JP5209310B2 - Photosensitive resin composition, cured product thereof, and film containing the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition that forms a cured film (cured product) having a high stress at break and excellent scratch resistance, and the cured film (cured product). Furthermore, the surface hardness of plastics such as polyester, acrylic, polycarbonate, polyethersulfone and the like, and a film having the cured film with less curling due to curing shrinkage, and further using the above resin composition and its cured product, The present invention relates to a next-generation high-density optical disk having a cured product with low water absorption and cure shrinkage and excellent transparency and durability.

  Currently, plastics are used in large quantities in industry, including the automobile industry, home appliance industry, and electrical and electronics industry. The reason why a large amount of plastic is used in this way is because it is lightweight, inexpensive, and has excellent optical properties in addition to its ease of processing and transparency. However, plastics have drawbacks such as being soft and easily scratched on the surface compared to glass and the like.

  In order to remedy these drawbacks, it is a common practice to coat the surface of plastic with a hard coating agent. As the hard coat agent, a thermosetting hard coat agent such as a silicon-based, acrylic-based, or melamine-based agent is used. In particular, silicon-based hard coating agents have been frequently used because of their high hardness and excellent quality. This high-value-added product such as glasses and lenses mostly uses this silicon-based hard coat agent. However, the silicon-based hard coat agent has a long curing time and is expensive, and cannot be said to be suitable as a hard coat agent for a continuously processed film. Attempts have also been made to add anti-reflection fillers to silicon hard coating agents, but because of the thermosetting resin, filler aggregation occurs during heating, and low reflectivity does not impair transparency. At present, there is no silicon hard coat.

  In recent years, radiation curable acrylic hard coating agents have been developed. The radiation curable hard coat agent is cured immediately by irradiation with radiation such as ultraviolet rays (active energy rays) to form a hard film, so that the processing speed is high, and the hardness, wear resistance, etc. are excellent. Since it has performance and is inexpensive in terms of total cost, it is now mainstream in the hard coat field. In particular, it is suitable for continuous processing of films such as polyester film, polyacrylate film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, and polyether sulfone film. Polyester film is laminated on glass for preventing shattering of glass or light-shielding film for automobiles, and for electronic materials such as touch panels, liquid crystal displays, CRT flat TVs (CRT displays), or iron plates of housings of household appliances such as refrigerators, and so on. In order to improve, it is widely used as a film on the surface of a whiteboard. In any of these applications, it is necessary to apply a hard coat so that the surface is not damaged.

  In recent years, the display surface of a CRT display or liquid crystal display provided with a film coated with a hard coat agent has a smooth surface, which makes it difficult to see the display screen due to reflection and causes eyes to become tired. ing. Therefore, depending on the application, a hard coat treatment having a surface reflection preventing ability is required. As a method for preventing surface reflection, a method in which an inorganic filler or a filler of organic fine particles is dispersed in a radiation curable resin is coated on a film, and the surface is made uneven to prevent reflection (AG treatment). A method of providing a multilayer structure in the order of a high refractive index layer and a low refractive index layer on a film to prevent reflection and reflection due to a difference in refractive index (AR processing), or AG / AR processing combining the above two methods There are methods.

  While a hard coat imparted with functionality is required, many studies for further improving the hardness (hardness) of the hard coat itself are still being conducted. For example, Patent Document 1 achieves an improvement in hardness by adding a polyfunctional urethane acrylate to a resin composition. However, since the curing shrinkage of the polyfunctional urethane acrylate used is large and there is a tendency to generate cracks and curl of the film, there is a limit to the amount of addition or composition.

  Also, CD (compact disc), MO (magneto-optical disc), CD-R (write-once compact disc), CD-RW (rewritable compact disc), etc. are common as optical disc recording media that have been put into practical use. is there. In these, a recording film and a reflective film are formed on a 1.2 mm polycarbonate substrate, and a protective layer of an ultraviolet curable coating agent is provided for the purpose of protecting them from external factors. In recent years, the polycarbonate thickness has been reduced to 0.6 mm, which is half the conventional thickness, in order to further improve the storage capacity, and the problem of birefringence of the polycarbonate substrate and the laser spot diameter can be reduced by bonding the two substrates together. DVD-R, DVD-RW, DVD-RAM, DVD + R, DVD + RW, and the like that have cleared the problem of being put into practical use. Each of them forms a recording film, a reflective film, etc. on a 0.6 mm polycarbonate substrate, and is provided with an ultraviolet curable protective layer or adhesive layer for the purpose of protection and adhesion as described above.

  However, as a recording medium corresponding to the increase in capacity in the age of digital broadcasting, the capacity of a DVD recording medium is still insufficient. Therefore, as a next-generation high-density optical disc, a type of optical disc is proposed, in which a recording layer and a 100 μm transparent layer are laminated on a substrate, and writing and reading are performed with blue laser light from the transparent cover layer side instead of a polycarbonate substrate ( Patent Document 2) has been put into practical use.

  As a method of forming this cover layer, there are a method of bonding a 100 μm transparent film and a method of forming a 100 μm layer on a recording film using an ultraviolet curable resin. As a method of forming an ultraviolet curable resin layer, The 2P method and the spin coater method have been proposed. As an ultraviolet curable resin formed on such a recording film, for example, 2P agents such as compositions described in Patent Document 3 and Patent Document 4 have been proposed. In addition, protective coating agents such as the compositions described in Patent Document 5, Patent Document 6, and Patent Document 7 have been proposed.

JP 2001-113648 A Japanese Patent Laid-Open No. 11-273147 JP-A-5-059139 JP-A-5-132534 Japanese Patent Laid-Open No. 3-131605 JP-A-3-172358 JP 2003-268263 A

While the thickness of the base film is limited, in order to develop a harder hard coat, materials such as hard materials are used, the degree of crosslinking is increased, the film thickness is set thicker, etc. There are problems such as generation of cracks and generation of curling by increasing the degree of crosslinking with a thick film.
The present invention provides an active energy ray-curable resin composition suitable for a hard coat that is capable of low-curl and thick-film coating and does not generate cracks, a cured film thereof, and a film having the cured film, and further shrinkage by curing. An object of the present invention is to provide a resin composition having a low rate and having a low warpage and excellent durability suitable for use in a transparent cover layer of a high-density optical disc.

