butylcatechol, 3-sec-butyl-4-tert-butylcatechol, 3-tert-butyl-5-sec-butylcatechol, 4-octylcatechol and 4-stearylcatechol, more preferably catechol And 4-tert-butylcatechol. It is particularly preferable to use 4-tert-butylcatechol. Examples of commercially available 4-tert-butylcatechol include DIC TBC-5P manufactured by Dainippon Ink and Chemicals, Inc.

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ in formula (12) and R ¹⁹ , R ²⁰ , R ²¹ and R ²² in formula (13) are specifically a hydrogen atom, a methyl group, Examples include propyl group, hexyl group, nonyl group, dodecyl group, iso-butyl group, sec-butyl group, tert-butyl group, neopentyl group, iso-hexyl group, tert-octyl group and the like.

  Among the compounds represented by the formula (12), hydroquinone, 2-hydroxyhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethyl) are preferable. Butyl) hydroquinone or 2,5-bis (1,1-dimethylbutyl) hydroquinone. Among the compounds represented by the formula (12), preferred are resorcinol (benzene-1,3-diol) and orcinol (5-methylbenzene-1,3-diol). Among the compounds represented by the formula (12), it is more preferable to use hydroquinone (benzene-1,4-diol) or 2-hydroxyhydroquinone (benzene-1,2,4-triol). As another compound represented by the formula (8), pyrogallol (1,2,3-trihydroxybenzene) is preferably used in the present invention.

  Among the compounds represented by the above formulas (10) to (13), the gallic acid or gallic acid ester represented by the formula (10) and the hydroquinone compound represented by the formula (12) are high temperature and high humidity. It is a particularly preferred compound among the compounds represented by the formula (8), which can particularly improve durability in the environment. Of the compounds represented by formula (8), gallic acid is the most preferred compound.

  The amount of the compound represented by the formula (8) added to the ultraviolet curable composition is preferably 0.05 to 10% by mass, more preferably 0.8%, based on the entire active energy ray curable composition. 1 to 10% by mass. It is still more preferable that it is 0.3-7 mass%, and it is especially preferable that it is 1-5 mass parts.

  An optical disk using an ultraviolet curable composition containing the active energy ray-curable compound of the present invention comprises a first reflective film for reflecting laser light for reading information on a first substrate, and further comprising An optical disc having a structure in which a resin layer made of a cured film of the ultraviolet curable composition is provided on a first reflective film. In the present specification, the reflection film is a translucent reflection film for reflecting laser light for reading information or a complete reflection film that does not substantially transmit the laser light. The optical disk using the ultraviolet curable composition containing the active energy ray-curable compound of the present invention is an optical disk having such a structure or an optical disk partially having such a structure. As such an optical disk, for example, a thin film of silver or a silver-based alloy is used as a light reflecting layer, and a resin layer made of a cured film of an ultraviolet curable composition is provided as a protective layer on the light reflecting layer. CD-ROM or CD-R is available. Further, for example, there is a DVD-5 in which a substrate having a light reflection layer made of silver or a silver-based alloy thin film is bonded to another substrate with an ultraviolet curable composition using the light reflection layer as an adhesive surface. is there.

  An optical disk using the ultraviolet curable composition containing the active energy ray-curable compound of the present invention is formed on a resin layer made of the cured film of the ultraviolet curable composition provided on the first reflective film. Further, a second substrate provided with a second reflective film for reflecting laser light for reading information is provided on the resin layer so that the resin layer and the second reflective film are in contact with each other. It may be an optical disc having the structure described above. As an optical disk having such a structure, at least one of two optical disk substrates provided with a reflective film for reflecting laser light for reading information has, for example, silver or silver as a main component on its surface. A bonding type of DVD-9, DVD-18, DVD-10, etc., in which the two optical disk substrates are bonded with the reflection films of the two substrates as the bonding surfaces. There is an optical disc.

