TW201115272A - UV curable resin composition, cured article and optical disc - Google Patents

Abstract

The present invention provides a novel UV curable resin composition, and cured article thereof and optical disc having cured article layer, the UV curable resin composition containing: (A) polysulfide, preferably the polysulfide represented by general formula (1) (wherein, n represents an integer from 2 to 6; R1, R2, R3, R4 respectively independently represents hydrogen atom or alkyl having carbon atom from 1 to 10; X respectively independently represents oxygen atom or sulfur atom); (B) photo-polymerizable compound; and (C) photopolymerization initiator. The resin composition of present invention is suitable as a resin coating layer of optical disc(for example, the adhesive DVD bonding layer or light transmission layer of blue-ray disc), especially in the optical disc having a reflective film comprising silver or silver alloy, by the function of the polysulfide, the durability of the optical disc is promoted.

Description

201115272 6. Technical Field of the Invention The present invention relates to a novel ultraviolet curable resin composition and a cured product thereof, and a disc having the cured layer (having a composition of silver or a silver alloy) The disc of the reflective film is better). [Prior Art] Nowadays, the DVD that has been put into practical use is roughly classified into a DVD-ROM in which information such as a movie has been recorded from the time of manufacture of the disc, and no information is recorded at the time of manufacture, and the consumer himself is in the pigment recording layer. The inorganic recording layer records a recording type DVD in the form of an educational message. The DVD-ROM is a DVD-9 in which the recording layer is a single-sided read layer and has a recording capacity of about 5 GB, and the recording layer is a single-sided read two-layer and has a recording capacity of about 9 GB. The recording layer is a DVD-10 having two layers on both sides and having a recording capacity of about 10 GB, and a recording layer having four layers of four sides and having a recording capacity of about 18 GB. Nowadays, DVD-9 has become the mainstream because of the recording capacity of movies that can be recorded for about two and a half hours. The DVD-9 is produced by laminating a 0. 6 mm polysulphonate substrate having a total reflection film made of an aluminum alloy and a 0.6 mm polycarbonate substrate having a semi-transparent reflective film. Translucent reflective films are dominated by silver or silver alloys that are inexpensive and have high reflectivity. On the other hand, recordable DVDs exist in various formats such as DVD-R, DVD+R, DVD-RW, DVD+RW, and DVD-RAM. The mainstream DVD-R, DVD-RW, DVD+R, and DVD+RW are now one-sided and one-layer. This type is produced by laminating a 0. 6 mm barrier polymer substrate and a 0.6 mm polycarbonate substrate having a recording layer composed of an organic dye or an inorganic compound and a reflective film layer. Reflective film layer 4 322273 201115272 The material is a silver or silver alloy that is inexpensive and has a high reflectivity. In addition, in recent years, the ancient p # i u. There is MM g = t (Blu-rayDlSc: B_HDDvD. In particular, the blue light & plastic substrate is formed into a recording layer and then in the layer of the layer, 1 with the light penetrating layer structure, and through the light penetrating layer Discs. Blu-ray discs are also the same as _ in the use of silver or silver alloy in the reflective film. The production version I is easy to oxidize due to silver or silver alloy, so there is a high temperature and high humidity ring silver or silver alloy anti-deterioration, The problem of the increase in the number of reading errors. In the patent document, a UV-curing type CD_R containing a compound containing an extension of the compound is used in the patent document, and the patent document 2 contains a proposal. Protective coating resin for UV-curable CD-R of silk sulfide compound. In addition, since the protective coating layer for CD-R generally has a film thickness of about 1 〇 Å and does not have the influence of stress after hardening, even a resin having a high crosslinking density and excellent heat resistance can easily be used. The warpage control is within specification. On the other hand, when a resin having a high heat resistance and a high crosslinking density is used as a light-transmissive layer such as an adhesive layer such as a DVD having a thick film thickness or a light-transmitting layer such as a Blu-ray disk, the warpage of the substrate becomes large, so that it is difficult to increase the resin. Its own heat resistance. In the case of the sigma, the alkyl thiol compound and the alkyl thioether compound are preliminarily based on the protective coating resin of the prior art, and it is not possible to sufficiently prevent light penetration of the adhesive layer such as a DVD or a Blu-ray disc. The condition in which the silver or silver alloy reflective film of the layer deteriorates. [Prior Art Document] 5 322273 201115272 [Patent Document 1] Japanese Patent No. 3861589 (Patent Document 2) Japanese Patent No. 4016669 (Invention) The object of the present invention is Developed an ultraviolet curable resin composition for improving the durability (especially wet heat durability) of a disc, particularly a disc having a reflective film made of silver or a silver alloy, which is used as a resin layer of a disc (also known as a resin layer) It is an ultraviolet curable resin composition or a photocurable resin composition). (Means for Solving the Problems) The inventors of the present invention have found that a polysulfide compound, for example, a polysulfide compound represented by the following formula (1), is added to an ultraviolet curable resin composition in order to solve the above problems. In the case of a cured film having a cured layer of the resin composition and having a reflective film made of silver or a silver alloy, compared to a cured layer having the same ultraviolet curable resin composition to which the polysulfide compound is not added The same optical disc has a significantly improved wet heat durability, and the present invention has been completed. According to the present invention, regardless of the kind of the photopolymerizable compound (resin) used in the ultraviolet curable resin composition or the characteristics (crosslinking density or heat resistance) of the resin composition, the optical disc (especially having silver or silver) In the optical disc of the reflective film formed of the alloy, the durability of the optical disc can be improved. That is, the present invention relates to the following (1) to (16). (1) An ultraviolet curable resin composition comprising: (A) a polysulfide 6 322273 201115272 compound, (B) a photopolymerizable compound, and (c) a photopolymerization initiator. (2) The ultraviolet curable resin composition according to the above (1), wherein the polysulfide compound is represented by the following formula (1):