  As a result of intensive studies to achieve the above object, the present inventors have found a photosensitive resin composition having a specific composition and completed the present invention.

That is, the present invention
(1) An isocyanate compound (A) which is a reaction product of a diisocyanate compound (a) and an alcohol compound (b) having at least two hydroxyl groups in the molecule, or one isocyanate group of the diisocyanate compound (a) is an isocyanurate ring A polyfunctional (meth) acrylate compound having one or more hydroxyl groups as a polyhydric alcohol (meth) acrylate compound and a polyfunctional compound in which all hydroxyl groups are ester-bonded (A) having a structure, A photosensitive resin obtained by reacting with a mixture (B) of a polyfunctional (meth) acrylate compound containing a (meth) acrylate compound;
(2) The photosensitive resin according to the above (1), wherein the alcohol compound (b) having at least two or more hydroxyl groups in the molecule has a weight average molecular weight of 100 to 1500;
(3) The photosensitivity according to (1) or (2) above, wherein the polyfunctional (meth) acrylate compound having one or more hydroxyl groups is pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate. resin;
(4) The photosensitive resin according to any one of (1) to (3) above, wherein the mixture (B) is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate;
(5) A photosensitive resin composition comprising the photosensitive resin according to any one of (1) to (4) above and a photopolymerization initiator (C);
(6) The photosensitive resin composition according to (5), further containing a polymerizable compound (D);
(7) The polymerizable compound (D) is (poly) ester (meth) acrylate (D-1), urethane (meth) acrylate (D-2), epoxy (meth) acrylate (D-3), (poly). Ether (meth) acrylate (D-4), alkyl (meth) acrylate or alkylene (meth) acrylate (D-5), (meth) acrylate (D-6) having an aromatic ring, (meth) having an alicyclic structure The photosensitive resin composition according to the above (6), which is one or more compounds selected from the group consisting of acrylate (D-7), a maleimide group-containing compound, a (meth) acrylamide compound, and an unsaturated polyester;
(8) A cured product of the photosensitive resin composition according to any one of (5) to (7) above;
(9) A film containing the cured product according to (8) above;
(10) The photosensitive resin composition according to any one of (5) to (7), which is a protective coating agent for optical disks;
(11) The cured product of the photosensitive resin composition according to (8), wherein the cured product has a water absorption rate (measurement temperature of 25 ° C.) of 2.0% or less and a cure shrinkage rate of 6% or less;
(12) The cured product according to (8) or (11) above, wherein the transmittance of the blue laser at a film thickness of 50 to 150 μm is 70% or more;
(13) An optical disc having the cured product layer according to (8), (11) or (12) above;
(14) The optical disc according to (13), wherein a cured product layer is formed on a side on which recording light and / or reproduction light is incident;
About.

The cured film (cured material) of the photosensitive resin composition of the present invention has low curl, less cracking, and can improve the hardness of the cured film. In addition to hard coat films that require high hardness, ink Various coating fields such as plastic paint, paper printing, metal coating, furniture coating, lining, adhesives, and insulation varnishes, insulating sheets, laminates, printed circuit boards, resist inks, semiconductor sealants, etc. in the electronics field It can be applied to many fields.
In addition, the resin composition of the present invention and the cured product thereof can provide a protective coating agent for a high-density optical disk having excellent transparency, low water absorption, and high durability with little warpage, and a cured product thereof. Therefore, the present invention is extremely useful for an optical disc that performs reading and / or writing using a blue laser.

  The photosensitive resin of the present invention is an isocyanate compound (A) that is a reaction product of a diisocyanate compound (a) and an alcohol compound (b) having at least two hydroxyl groups in the molecule, or one isocyanate of the diisocyanate compound (a). An isocyanate compound (A ′) in which the group forms an isocyanurate ring structure, a polyfunctional (meth) acrylate compound having one or more hydroxyl groups as a (meth) acrylate compound of a polyhydric alcohol, and all hydroxyl groups are esters It is obtained by reacting with a mixture (B) of a polyfunctional (meth) acrylate compound containing a bonded polyfunctional (meth) acrylate compound.

  Examples of the diisocyanate compound (a) in the present invention include compounds in which two isocyanate groups are substituted on a chain saturated hydrocarbon, a cyclic saturated hydrocarbon, and an aromatic hydrocarbon. Specifically, for example, tetramethylene Chain saturated hydrocarbon diisocyanates such as diisocyanate, hexamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane Diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, norbornene diisocyanate, etc. Aromatic diisocyanates such as a saturated saturated hydrocarbon diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalene diisocyanate Although it is mentioned, it is not limited to this. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  Although it does not specifically limit as an alcohol compound (b) which has at least 2 or more hydroxyl group in a molecule | numerator, The compound whose weight average molecular weight is 100-1500 is preferable, Specifically, for example, polybutylene glycol, polytetramethylene glycol, Polyether polyols such as polypropylene glycol and polyethylene glycol, polyethylene glycol adipate, poly 1,4-butanediol adipate, polyester polyols such as polycaprolactone, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentyl Glycols such as glycol, cyclohexane dimethylol, hydrogenated bisphenol A, hydrogenated bisphenol F, spiro skeleton-containing alcohol, tricyclodecanedi Cycloaliphatic alcohols such as tyrol, pentacyclopentadecane dimethylol or alkylene oxide adducts thereof, branched or linear long-chain alkyl diols such as hydrogenated polybutadiene diols, bisphenols such as bisphenol A and bisphenol F, bisphenols By reaction of polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol, alkylene oxide adducts of these polyols, and polybasic acids such as adipic acid Examples thereof include polyester polyols obtained and polycarbonate polyols.