As the optical disk substrate, those usually used as optical disk substrates can be used, and in particular, a polycarbonate substrate can be suitably used. Various materials can be used as the reflective film for reflecting the laser beam for reading information. For example, aluminum, gold, gold alloy, silver, silver alloy, silicon compound, etc. can be used. Among them, it is preferable to use silver or an alloy containing silver as a main component for the optical disk of the present invention. Examples of the “alloy containing silver as a main component” used in optical disks include silver alloys having a silver to gold ratio (Ag _X Au _Y ) described in US Pat. It is done.
0.9 <x <0.999
0.001 ≦ _Y ≦ 0.10

  The type of the optical disk is preferably a read-only DVD “DVD-5”, “DVD-10”, “DVD-9” and “DVD-18”, writable DVD-R, DVD + R, rewritable type DVD-RW, DVD + RW, DVD-RAM, and the like, particularly preferably “DVD-9” and “DVD-18”.

  Further, the optical disk is not limited to these. For example, the thickness of an optical disk substrate having a thickness of about 1.1 mm, for example, on a thin film of silver or a silver-based alloy as a main component by a cured film of the composition. A protective layer or a cover layer or a light transmission layer of about 0.1 mm may be formed, that is, a type suitable for blue-violet laser light as information reading and writing laser light, or similar to DVD It may be a SACD (Super Audio CD) having a structure in which two substrates having a thickness of 0.6 mm are bonded together.

  Hereinafter, examples of manufacturing “DVD-5”, “DVD-10”, “DVD-9”, and “DVD-18” will be described. Examples of the optical disk using the ultraviolet curable composition containing the active energy ray-curable compound of the present invention are not limited to these. Moreover, the ultraviolet curable composition used by the following manufacture example means the ultraviolet curable composition containing the active energy ray curable compound used by this invention.

(Production of DVD-9)
One optical disk substrate (A: second substrate) in which a metal thin film (second reflective film) of 40 to 60 nm is laminated on the unevenness called pits carrying recording information, and called pits carrying recording information A substrate for optical disk (B: first substrate) 1 in which a semi-transparent reflective film (semi-transparent reflective film: first reflective film) of 10 to 30 nm of silver or an alloy containing silver as a main component is laminated on unevenness. Prepare a sheet.

  As the second reflective film, for example, a film mainly composed of aluminum, silver, or an alloy composed mainly of silver can be used. Further, as the optical disk substrate, those known as optical disk substrates can be used. For example, amorphous polyolefin, polymethyl methacrylate, polycarbonate and the like can be mentioned, and it is particularly preferable to use a polycarbonate substrate.

  Next, the ultraviolet curable composition was applied onto the metal thin film (second reflective film) of the substrate (A: second substrate), and a translucent reflective film (first reflective film) was further laminated. UV curing applied to the surface of the metal thin film (second reflection film) so that the film surface of the semi-transparent reflection film (first reflection film) is an adhesive surface of the substrate (B: first substrate). It is bonded to a substrate (A: second substrate) through a mold composition, and ultraviolet light is irradiated from one or both surfaces of the bonded two substrates to bond them to make “DVD-9”.

(Manufacture of DVD-18)
Further, after manufacturing the DVD-9, the metal thin film (second reflective film) formed on the substrate (A: second substrate) is left on the substrate (B: first substrate) side. By peeling only the substrate (A: second substrate), the substrate (B: first substrate) / translucent reflective film (first reflective film) / cured film of the ultraviolet curable composition / metal thin film A disk intermediate body in which (second reflective film) is sequentially laminated is produced. Two such disk intermediates are prepared. Next, by using the metal thin film (first reflective film) of the two disc intermediates as an adhesive surface, and bonding them so that they face each other, “DVD-18” is obtained.