(wherein 'n represents an integer of 2 to 6; and Ri, R2, R3, and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and hydrazine independently represents an oxygen atom or a sulfur atom). (3) The ultraviolet curable resin composition according to the above (2), wherein the polysulfide compound (A) represented by the formula (1) is a formula (2), a formula (3) or a formula (4) Shown as follows:

(2)

7 322273 201115272 A composition comprising at least one of (B-1) oxime oxy (meth) acrylate acid or urethane thiol acrylate as a photopolymerizable compound (B) ). (6) The ultraviolet curable resin composition according to the above (5), further comprising (B-2) (fluorenyl) acrylate monomer as the photopolymerizable compound (B). (7) The ultraviolet curable resin composition according to the above (6), wherein the (meth)acrylic acid acetal monomer (B-2) is selected from the group consisting of dicyclopentyloxy (meth)acrylate , propylene di Sf. di(methyl) acrylate vinegar, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di(meth) acrylate, phenoxy phenoxy acrylate Ester, stupid oxy polyethylene glycol (fluorenyl) acrylate, ethylene oxide modified (mercapto) acrylic acid, phenoxy ethoxylate, (mercapto) propionate: acid 2-pyridyl-3-phenoxy At least one of a group of propylene and ethylene oxide modified bisphenol A di(meth) acrylate. (8) The ultraviolet curable resin composition according to any one of the above (5), further comprising a phosphoric acid (mercapto) acrylate as the photopolymerizable compound (B). (9) The ultraviolet curable resin composition according to the above (1) to (8), wherein the photopolymerization initiator (C) is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone and 2-benzyl group- 2-Dimethylamino-1-(4-(N-morphinyl)phenyl)butan-1-one, 2,4,6-trimercaptobenzylidene diphenylphosphine oxide, double (2,4,6-Trimethylbenzylidene)phenylphosphine oxide, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, 2 -hydroxy-1- 8 322273 201115272 { 4-[4-(2-hydroxy-2-methyl-propenyl) benzyl; Iphenyl hydrazine-2-methyl-'propane-1 ketone, and 1-[4-(2-Hydroxyethoxy)phenyl]2 is at least '~ species in the group consisting of benzyl-2-methyl-indole-propyl __1_ copper. (10) The use of the ultraviolet curable resin composition according to any one of the above (1) to (9), which is a resin cured layer for forming a disc. (11) The use according to the above (10), wherein the resin cured layer of the optical disk is an adhesive layer or a light transmissive layer. (12) The use of the ultraviolet curable resin composition according to any one of the above (1) to (9), which is for use in a disc having a reflective film made of silver or a silver alloy. (13) A cured product obtained by irradiating an ultraviolet ray-curable resin composition according to any one of the above (1) to (9) with an active energy ray. (14) An optical disk comprising a cured layer of the ultraviolet curable resin composition according to any one of the above items (9) to (9). (15) The optical disk of the above-mentioned (1) to (9) is irradiated with active energy by coating the optical disk substrate having a reflective film made of silver or a silver alloy. The line comes. (16) The use of the polysulfide compound of the following formula (1)* as an additive for the external curable resin composition:

322273 201115272 (wherein, _n represents an integer from 2 to 6; R|, R2, R3, and R4 respectively represent a surface of a non-hydrogen atom or a carbon number of 1 to 1 G; X respectively represents an oxygen atom or a sulfur atom; ). (Effects of the Invention) The novel ultraviolet curable type of the polysulfide compound (a) of the present invention is suitable for the hardened layer of the tree. In particular, the ultraviolet curable type of the multi-carbon compound (A) represented by the formula (1) of the present invention is used, and the product is used for a resin cured product of a disc using silver or a silver alloy in a reflective film. a layer (especially an adhesive layer such as a DVD or a light-transmitting layer such as a Blu-ray disc), and even if the cured product of the resin composition is not highly crosslinked, it can impart durability to the optical disc, and can be provided at a high temperature A disc with high reliability when wet for a long time. [Embodiment] The ultraviolet curable resin composition of the present invention contains a polysulfide compound, a photopolymerizable compound, and a photopolymerization initiator. The amount of the polysulfide compound (A) is from 0.001 to 1% by weight, the photopolymerization initiator (〇〇. 5 to 20% by weight, and the photopolymerizable compound (B), based on the total amount of the resin composition. For the remainder, further, if necessary, may contain any additives 〇 to a range of about 5% of the reset %, preferably in the range of about 2% by weight. Further, relative to the total amount of the resin composition The total of the polysulfide compound (A) and the photopolymerization agent (6) is preferably 2 to 2% by weight, and more preferably 8 to 98% by weight of the photopolymerizable compound (β). In the invention, unless otherwise specified, % is % by weight, and parts are parts by weight. 322273 10 201115272 The polysulfide compound (A) contained in the composition of the present invention is a compound of the above formula (1). Further, in the compound of the general formula, a compound of the formula is preferred. L, R3 and 匕 are each independently a hydrogen atom or a number of carbon atoms 丨 to 3, and both are oxygen atoms, η (2) A polysulfide compound as described in (1) above, wherein Llh and R4 are all The polysulfide compound according to the above (1) or (2), wherein all of h, ruthenium, osmium and R4 are hydrogen atoms.

The compounds represented by the following formulas (2) to (4) are exemplified as preferred examples of the compound. Among them, a compound represented by the following formula (2) is more preferable.