The reaction of the diisocyanate compound (a) for obtaining the isocyanate compound (A) used in the production of the photosensitive resin of the present invention and the alcohol compound (b) having at least two hydroxyl groups in the molecule is carried out after the reaction with an isocyanate group. Charge in the equivalent relationship that remains. If the charge amount of the alcohol compound (b) is reduced and the charge ratio is increased, the resulting isocyanate compound (A) is almost free from substances derived from the alcohol compound, and the occurrence of cracks in the photosensitive resin composition increases. It becomes easy. On the other hand, when the charging ratio is reduced, the molecular weight increases and the curability of the photosensitive resin composition tends to be affected.
Specifically, the OH group of the alcohol compound (b) is 0.1 to 0.9 mol, preferably 0.20 to 0.85 mol with respect to 1.0 mol of the NCO group of the diisocyanate compound (a). That's fine.

  The reaction can be performed without a solvent, but may be performed in a solvent in order to improve workability when the viscosity of the product is high. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol dimethyl ether. , Glycol diethers such as dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, dialkyl glutarate (eg, dimethyl glutarate), esters such as dialkyl succinate (eg, dimethyl succinate), dialkyl adipate (eg, dimethyl adipate), γ-butyrolactone, etc. These include cyclic esters, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, and other petroleum solvents, and a mixed solvent thereof may be used.

The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C.
The end point of the reaction may be confirmed by reducing the amount of isocyanate by, for example, IR (infrared absorption spectrum) or back titration with an acid by reacting the remaining isocyanate with an excess base.

A catalyst may be added for the purpose of shortening the reaction time of the reaction, and either a basic catalyst or an acidic catalyst may be used as the catalyst.
Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine.
Examples of acidic catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin 2-ethylhexanoate, octyltin trilaurate, dibutyltin Examples include Lewis acid catalysts such as dilaurate and octyltin diacetate. When adding these catalysts, the addition amount is 0.1-1 weight part normally with respect to 100 weight part of isocyanate compounds (A) to produce | generate.

  The isocyanate compound (A ′) used in the production of the photosensitive resin of the present invention is a compound having an isocyanurate ring structure which is a trimer formed by one isocyanate group of the diisocyanate compound (a). Specifically, a trimer of tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate can be used.

Polyfunctional (meth) acrylate compounds having one or more hydroxyl groups and polyfunctional (meth) acrylates in which all hydroxyl groups are ester-bonded as (meth) acrylate compounds of polyhydric alcohols used in the production of the photosensitive resin of the present invention Although it does not specifically limit as a mixture (B) containing a compound, Specifically, it is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra One or more polyfunctional (meth) acrylates selected from the group consisting of (meth) acrylate, dipentaerythritol tri (meth) acrylate and dipentaerythritol di (meth) acrylate and dipentaerythritol hexa (meth) acrylate Mixtures over preparative; mixtures of trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate. These may further be used multiple mixtures thereof.
The mixture (B) is preferably a mixture containing pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate, and particularly a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The ratio of the polyfunctional (meth) acrylate compound having one or more hydroxyl groups in the mixture (B) is 20 to 95% by weight of the entire mixture (B) including the polyfunctional (meth) acrylate compound in which all hydroxyl groups are ester-bonded. Degree.

The polyfunctional (meth) acrylate compound having one or more hydroxyl groups as the polyhydric alcohol (meth) acrylate compound used in the production of the above-described photosensitive resin of the present invention and the polyfunctional (meta) having all hydroxyl groups ester-bonded As the mixture (B) containing an acrylate compound, a reaction product obtained by subjecting a polyhydric alcohol to a (meth) acrylate reaction may be used.
Furthermore, you may use it, adding the polymeric compound (D) mentioned later.

  The photosensitive resin of the present invention is obtained by the reaction of the isocyanate compound (A) or the isocyanate compound (A ′) with a mixture (B) of a polyfunctional (meth) acrylate compound. The equivalence relation is charged so that there is no more. Specifically, preferably, the OH group of the polyfunctional (meth) acrylate compound mixture (B) is 1.0 to 3.0 mol, more preferably 1.0 to 2.0 mol, relative to 1.0 mol of the NCO group of the isocyanate compound. You just have to be prepared.

The reaction can be carried out without a solvent, but the same solvent as the solvent that may be used in the reaction of the diisocyanate compound (a) and the alcohol compound (b) having at least two hydroxyl groups in the molecule. It may be carried out in the inside, or may be carried out by adding a polymerizable compound (D) described later, and may be carried out in the polymerizable compound (D).
The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C.
The end point of the reaction can be confirmed by reducing the amount of isocyanate, for example, IR, or reacting the remaining isocyanate with an excess base and performing back titration with an acid.
For the purpose of shortening the reaction time of the reaction, a compound similar to the catalyst that may be used in the reaction of the diisocyanate compound (a) and the alcohol compound (b) having at least two hydroxyl groups in the molecule is added. The amount of addition may be the same.

Usually, a polymerization inhibitor such as p-methoxyphenol is added to the mixture (B) of the polyfunctional (meth) acrylate compound, but hydroquinone, p-methoxyphenol, 2, 4 are added during the reaction. -A polymerization inhibitor such as dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, phenothiazine and the like may be newly added. When a polymerization inhibitor is added, the amount used is 0.01 to 1% by weight based on the mixture (B) of the polyfunctional (meth) acrylate compound.
In addition, as content of the photosensitive resin in the photosensitive resin composition of this invention, when the solid content of the photosensitive resin composition is 100 weight%, 5-90 weight% normally, Preferably it is 10-86 weight% %.

  The photosensitive resin composition of the present invention may further contain a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited, and specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl Acetophenones such as 2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as xanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethyl Benzophenones such as aminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. The addition ratio of these is usually 0.01 to 30% by weight, preferably 0.1 to 25% by weight, when the solid content of the photosensitive resin composition is 100% by weight.

  These may be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, and N, N-dimethylaminobenzoic acid. You may use in combination with reaction promoters, such as benzoic acid derivatives, such as acid isoamyl ester. When these reaction accelerators are used, the amount added is 100% by weight or less based on the photopolymerization initiator (C).