(Production of DVD-10)
A second substrate for an optical disk (C1: first substrate) and (C2) in which a reflection film of 40 to 60 nm made of silver or an alloy containing silver as a main component is laminated on irregularities called pits that carry recording information. : A second substrate). An ultraviolet curable composition is applied on the reflective film (first reflective film) of one substrate (C1: first substrate), and the other substrate (C2: second substrate) is applied to the reflective film (second substrate). Substrate (C1: first substrate) via the composition applied to the reflective film (first reflector film) surface of the substrate (C1: first substrate) so that the film surface of the reflector film becomes an adhesive surface. 1 substrate), and ultraviolet rays are irradiated from one or both surfaces of the two bonded substrates to bond them together to make “DVD-10”.

(Production of DVD-5)
An optical disk substrate (D: first substrate) is prepared in which a first reflective film having a thickness of 40 to 60 nm made of silver or an alloy containing silver as a main component is laminated on irregularities called pits that carry recording information. Separately, an optical disk substrate (E) having no pits is prepared. An ultraviolet curable composition is applied onto the first reflective film of the substrate (D: first substrate), and the substrate (D: first substrate) and the substrate (E) are bonded together via the composition. Then, ultraviolet rays are irradiated from one or both surfaces of the two bonded substrates to bond them together to make “DVD-5”.

  The ultraviolet irradiation can be performed by a continuous light irradiation method using, for example, a metal halide lamp, a high pressure mercury lamp, or the like, or by a flash light irradiation method described in US Pat. No. 5,904,795. The flash irradiation method is more preferable in that it can be cured efficiently.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

<Synthesis Example-1>
621 parts of castor oil fatty acid (acid value 180.7 KOHmg / g Toyokuni Oil), bisphenol A type epoxy manufactured by Dainippon Ink & Chemicals, Inc. in a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet, and a thermometer 384 parts of resin epiclone 850 and 2 parts of triphenylphosphine are added, and the temperature is raised to 110 ° C. while stirring. After reacting at 110 ° C. for 6 hours, dehydration under reduced pressure at 30 mmHg or less for 1 hour and cooling, an epoxy ester <E-1> having an acid value of 1.6 KOHmg / g was obtained.

<Synthesis Example-2>
625 parts of 12-hydroxystearic acid (acid number 179.6 KOHmg / g Toyokuni Oil), bisphenol manufactured by Dainippon Ink & Chemicals, Inc. in a reactor equipped with a stirrer equipped with a reflux condenser, a nitrogen inlet tube, and a thermometer 384 parts of A-type epoxy resin Epicron 850 and 2 parts of triphenylphosphine are added, and the temperature is raised to 110 ° C. while stirring. After reaction at 110 ° C. for 6 hours, dehydration under reduced pressure at 30 mmHg or less for 1 hour and cooling, an epoxy ester <E-2> having an acid value of 2.2 KOHmg / g was obtained.

<Synthesis Example-3>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet tube, and a thermometer, 348 parts of Plaxel FA2D (ε-caprolactone 2-mol adduct of 2-hydroxyethyl acrylate) manufactured by Daicel Chemical Industries, Ltd., 0.26 of methoquinone Part, 174 parts of TDI-100 (2,4-tolylene diisocyanate) manufactured by Mitsui Takeda Chemical Co., Ltd. were reacted at 40 to 45 ° C. for 6 hours to obtain <HU-2> with NCO% of 8.1%.

<Synthesis Example-4>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air introduction tube, and a thermometer, 458 parts of Plaxel FA3 (ε-caprolactone 3-mole adduct of 2-hydroxyethyl acrylate) manufactured by Daicel Chemical Industries, Ltd., 0.32 of methoquinone Part, 2,4-tolylene diisocyanate 174 parts, and reacted at 40-45 ° C. for 6 hours to obtain <HU-3> with NCO% 6.7%.

<Synthesis Example-5>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet tube, and a thermometer, 686 parts Plaxel FA5 (2-hydroxyethyl acrylate ε-caprolactone 5-mol adduct) manufactured by Daicel Chemical Industries, Ltd., and methoquinone 0.32 Part, 2,4-tolylene diisocyanate 174 parts, and reacted at 40-45 ° C. for 7 hours to obtain <HU-5> with NCO% 4.9%.