Formula (4) Γ\

For example, it can be produced by the method described in Japanese Laid-Open Patent Publication No. 322273, No. 2011-201122, 2002-524442, or a method based thereon. For example, the compound of formula (2) can be cooled to -78 ° C by morpholine petroleum ether solution, followed by the addition of di-gasified disulfide, and stirred at -78 t for 15 minutes, after which It was made by stirring at room temperature for 30 minutes. Further, as the compound represented by the formula (1), a commercially available compound can also be used. As a commercially available compound, the compound represented by the formula (2) can be obtained from Vulnoc RTMR (manufactured by Ouchi Shinko Chemical Co., Ltd.) or Actor RTMR (Kawaguchi Chemical Industry Co., Ltd.). 3%至0. 3重量百分比更优选更优选。 The 5% to 0. 3% by weight. . When the content is more than 1% by weight, the amount of 001% by weight is less than 1% by weight. Conversely, the coating film made of silver or a silver alloy tends to be deteriorated under the high temperature and high humidity test. The photopolymerizable compound (B) contained in the composition of the present invention is preferably a (fluorenyl) acrylate compound. The (mercapto) acrylate compound may, for example, be a compound having one or more (1 to 6) (fluorenyl) acrylonitrile groups, and the type thereof is not particularly limited. Preferred examples of the (fluorenyl) acrylate compound include (B-1) epoxy (meth) acrylate and urethane (fluorenyl) acrylate. A (meth) acrylate compound other than the component (B-1), or a (B-2) (fluorenyl) acrylate monomer may also be used. In the present invention, it is preferred to contain at least the component (B-1) as the component (B). It is more preferable to use the component (B-1) and the component (B-2) in combination. 12 322273 201115272 Further, in the present invention, "(meth) propyl ketone acid acrylate or acryl vinegar". As long as at least one of the epoxy group (f-group) acetoacetate and/or brain-braine (methyl) acetoacetate containing the component (B-1) in the resin composition of the present invention is 3 The resin of the present invention having a % oxy (meth) acrylate has a rain test t. In addition, the aspect containing both epoxy (T-based) acryl vinegar and urethane (methyl) propyl pure vinegar is also the invention of the invention, the olefin 1) is a modified hardened oil base _ epoxide Two (: base): = a preferred epoxy group (a, which should be obtained. The glycerol group _ epoxidation can be scaled by the following condensed (methyl) acrylic acid (methyl) The above-mentioned glycidyl ether of the epoxy obtained by the reaction of acrylic acid, and the cyclodextrose adduct u e2 J, which can be exemplified by the following: a double genus, a bis bis glycerin surface η 5 epoxy burning adduct Preferably, or hydrogenation of di-C4 alkanediol, or C2 to Cl0 aliphatic diol or poly-C2 group) C1 to C3 alkane (alkane is also ether, etc.. The above-mentioned double genus is double (4-hydroxy stupid) It is preferred that bisphenol A and bis-F are substituted by halogenation (hal〇geno), and the glycidyl group is preferably 4'^^. The ring-type ring-type bisphenol hydrazine or its alkylene oxide is added. Specific examples include, for example, glycidyl ether, hydrogenation, ring-modified double (four), two oil-based i, and the like, bisphenol A, oxime, and acetylene adduct.