  The photosensitive resin composition of the present invention may further contain a polymerizable compound (D). Examples of the polymerizable compound (D) include a compound having a (meth) acryloyloxy group, a maleimide group-containing compound, a (meth) acrylamide compound, and an unsaturated polyester.

  Examples of the compound having a (meth) acryloyloxy group include (poly) ester (meth) acrylate (D-1), urethane (meth) acrylate (D-2), epoxy (meth) acrylate (D-3), (poly ) Ether (meth) acrylate (D-4), alkyl (meth) acrylate or alkylene (meth) acrylate (D-5), (meth) acrylate (D-6) having an aromatic ring, and having an alicyclic structure (meta) ) Acrylate (D-7) and the like.

  Examples of maleimide group-containing compounds include Nn-butylmaleimide, Nn-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate. Monofunctional aliphatic maleimides such as N-cyclohexylmaleimide; monocyclic malefunctional maleimides such as N-cyclohexylmaleimide; N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) ) Aliphatic bismaleimides such as carbonate; Alicyclic bismaleimides such as 1,4-dimaleimidocyclohexane and isophorone bisurethane bis (N-ethylmaleimide); obtained by esterification of maleimidoacetic acid and polytetramethylene glycol (Poly) ester (Poly) maleimide obtained by esterification of carboxymaleimide derivatives such as maleimide compound and various (poly) ols by esterification of maleimide caproic acid with pentaerythritol tetraethylene oxide adduct Compounds and the like.

  Examples of (meth) acrylamide compounds include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide.

  Examples of the unsaturated polyester include fumaric acid esters such as dimethyl maleate and diethyl maleate; and esterification reaction products of polyunsaturated carboxylic acids such as maleic acid and fumaric acid and polyhydric alcohols.

  (Poly) ester (meth) acrylate (D-1) as a compound having a (meth) acryloyloxy group is a general term for (meth) acrylate having one or more ester bonds in the main chain, for example, caprolactone-modified 2 -Monofunctional (poly) esters such as hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate (Meth) acrylates; hydroxypivalate ester neopentyl glycol di (meth) acrylate; caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate; epichlorohydrin modification Di (meth) acrylate of phthalic acid: Triol mono, di or tri obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of trimethylolpropane or glycerin (Meth) acrylate: mono, di, tri or tetra of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol or ditrimethylolpropane (Meth) acrylate: Triol mono- or poly (meth) acrylate triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of dipentaerythritol , Tetraol, pen Mono (meth) acrylate or poly (meth) acrylate of polyhydric alcohol such as all or hexaol; (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl Diol components such as -1,5-pentanediol and hexanediol and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid (Meth) acrylates of polyester polyols which are reaction products of polybasic acids such as 5-sodiumsulfoisophthalic acid or their anhydrides; the diol component and polybasic acids or their anhydrides and ε-caprolactone, γ- Butyrolactone, δ-valerola Examples include polyfunctional (poly) ester (meth) acrylates such as (meth) acrylates of cyclic lactone-modified polyester diols made of kuton and the like.

  Urethane (meth) acrylate (D-2) as a compound having a (meth) acryloyloxy group is a general term for (meth) acrylate having one or more urethane bonds in the main chain, and at least one (meth) acryloyl. It is a (meth) acrylate compound obtained by the reaction of a hydroxy compound having an oxy group (D-2-I) and an isocyanate compound (D-2-B).

  Examples of the hydroxy compound (D-2-i) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-hydroxy-3- Examples thereof include phenoxypropyl (meth) acrylate, a ring-opening reaction product of (meth) acrylate compound having a hydroxyl group and ε-caprolactone.

  Examples of the isocyanate compound (D-2-ro) include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate and naphthalene diisocyanate; aliphatic or alicyclic such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Diisocyanates having a structure; one or more burettes of isocyanate monomers; trimerizing these diisocyanate compounds Polyisocyanate isocyanurate and the like; polyisocyanate compounds obtained by the urethanization reaction of these diisocyanate compounds and the polyol compounds.

  The reaction of the hydroxy compound (D-2-i) having at least one (meth) acryloyloxy group and the isocyanate compound (D-2-ro) is carried out by reacting the isocyanate compound (A) or the isocyanate compound (A ′ ) And the polyfunctional (meth) acrylate compound mixture (B).

The epoxy (meth) acrylate (D-3) as a compound having a (meth) acryloyloxy group is a (meth) acrylate obtained by reacting a compound containing one or more epoxy groups with (meth) acrylic acid. A generic term for compounds.
Examples of the compound containing one or more epoxy groups include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether; bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol -S type epoxy resin, bisphenol type epoxy compound such as epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane; hydrogenated bisphenol-A type epoxy Resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Hydrogenation bis such as epoxy compounds Enol type epoxy compounds; halogenated bisphenol type epoxy compounds such as brominated bisphenol-A type epoxy resin and brominated bisphenol-F type epoxy resin; alicyclic diglycidyl ether compounds such as cyclohexanedimethanol diglycidyl ether compound; Aliphatic diglycidyl ether compounds such as 6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether; polysulfide type diglycidyl ether compounds such as polysulfide diglycidyl ether; phenol novolac type epoxy resin, Cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, bife Lumpur type epoxy resin, bisphenol -A novolac epoxy resins, naphthalene skeleton-containing epoxy resins, heterocyclic epoxy resins.

  Epoxy (meth) acrylate (D-3) can be obtained by subjecting a compound containing these epoxy groups and (meth) acrylic acid to normal reaction conditions.

  (Poly) ether (meth) acrylate (D-4) as a compound having a (meth) acryloyloxy group is a general term for (meth) acrylate having one or more ether bonds in the main chain, for example, butoxyethyl (Meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin modified butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, Monofunctional (poly) ether (meth) acrylates such as phenoxyethyl (meth) acrylate and nonylphenoxypolyethylene glycol (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( ) Alkylene glycol di (meth) acrylates such as acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran , Polyfunctional (meth) derived from polyhydric hydroxyl compounds such as hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol and (meth) acrylic acid Acrylates: Di (meth) acrylates of diols in which 1 mol or more of cyclic ether such as ethylene oxide, propylene oxide, butylene oxide is added to 1 mol of neopentyl glycol; bisphenol A, Di (meth) acrylates of alkylene oxide modified products of bisphenols such as Sphenol F and bisphenol S; alkylene oxide modified products of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S ) Acrylate; mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of trimethylolpropane or glycerol; pentaerythritol or ditrile Mono-, di-, tri- or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide to 1 mol of methylolpropane; Multifunctional (poly) ether (meth) acrylates such as 3-6 functional (meth) acrylates of hexaol in which 1 mol or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide are added to 1 mol of intererythritol Is mentioned.