<Comparative Example-1>
A reactor equipped with a stirrer equipped with a reflux condenser, nitrogen, air inlet tube, and thermometer was charged with 348 parts of 2,4-tolylene diisocyanate at room temperature while blowing nitrogen, and PTG850 (Hodogaya Chemical Co., Ltd.) Polytetramethylene ether glycol) 850 parts are slowly charged at 45 ° C. or less over 1 hour, the reaction is continued at 45 to 55 ° C., and when NCO% becomes 7% after 3 hours, 0.7 part of methoquinone, 2-hydroxy Charge 232 parts of ethyl acrylate and 0.3 part of stannous octylate, gradually increase the temperature to 75 ° C. while controlling the temperature, react at 75 ° C. for 6 hours, and react until NCO% reaches 0.01% To obtain urethane acrylate <UA-1>. The molecular weight determined by GPC measurement was a number average molecular weight (Mn 1950), a weight average molecular weight (Mw 3490), and (Mw / Mn) was 1.79.

<Comparative Example-2>
A reactor equipped with a stirrer equipped with a reflux condenser, nitrogen, air inlet tube, and thermometer was charged with 444 parts of isophorone diisocyanate and 760 parts of Toyokuni Oil Castor diol (molecular weight 760) while blowing nitrogen. When the NCO% reaches 7%, 0.6 parts of methoquinone, 235 parts of 2-hydroxyethyl acrylate, and 0.8 parts of stannous octylate are added, and the temperature is gradually raised to 75 ° C. while controlling the temperature. Warm, react at 75 ° C. for 8 hours and react until NCO% is 0.07% to obtain urethane acrylate <UA-2>. The molecular weight determined by GPC measurement was a number average molecular weight (Mn 1610), a weight average molecular weight (Mw 3100), and (Mw / Mn) was 1.92.

<Example-1>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet tube, and a thermometer, 1001 parts of the epoxy ester <E-2> shown in Synthesis Example 2, 1044 parts of <HU-2> in Synthesis Example-3, 1.0 part of methoquinone and 0.4 part of tin octylate were added and reacted at 75 ° C. for 5 hours to obtain <GJ-1> having an NCO% of 0.02%. The molecular weight by GPC measurement was a number average molecular weight (Mn 2860), a weight average molecular weight (Mw 5780), and (Mw / Mn) was 2.02.

<Example-2>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air inlet tube, and a thermometer, 997 parts of the epoxy ester <E-1> shown in Synthesis Example 1 and 1044 parts of <HU-2> in Synthesis Example-3, 1.1 parts of methoquinone and 0.45 parts of tin octylate were added and reacted at 75 ° C. for 5 hours to obtain <GJ-2> having an NCO% of 0.03%. The molecular weight by GPC measurement was a number average molecular weight (Mn 2860), a weight average molecular weight (Mw 5600), and (Mw / Mn) was 1.96.

<Example-3>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air introduction tube, and a thermometer, 997 parts of the epoxy ester <E-1> shown in Synthesis Example 1, 1264 parts of <HU-3> in Synthesis Example-3, 1.0 part of methoquinone and 0.4 part of tin octylate were added and reacted at 75 ° C. for 5 hours to obtain <GJ-3> having an NCO% of 0.03%. The molecular weight determined by GPC measurement was a number average molecular weight (Mn 2800), a weight average molecular weight (Mw 6670), and (Mw / Mn) was 2.38.

<Example-4>
In a reactor equipped with a stirrer equipped with a reflux condenser, an air introduction tube, and a thermometer, 997 parts of the epoxy ester <E-1> shown in Synthesis Example 1, 632 parts of <HU-3> in Synthesis Example-3, <GU-4> in which <HU-5> 860 parts of Synthesis Example-4, 1.3 parts of methoquinone, and 0.5 parts of tin octylate were added and reacted at 75 ° C. for 5 hours to have an NCO% of 0.03%. > Was obtained. The molecular weight by GPC measurement was a number average molecular weight (Mn1980) and a weight average molecular weight (Mw5020), and (Mw / Mn) was 2.54.