Kb compound (also known as bis-A epoxide 322273 13 201115272); bisphenol F or its alkylene oxide adduct dioxin, hydride bisphenol F or its alkylene oxide addition Diglycidyl ether cage 'bisphenol F type epoxy compound (also known as bisphenol F type epoxy compound); 7, ̄ ~ alcohol diglycidyl scale, propylene glycol diglycidyl hydrazine, neopentyl Diacid glycerin _ ether, butanediol diglycidyl ether, hexanediol dimethyl glyceryl ether, cyclohexane didecyl diglycidyl ether, etc. C2 to C8 lipopeptide Alcohol diglycidyl ether; polyglycol diglycidyl ether, etc. (Γ 〆 diglycidyl hydrazine. ^ C4^-i|) Hydroglycidyl ether type The epoxy (mercapto) acrylate It can be obtained by reacting an escaping epoxy compound with (meth)acrylic acid. The reaction is more specifically described as follows. Relative to the epoxy group of the glycidyl ether type epoxy compound, the (meth)acrylic acid is reacted in a ratio of from 0.9 to 1.5 moles (more preferably 〇·95 to i丄 molar). . The reaction temperature is preferably from 80 to 121 TC, and the reaction time is from about 10 to 35 hours. In order to promote the reaction, it is preferred to use a catalyst such as triphenylphosphine, TAP, triethanolamine or vaporized tetraethylammonium. Further, in the reaction, a polymerization inhibitor (e.g., p-methoxyphenol, methylhydroquinone or the like) may be used. The preferred epoxy (indenyl) acrylates in the present invention are reacted with (meth)acrylic acid as described above, in the form of a sulphur-fired adduct or a hydrogenated gemini-glycidyl ether. Preferably, the obtained bisphenol diglycidyl ether di(meth) acrylate is bis(4-hydroxyphenyl) C1 to C3 alkane (the alkane may also have a tooth substitution), and the alkylene oxide adduct thereof Further, bisphenol diglycidyl ether obtained by reacting hydride diglycidyl ether with (mercapto)acrylic acid is preferred as 14 322273 201115272 (meth) acrylate. In the bis(meth)acrylic acid vinegar of bisphenol diglycidyl ether, the two-year-old class A, which is obtained from the above-mentioned double-group A epoxy compound, is a ketoxy di(meth)acrylate. Preferably, one of bisphenol A diglycidyl ether (mercapto) acrylate is more preferred. Further, the above-mentioned intermediate alkylene oxide adduct is preferably a C2 to C5 alkylene oxide adduct, and more preferably a (b) epoxy-oxygen addition product. In the present invention, the molecular weight of the epoxy group (meth) acrylate (B-1) is usually from about 400 to about 1 oooo, preferably from about 5 Torr to about 1 Torr. In addition, it is preferably about 400 to 5,000 depending on the case, and preferably about 4 to 3 inches. The urethane (meth) acrylate which can be used in the present invention has a mechanical property (such as a DVD or a Blu-ray disc, etc.) which enhances a cured layer of a resin obtained by using the ultraviolet curable resin composition of the present invention. The function of the sulphate and the sulphonic acid acylate can be obtained by reacting a polyol, an organic polyisocyanate and a hydroxy(indenyl)acrylic acid vinegar compound. For example, aliphatic polyols (for example, neopentyl glycol, 3-hydrazino-1,5-pentanediol, ethylene glycol 'propylene glycol, 1> 4-butanediol, hexanediol, trimethylolpropane, Pentaerythritol, tricyclodecanedimethylol, bis[hydroxymethyl]cyclohexane, etc., from the aliphatic polyols and polybasic acids (eg, succinic acid, phthalic acid, hexahydroortylene) Dicarboxylic anhydride (}16 妨}17 heart 叩111:1^1. Such as} 1 deduction ^ ^), terephthalic acid, adipic acid, azelaic acid, tetrahydroterephthalic anhydride, etc.) 322273 15 201115272 Polyester polyol, from polyols and caprolactone Caprolactone) a caprolactone obtained by the reaction, a polycarbonate polyol (for example, a polycarbonate diol obtained by reacting 1,6-hexanediol with diphenyl carbonate, or the like) or a polyether polyol ( For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide modified bisphenol A, etc., etc. Among them, polyether polyols are preferred, and C2 to C6 alkanediols are used. Preferably, polypropanol or polytetramethylene glycol is more preferred. The molecular weight is preferably from about 1Q0 to about 10,000, preferably from about 300 to about 3,500, more preferably from about 300 to about 2,500. The polyisocyanate may, for example, be a diisocyanate compound, such as a C6 to c13 smo-diisocyanate which may be substituted with a ketone group, and the diisocyanate may specifically be, for example, isophorone. Diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate or diphenyl decane _4,4-diisocyanate, etc., preferably isophorone diisocyanate or decyl diisocyanate. Isophorone diiso Cyanate esters are more preferred. Further preferred hydroxy (meth) acrylate compounds, such as: hydroxy substituted C2 to C10 aliphatic (meth) acrylate or hydroxy caprolactone (meth) acrylate An ester or the like, wherein a C2 to ci〇 aliphatic (fluorenyl) acrylate substituted with a hydroxy group is more preferred. A hydroxy-substituted C2 to C10 aliphatic (fluorenyl) acrylate may, for example, be a hydroxyethyl (meth) acrylate. (fluorenyl) hydroxypropyl acrylate, hydroxybutyl (meth) acrylate, dihydroxydecylcyclohexyl mono(decyl) acrylate, etc., preferably hydroxyethyl (meth) acrylate. 