  The alkyl (meth) acrylate or alkylene (meth) acrylate (D-5) as a compound having a (meth) acryloyloxy group is a linear alkyl or halogen atom optionally substituted with a halogen atom and / or a hydroxyl group, and / Or generic name of branched alkyl (meth) acrylate optionally substituted with a hydroxyl group, for example, monofunctional such as octyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, etc. (Meth) acrylates; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meta) a Dilates of hydrocarbon diols such as relate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate ) Acrylates; trimethylolpropane mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), glycerin Triols such as mono (meth) acrylate or poly (meth) acrylate, mono or poly (meth) acrylate of pentaerythritol, mono or poly (meth) acrylate of ditrimethylolpropane, mono or poly (meth) acrylate of dipentaerythritol, Tetraol, hexaol, etc. Mono- or poly (meth) acrylates of alcohols; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. .

  The (meth) acrylate (D-6) having an aromatic ring as a compound having a (meth) acryloyloxy group is a general term for a (meth) acrylate having an aromatic ring in the main chain or a side chain. And monofunctional (meth) acrylates such as meth) acrylate and benzyl (meth) acrylate; di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate.

  The (meth) acrylate (D-7) having an alicyclic structure as a compound having a (meth) acryloyloxy group is an alicyclic ring which may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain. A general term for (meth) acrylates having a formula structure, for example, monofunctional (having an alicyclic structure such as cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate) (Meth) acrylates; di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; polyfunctional (meth) having an alicyclic structure such as tricyclodecane dimethylol di (meth) acrylate Acrylates; oxygen atoms in the structure of tetrafurfuryl (meth) acrylate, etc. Alicyclic (meth) acrylate having.

  Examples of the polymerizable compound (D) that may be contained in the photosensitive resin composition of the present invention include, in addition to the above-described compounds, a reaction product of (meth) acrylic acid polymer and glycidyl (meth) acrylate or glycidyl. Poly (meth) acrylic polymer (meth) acrylate such as a reaction product of (meth) acrylate polymer and (meth) acrylic acid; (meth) acrylate having amino group such as dimethylaminoethyl (meth) acrylate; Tris (meth) Examples include isocyanurate (meth) acrylates such as acryloxyethyl isocyanurate; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates; melamine (meth) acrylates, and the like. Compound (A ′) and polyfunctional ( As long as it is a compound having a mixture (B) a photosensitive resin composition obtained by reacting a copolymerizable with data) acrylate compounds can be used without particular limitations.

  In the photosensitive resin composition of the present invention, preferred as the polymerizable compound (D) used when applied on a film and cured is a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetraacrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, a mixture of dipentaerythritol di (meth) acrylate and dipentaerythritol hexa (meth) acrylate, trimethylolpropane di ( And a mixture of (meth) acrylate and trimethylolpropane tri (meth) acrylate.

  In the photosensitive resin composition of the present invention, when the photosensitive resin composition of the present invention is used as an optical disk protective coating agent, preferred as the polymerizable compound (D) are neopentyl glycol di (meth) acrylate, tricyclo Decane dimethylol di (meth) acrylate, hydroxypivalaldehyde-modified trimethylolpropane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentanyl di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified trimethylo Rupuropantori (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate.

  When the polymerizable compound (D) is contained in the photosensitive resin composition of the present invention, the content thereof is the isocyanate compound (A) or the mixture (B) of the isocyanate compound (A ′) and the polyfunctional (meth) acrylate compound. The amount is preferably about 10 to 2000% by weight, particularly preferably about 50 to 1000% by weight, based on 100% by weight of the resin composition obtained by reacting.

  The photosensitive resin composition of the present invention includes a non-reactive compound, an inorganic filler, an organic filler, a silane coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, and an antioxidant depending on the application. An agent, an ultraviolet absorber, a flame retardant, a pigment, a dye, and the like can be appropriately contained.

  Non-reactive compounds are low-reactivity or non-reactive liquid or solid oligomers and resins, such as (meth) acrylic acid alkyl copolymers, epoxy resins, liquid polybutadiene, dicyclopentadiene derivatives, Examples include saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, and the like.

  Examples of inorganic fillers include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica , Barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen atom, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group such as a group.

  Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethyl methacrylate resin, fluororesin, nylon 12 , Nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin and the like.

  Any known and commonly used tackifiers, antifoaming agents, leveling agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, pigments and dyes can be used in the photosensitive resin composition of the present invention. It can contain without a restriction | limiting especially in the range which does not impair sclerosis | hardenability and a resin characteristic.

  The photosensitive resin composition of the present invention can be obtained by mixing the above-described components, and the order and method of mixing are not particularly limited.

  The photosensitive resin composition of the present invention does not need to contain a solvent in particular. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetates such as ethyl acetate and butyl acetate, aromatics such as benzene, toluene and xylene It may be used after being diluted with an organic solvent used for dissolving a group hydrocarbon or other usually photosensitive resin composition.

  The photosensitive resin composition of the present invention can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm, that is, active energy rays, and a cured product thereof is also included in the present invention.

  Examples of the source of the active energy ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, a short arc lamp, helium and cadmium. A laser, an argon laser, an excimer laser, sunlight, etc. are mentioned.

  The photosensitive resin composition of the present invention comprises a metal such as ink, aluminum, iron and copper; a plastic such as vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, polyethylene and polypropylene; a ceramic such as glass; wood; paper; It can be used for applications such as coating agents such as fibers, surface treatment agents, binders, plastic materials, molding materials, laminates, adhesives, and pressure-sensitive adhesives. Moreover, the film containing the hardened | cured material of the photosensitive resin composition of this invention is also contained in this invention.