<Preparation of UV curable composition and cured coating film>
Each composition blended according to the composition shown in Table 1 below was heated at 60 ° C. for 3 hours, stirred and dissolved to prepare an ultraviolet curable composition for each application example. The viscosity of each composition was measured with an E-type viscometer at 25 ° C.

The composition prepared as shown in the following table was applied to each substrate with a draw down rod # 6 and irradiated with ultraviolet rays under the following curing conditions to obtain a cured coating film.
Irradiation device: UV irradiation device manufactured by Igraphic Co., Ltd. Metal halide lamp: 120w, Conveyor speed: 10m / min, Irradiation amount: 230mJ / cm

<MEK rubbing test>
The MEK reagent grade 1 is soaked in a cotton swab (Kawamoto Sangyo Co., Ltd. # 103), rubbed at the same location, and the number of reciprocations until the coating film is peeled off and the substrate is exposed is noted. (Represents solvent resistance and UV curability.)

<Adhesion test>
Cross-cut-Adhesive tape peeling: Polycarbonate substrate (PC substrate) "EC100C" manufactured by Tsutsunaka Plastic Industry Co., Ltd. 0mm thickness 25 pieces of 6 cuts that intersect perpendicularly to 1 cm ² on the coated and cured coating on the PC substrate An adhesive tape peeling test is performed in which a grid pattern of / cm ² is made, and an adhesive tape is applied and peeled off. The number a of squares not peeled off from the substrate is expressed as a / 25, and 25/25 is excellent in close contact and indicates that none of the squares were peeled off.

<Transparency of coating film>
The transparency of the coating applied and cured on the PC substrate is visually observed, and the transparent one is transparent and the opaque one is turbid.

<Itching test>
Tosero Co., Ltd. biaxially stretched polypropylene film “OP U-1” 40 μm The film coated and cured on the corona-treated surface was rubbed with the film strongly 10 times.

表１

表１中、粘度の単位はｍＰａ・ｓ／２５℃

Table 1

In Table 1, the unit of viscosity is mPa · s / 25 ° C.

The compounds in Table 1 are as follows.
EOTMPTA: Aronix M-350 Toagosei Co., Ltd. (trimethylolpropane triethoxytriacrylate)
PHOTOMER4017: Cognis Japan Co., Ltd. (1,6-hexanediol diacrylate)
BPE4-A: Light acrylate BP4EA manufactured by Kyoeisha Chemical Co., Ltd. (diacrylate of bisphenol A ethylene oxide 4 mol adduct)
PHE: Osaka Organic Chemical Industry Co., Ltd. V # 192 Phenoxyethyl acrylate THFA: Osaka Organic Chemical Industry Co., Ltd. V # 150 Tetrahydrofurfuryl acrylate PM-2: Kayamar PM-2 Nippon Kayaku Co., Ltd. 2- Methacryloxyethyl acid phosphate Irg. 651: Irgacure 651 manufactured by Ciba Specialty Chemicals (2,2-dimethoxy-1,2-diphenylethane-1-one)
TPO: Darocur TPO Ciba Specialty Chemicals (2,4,6-trimethylbenzoyldiphenylphosphine oxide)
V-5530: Unidic V-5530 manufactured by Dainippon Ink & Chemicals, Inc. (bisphenol A skeleton epoxy acrylate)
OPP film: Biaxially stretched polypropylene film “OP U-1” manufactured by Tosero Co., Ltd. 40μm inner corona treatment

  In Application Example 7, the MEK rubbing test is inferior, in Application Example 8, the adhesion to the OPP film is inferior, and in Application Example 9, the adhesion to the OPP film and the transparency are inferior. On the other hand, Application Examples 1 to 6 have high MEK rubbing resistance (solvent resistance), excellent curability, and excellent transparency and adhesion to a polyolefin film.