  Specifically, planographic relief ink, flexographic ink, gravure ink, screen ink and other ink fields, glossy field, paper coating material field, woodworking paint field, beverage can coating material or printing ink field, flexible packaging film The coating agent, printing ink or pressure-sensitive adhesive, thermal paper, thermal film coating agent, printing ink, adhesive, pressure-sensitive adhesive, or optical fiber coating agent.

  When the resin composition of the present invention is used as a resin composition for an optical disk, it is desirable that the viscosity at 25 ° C. measured with a B-type viscometer is 100 to 5000 mPa · S, and the curing shrinkage when cured. The rate is preferably 6% or less, and the water absorption of the cured product (measurement temperature 25 ° C.) is preferably 2.0% or less.

  The protective coating agent for an optical disk using the resin composition of the present invention may be any coating method as long as the film thickness can be 50 to 100 μm. Examples of the coating method include spin coating, 2P, and roll. Examples thereof include a coating method and a screen printing method.

In addition, since a blue laser of about 400 nm is used for reading and / or writing in the next generation high-density optical disc, the transmittance around 400 to 500 nm is 70% or more in a cured product with a film thickness of 50 to 150 μm. It is preferable.
Furthermore, in the optical disk according to the present invention, it is preferable that the cured product layer of the ultraviolet curable resin composition is formed on the recording light and / or reproducing light incident side.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to the following Example. The molecular weight is a weight average molecular weight, and is measured by GPC (gel permeation chromatography).

Example 1
To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, 97.8 g of Takelac U-2410T (poly 1,4-butanediol adipate made by Mitsui Takeda Chemical, hydroxyl value 114.8 mgKOH / g) OH: 0.2 mol equivalent) and 44.5 g of isophorone diisocyanate (NCO: 0.4 mol equivalent) were added and reacted at 80 ° C., and the reaction was continued until the OH group reacted and the NCO content reached the theoretical value. Thereafter, the internal temperature was lowered to 50 ° C., 0.122 g of 4-methoxyphenol as a polymerization inhibitor and 0.122 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and pentaerythritol triacrylate and pentaerythritol tetraacrylate were stirred. A mixture (parts by weight: 65/35, hydroxyl equivalent: 458.9 Eq) of 101.0 g (OH: 0.22 mol equivalent) was added in three portions so that the internal temperature did not exceed 70 ° C. and added. Thereafter, the reaction was carried out at 70 ° C., and the end point of the reaction was determined when the NCO content was 0.1% or less. The obtained photosensitive resin (C-1) had a viscosity of 33.1 Pa · s (E-type viscometer, 60 ° C.) and Mw = 7,400 (GPC measurement, polystyrene conversion).

Example 2
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 87.7 g (OH: 0.2 mol) of PTG-850 (Hodogaya Chemicals polytetramethylene glycol, hydroxyl value 127.9 mgKOH / g). Equivalent) and 44.5 g (NCO: 0.4 mol equivalent) of isophorone diisocyanate were added and reacted at 80 ° C., and the reaction was continued until the OH group reacted and the NCO content reached the theoretical value. Thereafter, the internal temperature was lowered to 50 ° C., 0.117 g of 4-methoxyphenol as a polymerization inhibitor and 0.117 g of dibutyltin dilaurate as a urethanization reaction catalyst were added and stirred until uniform, and pentaerythritol triacrylate and pentaerythritol tetraacrylate were stirred. A mixture (parts by weight: 65/35, hydroxyl equivalent: 458.9 Eq) of 101.0 g (OH: 0.22 mol equivalent) was added in three portions so that the internal temperature did not exceed 70 ° C. and added. Thereafter, the reaction was carried out at 70 ° C., and the end point of the reaction was determined when the NCO content was 0.1% or less. The obtained photosensitive resin (C-2) had a viscosity of 23.9 Pa · s (E-type viscometer, 60 ° C.) and Mw = 7,800 (GPC measurement, polystyrene conversion).

Example 3
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 30.4 g (OH: 0.2 mol equivalent) of a diol compound represented by the following formula (1), 44.5 g (NCO: NCO: 0.4 mol equivalent) was added and reacted at 90 ° C., and the reaction was continued until the OH group reacted and the NCO content reached the theoretical value. Thereafter, the internal temperature is lowered to 50 ° C., and 0.088 g of 4-methoxyphenol as a polymerization inhibitor, 0.088 g of dibutyltin dilaurate as a urethanization reaction catalyst, and 44.0 g of MEK (2-butanone) as a reaction solvent are added to be uniform. To a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 65/35, hydroxyl equivalent: 458.9 Eq) with an internal temperature of 70 ° C. In order not to exceed, the mixture was charged in three portions, and the reaction was carried out at 70 ° C. after the addition. The obtained photosensitive resin (C-3) had a viscosity of 14.0 Pa · s (E-type viscometer, 25 ° C.) and Mw = 3,500 (GPC measurement, polystyrene conversion).

Example 4
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 39.3 g (OH: 0.4 mol equivalent) of a diol compound represented by the following formula (2), 88.9 g (NCO: 0.8 mol equivalent) was added and reacted at 90 ° C., and the reaction was continued until the OH group reacted and the NCO content reached the theoretical value. Thereafter, the internal temperature is lowered to 50 ° C., and 0.165 g of 4-methoxyphenol is added as a polymerization inhibitor, 0.165 g of dibutyltin dilaurate is added as a urethanization reaction catalyst, and 82.5 g of MEK (2-butanone) is added as a reaction solvent. To a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 65/35, hydroxyl group equivalent: 458.9 Eq) of 201.9 g (OH: 0.44 mol equivalent) In order not to exceed, the mixture was charged in three portions, and the reaction was carried out at 70 ° C. after the addition. The obtained photosensitive resin (C-4) had a viscosity of 5.8 Pa · s (E-type viscometer, 25 ° C.) and Mw = 2,900 (GPC measurement, converted to polystyrene).