Manufacturing method of optical disc <Preparation of optical disc composition and optical disc sample>
An optical disk sample was prepared by the method described below using the ultraviolet curable composition prepared in Application Example 4 (production of a DVD-9 test disk).
One polycarbonate substrate (A) for optical disc in which an aluminum metal thin film (reflective layer) of 40 to 60 nm is laminated on the irregularities called pits carrying recording information, and 15 nm on the irregularities called pits carrying recording information One optical disk polycarbonate substrate (B) on which a semi-transparent film (semi-transparent reflective layer) of an alloy mainly composed of silver is laminated is prepared.
Next, the ultraviolet curable composition of the present invention is applied on the metal thin film of the substrate (A), and the substrate (B) on which the semitransparent film is laminated is further bonded to the film surface of the semitransparent film as the adhesive surface. As such, the substrate (A) was superposed through the ultraviolet curable composition of the present invention applied to the metal thin film surface. Subsequently, it was rotated with a spin coater so that the film thickness of the cured coating film was about 50 to 60 μm. Next, using a “xenon flash irradiation device SBC-04 type” manufactured by Ushio Electric Co., Ltd., a 10-shot ultraviolet ray was irradiated in air from the substrate side with the silver alloy translucent film at a set voltage of 1800 V. A DVD-9 test disk using an ultraviolet curable composition was prepared.

The optical disk of the present invention using the ultraviolet curable composition for optical disks of Application Example 4 is sufficiently cured and has excellent adhesiveness that does not peel even in a drop test from 100 cm.
Furthermore, there is no warping or distortion of the optical disk.

Claims (6)

Hydroxy fatty acid (A);
An epoxy compound (B) having one or more glycidyl groups;
An active energy ray-curable compound obtained by reacting an isocyanate group and a compound (C) having an acryloyl group in the same molecule. The hydroxy fatty acid (A) is represented by the formula (1)

(Wherein R ¹ represents an alkylene group having 2 to 30 carbon atoms which may have a branched chain or an alkenylene group having 2 to 30 carbon atoms which may have a branched chain). The active energy ray-curable compound according to claim 1, which is a compound. The epoxy compound (B) having one or more glycidyl groups is represented by the formula (2)

(Wherein Y represents —SO ₂ —, —CH ₂ —, —CH (CH ₃ ) — or —C (CH ₃ ) ₂ —, and n represents an integer of 0 to 8). The active energy ray-curable compound according to claim 1, which is a compound. The compound (C) having an isocyanate group and an acryloyl group in the same molecule is represented by the formula (3)

(Wherein R ² is a hydrogen atom or a methyl group, R ³ is a C 1-8 alkylene group which may have a branched chain, and R ⁴ is a carbon which may have a branched chain or a ring structure. Represents a hydrocarbon group of formula 1 to 16, X is a single bond, formula (4)

(Wherein R ⁵ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and m represents an integer of 1 to 10) or formula (5)

(Wherein R ⁶ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and p represents an integer of 1 to 10). The active energy ray-curable compound according to claim 1, wherein the compound is represented by the formula: Formula (6)

(In the formula, R ¹ represents an alkylene group having 2 to 30 carbon atoms which may have a branched chain or an alkenylene group having 2 to 30 carbon atoms which may have a branched chain, and Y represents —SO _2. -, -CH _2- , -CH (CH ₃ )-or -C (CH ₃ ) ₂ -is represented, and Z is -OH or formula (7)

(Wherein R ² is a hydrogen atom or a methyl group, R ³ is a C 1-8 alkylene group which may have a branched chain, and R ⁴ is a carbon which may have a branched chain or a ring structure. A hydrocarbon group of formulas 1 to 16, X is a single bond, formula (4)

(Wherein R ⁵ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and m represents an integer of 1 to 10) or formula (5)

(In the formula, R ⁶ represents an alkylene group having 1 to 8 carbon atoms which may have a branched chain, and p represents an integer of 1 to 10). Does not become —OH, and n represents an integer of 0 to 8. ). An active energy ray-curable compound represented by: An active energy ray-curable composition comprising the active energy ray-curable compound according to any one of claims 1, 2, 3, 4 and 5.