Example 5
In a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device, 43.7 g (OH: 0.4 mol equivalent) of a diol compound represented by the following formula (3), 88.9 g (NCO: 0.8 mol equivalent) was added and reacted at 90 ° C., and the reaction was continued until the OH group reacted and the NCO content reached the theoretical value. Thereafter, the internal temperature is lowered to 50 ° C., and 0.167 g of 4-methoxyphenol as a polymerization inhibitor, 0.167 g of dibutyltin dilaurate as a urethanization reaction catalyst, and 83.6 g of MEK (2-butanone) as a reaction solvent are added to be uniform. To a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 65/35, hydroxyl group equivalent: 458.9 Eq) of 201.9 g (OH: 0.44 mol equivalent) In order not to exceed, the mixture was charged in three portions, and the reaction was carried out at 70 ° C. after the addition. The obtained photosensitive resin (C-5) had a viscosity of 15.2 Pa · s (E-type viscometer, 25 ° C.) and Mw = 3,000 (GPC measurement, polystyrene conversion).

Example 6
To a reactor equipped with a reflux condenser, stirrer, thermometer, and temperature controller, add 0.067 g of 4-methoxyphenol as a polymerization inhibitor and 0.067 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stir until uniform. Then, 101.0 g (OH: 0.22 mol equivalent) of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 65/35, hydroxyl group equivalent: 458.9 Eq) was added to adjust the internal temperature to 50 ° C. . Subsequently, 33.6 g (NCO: 0.2 mol equivalent) of TPA-100 (hexamethylene diisocyanate trimer: isocyanurate ring-containing compound) was added in three portions so that the internal temperature did not exceed 70 ° C, and added. Thereafter, the reaction was carried out at 70 ° C., and the end point of the reaction was determined when the NCO content was 0.1% or less. The obtained photosensitive resin (C-6) had a viscosity of 12.6 Pa · s (E-type viscometer, 60 ° C.) and Mw = 6,200 (GPC measurement, polystyrene conversion).

Example 7
To a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature controller, add 0.161 g of 4-methoxyphenol as a polymerization inhibitor and 0.161 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stir until uniform. Then, 288.5 g (OH: 0.22 mol equivalent) of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (parts by weight mixing ratio: 40/60, hydroxyl group equivalent: 1311.3 g / Eq) was added to adjust the internal temperature. The temperature was 50 ° C. Subsequently, 33.6 g (NCO: 0.2 mol equivalent) of TPA-100 (hexamethylene diisocyanate trimer: isocyanurate ring-containing compound) was added in three portions so that the internal temperature did not exceed 70 ° C, and added. Thereafter, the reaction was carried out at 70 ° C., and the end point of the reaction was determined when the NCO content was 0.1% or less. The obtained photosensitive resin (C-7) had a viscosity of 36.0 Pa · s (E-type viscometer, 60 ° C.) and Mw = 11,200 (GPC measurement, polystyrene conversion).

Comparative Synthesis Example A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (parts by weight mixing ratio: 65/35, hydroxyl group equivalent: 458.9 Eq) was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature control device. ) 101.0 g (OH: 0.22 mol equivalent), 0.067 g of 4-methoxyphenol as a polymerization inhibitor, 0.067 g of dibutyltin dilaurate as a urethanization reaction catalyst, and stirred at 70 ° C. until uniform, isophorone diisocyanate 17 0.8 g (NCO: 0.16 mol equivalent) was added dropwise over 3 hours. After the addition, the mixture was reacted at 70 ° C., and the point where the NCO content was 0.1% or less was set as the end point of the reaction to obtain a photosensitive resin (H-1).

Examples 8-13, Comparative Example 1
In (C-3) and (C-4) obtained in Examples 3 and 4, MEK, which is a solvent, was distilled off in advance to obtain only the resin content, and the other resins were left as they were in Table 1 below. A resin composition was obtained with the composition shown, and the resin composition was coated on a stainless steel plate with a wall made of gum tape (thickness: 200 μm) using a bar coater, and the lamp height was 10 cm under a nitrogen atmosphere. Ultraviolet rays were irradiated at a conveyance speed of 5 m / min to obtain a cured film having a thickness of about 200 μm.

Test example 1
The following items were evaluated for the films obtained in Examples 8 to 13 or Comparative Example 1, and the results are shown in Table 2.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film was measured using pencil scratching. That is, a pencil was applied to the film to be measured at an angle of 45 degrees, a 1 kg load was applied from above, and the film was scratched for about 5 mm to confirm the degree of scratches.

(Tensile test)
The film was cut into 1.0 cm × 4.0 cm, and the following data was measured using a Tensilon (tensile tester).
1: Young's modulus 2: Stress at break 3: Elongation at break

  The results in Table 2 indicate that a film that can be stretched while maintaining a relatively high Young's modulus and a high stress at break can be obtained by using the photosensitive resin composition of the present invention.

Examples 14-19, Comparative Example 2
In (C-3) and (C-4) obtained in Examples 3 and 4, MEK, which is a solvent, was distilled off in advance to obtain only the resin content, and the other resins were left as they were in Table 3 below. A resin composition was obtained with the composition shown, and the obtained resin composition was applied to an easy adhesion treatment polyester film (manufactured by Toyobo Co., Ltd .: A-4300, film thickness 188 μm) using a bar coater (No. 20) , After standing in a drying oven at 80 ° C. for 1 minute, using a 120 W / cm high-pressure mercury lamp in an air atmosphere, irradiating with ultraviolet rays at a conveying speed of 5 m / min from a distance of 10 cm from the lamp height, 15 μm) was obtained.

Test example 2
The following items were evaluated for the films obtained in Examples 14 to 19 or Comparative Example 2, and the results are shown in Table 4.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film was measured using pencil scratching. That is, on a polyester film having a cured film to be measured, a pencil was applied at a 45 degree angle and a 1 kg load was applied from above to scratch about 5 mm to confirm the degree of scratching. Take 5 measurements and count the number of scratches.
Evaluation 5/5: No damage in 5 out of 5 times 0/5: All scratches occurred in 5 times

(Abrasion resistance test)
A load of 200 g / cm ² was applied on steel wool # 0000, 10 reciprocations were performed, and the state of the scratch was judged visually.
Evaluation ○: No scratch ×: Scratch occurrence

(Adhesion)
In accordance with JIS K 5400, 100 vertical grids are made by making 11 vertical and horizontal cuts at 1 mm intervals on the surface of the film. When cellophane tape (registered trademark) was brought into close contact with the surface and peeled off at once, the number of cells remaining without peeling was displayed.

(curl)
A polyester film having a cured film to be measured was cut into 5 cm × 5 cm, left in an oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four sides that floated on a horizontal table was measured, and the average value was taken as the measured value (unit: mm). At this time, the curl of the base material itself was 0 mm.

(appearance)
Surface cracks, whitening, cloudiness, etc. were judged visually.
Evaluation ○: Good △: Microcracking ×: Significant cracking

  The results shown in Table 4 indicate that the film coated with the photosensitive resin composition of the present invention has excellent performance such as high pencil hardness and scratch resistance, little curling, and almost no cracks. ing.

Test Example 3 (Examples 20 to 25, Comparative Example 3)
Using the compound (C-1) obtained in Example 1 and the compound (C-6) obtained in Example 6, a resin composition having the blending ratio shown in Table 5 below was prepared, and protection for optical disks Evaluation as a coating agent was performed. The parts in Table 5 are parts by weight.

In addition, the symbol of each composition shown in the table | surface is as follows.
UX-6101: polyester urethane acrylate (molecular weight; 2700 ± 500), Nippon Kayaku Co., Ltd. R-684: dicyclopentanyl di (meth) acrylate, Nippon Kayaku Co., Ltd. R-604: hydroxypivalaldehyde modified tri Methylolpropane di (meth) acrylate, Nippon Kayaku Co., Ltd. PHE: Phenoxyethyl (meth) acrylate, Daiichi Kogyo Seiyaku Co., Ltd. LA: Lauryl acrylate, Nippon Oil & Fats Inc. 184: 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator manufactured by Ciba Specialty Chemicals

(viscosity)
The measurement was performed using a B-type viscometer.

(Curing shrinkage)
A value calculated from the following formula (1) from the liquid specific gravity before curing at 25 ° C. and the film specific gravity at 25 ° C. obtained by curing.
Curing shrinkage = (film specific gravity−liquid specific gravity) / film specific gravity × 100 (1)

(Water absorption rate)
It was set as the value obtained by the method based on JIS K-7209 7.2.1.

(Transmittance)
The resin was applied to a polycarbonate substrate by spin coating to a thickness of 100 ± 10 μm, and after UV curing, the transmittance at 405 nm was measured using the polycarbonate substrate as a reference.

(warp)
A DVD sputtered aluminum was used. Each of the compositions shown in Table 5 was applied onto a DVD substrate that had been sputtered with aluminum by a spin coater to form a coating film having an average film thickness of 100 μm. The coating film was cured with a UV irradiation machine (CS-30L manufactured by Nippon Battery Co., Ltd., 80 w / cm high-pressure mercury lamp) at a height of 10 cm and an energy amount of 1000 mj / cm ² . The obtained test piece was allowed to stand for 24 hours and then placed on a glass plate to evaluate warpage.
○ ... Almost no warpage.
Δ: When one side of the test piece is pressed with a finger, the opposite side is lifted, but it is 2 mm or less.
X: When one side of the test piece is pressed with a finger, the opposite side is lifted by 5 mm or more.

(durability)
The test piece used for the evaluation of the warp was used and left in an environment of 80 ° C. and 85% RH for 500 hours. The state of the reflective film was visually observed.
○: No change is seen in the reflective film immediately after bonding.
Δ: Discoloration or pinholes are slightly seen in the reflective film.
×: Discoloration or large pinholes are seen in the reflective film

  From the results shown in Table 5, the resin composition of the present invention and the cured product thereof provide a protective coating agent for high-density optical discs having excellent transparency and low water absorption and high durability with little warpage, and a cured product thereof. It is extremely useful for optical discs that read and / or write using a blue laser.

Claims (10)

An isocyanate compound (A ), which is a reaction product of a diisocyanate compound (a) and an alcohol compound (b) having at least two hydroxyl groups in the molecule, and one or more hydroxyl groups as a (meth) acrylate compound of a polyhydric alcohol. A photosensitive resin obtained by reacting a polyfunctional (meth) acrylate compound and a mixture (B) of a polyfunctional (meth) acrylate compound containing a polyfunctional (meth) acrylate compound in which all hydroxyl groups are ester-bonded; polymerization initiator (C), and the polymerizable compound (D) as neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, hydroxypivalaldehyde-modified trimethylolpropane di (meth) acrylate, hydroxy Neopentyl glycol pivalate (Meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di ( One or more selected from the group consisting of (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, and tris [(meth) acryloxyethyl] isocyanurate A protective coating agent for optical disks containing a compound .   The protective coating agent for optical disks according to claim 1, wherein the alcohol compound (b) having at least two hydroxyl groups in the molecule has a weight average molecular weight of 100 to 1,500.   The protective coating agent for optical disks according to claim 1 or 2, wherein the polyfunctional (meth) acrylate compound having one or more hydroxyl groups is pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate.   The protective coating agent for optical disks according to any one of claims 1 to 3, wherein the mixture (B) is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. Hardened | cured material of the protective coating agent for optical discs as described in any one of Claims 1-4 . A film containing the cured product according to claim 5 . The cured product of the protective coating agent for an optical disk according to claim 5 , wherein the water absorption (measured temperature: 25 ° C) of the cured product is 2.0% or less and the curing shrinkage is 6% or less. The cured product according to claim 5 or 7 , wherein the transmittance of the blue laser at a film thickness of 50 to 150 µm of the cured product is 70% or more. An optical disk having the cured product layer according to claim 5, 7 or 8 . The optical disk according to claim 9 , wherein a cured product layer is formed on a side on which recording light and / or reproduction light is incident.