16 322273 201115272 The reaction is carried out, for example, as follows. ^卩' First, the polyol and the organic polyisocyanate, preferably the isocyanate of the organic polyisocyanate of the oxime, are reacted in a ratio of 1.1 to 2.0 equivalents to synthesize adenine. Polymer. The reaction/dish ratio is preferably 70 to 90 C. Next, the obtained leg is preferably reacted with a transbasic (meth) acrylate by one equivalent of an isocyanato group of the urethane oligomer, and the hydroxyl equivalent of the hydroxy (meth) acrylate compound is 1 The reaction temperature to obtain the desired urea sulphate (methyl) in a ratio of 1.5 equivalents is preferably 7 Torr. ~ θ is preferably a urethane (meth) acrylate at this time, a polyether polyol (preferably a poly C 2 to C 6 calcinol), an isocyanate compound (for example, a C6 to C13 hydrocarbon which can be substituted by a mercapto group) The isocyanate) and the hydroxy(indenyl) acrylate compound (C2 to C10 aliphatic (meth) acrylate substituted with a hydroxy group are preferred) The urethane (meth) acrylate obtained by the reaction is preferred. Further, the above urethane (mercapto) acrylate can also be obtained, for example, from UX-6101 (polymerized urea-acetic acid acetal: manufactured by Nippon Chemical Co., Ltd.). The molecular weight of the urea-based (meth) acrylate (B-1) is usually from about 4 to about 10,000, preferably from about 500 to 10,000, preferably from about 5 to about 4,000, and from about 500 to about 3,000. good. In the resin composition of the present invention, as the component (B-1), at least one of an epoxy group (meth) acrylate or a urea (meth) acrylate is preferable. It is preferred to contain at least $enyloxy(indenyl)acrylic acid g. Further, as the (meth) acrylate monomer of the (B-2) component of the present invention, the epoxy group (mercapto) acrylate and the ureido acrylate are also used as the (meth) acrylate monomer of the present invention (B-2). The (mercapto) acrylate monomer other than the above component (B-1) may be any of a mono(indenyl)propionate compound or a poly(indenyl)propionate compound, and Special restrictions. (meth) acrylate monomers having from about 丨 to 6 (meth) propylene groups are usually used. Further, those having 7 or more (meth) acrylonitrile groups may be used as the case may be. The component (B-2) is usually used in combination with the above (β-丨) component. The (fluorenyl) acrylate monomer which can be used as the component (B-2) also contains a phosphoric acid (meth) acrylate which will be described later. Since phosphoric acid (meth) acrylate can be distinguished from other (mercapto) acrylate monomers, it is used in other items to be described later. For example, as a (β-2) component, a preferred (fluorenyl) acrylonitrile-based (fluorenyl) acrylate monomer (also referred to as a mono(meth) acrylate compound) can be used as the (β-2) component. The compounds shown below are listed. Benzooxyethyl (meth)acrylate, phenoxypolyethylene glycol (mercapto) acrylate, phenyl cyanoacrylate, tetrahydrofurfury (meth) acrylate, morpholine ( Methyl) acrylate, (meth) propyl acetoacetate phenyl glycidol vinegar, (methyl) propyl benzoic acid 2 propyl acetonate, (meth) acrylic acid laurel vinegar, (meth) acrylate bismuth vinegar , (meth)acrylic acid stearin, (meth)acrylic acid isooctyl ester, (mercapto)acrylic acid tridecane vinegar, ethoxy diethylene glycol (T-based) propylene glycol δ, 曱 oxygen Di- or tri-propanediol (mercapto) acrylic acid vinegar, bicyclopyrene (methyl) propylene vinegar, (methyl) acrylic acid pinged Usob (10) yl vinegar, (methyl) propyl benzoate dicyclopentane Diethyleneoxyacetate, propylene^322273 18 201115272 Dicyclopentenyl acid ester (for example: FANCRYLrtmFA-511A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl acrylate (for example: Hitachi Chemical Co., Ltd.) Company-made FANCRYLrtmFA-512A), dicyclopentenyl methacrylate (for example: Hitachi Chemical Industry Co., Ltd. Company-made FANCRYLrtmFA-512M), dicyclopentanyl acrylate (for example: FANCRYLrtmFA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (for example, FANCRYLRTM FA-513M manufactured by Hitachi Chemical Co., Ltd.), Ibumantane acrylate (for example, Adamantate AA manufactured by Idemitsu Kosan Co., Ltd.), 2-mercapto-2-adamantyl acrylate (for example, Adamantate MA manufactured by Idemitsu Kosan Co., Ltd.), 2-B acrylic acid Alkyl-adamantyl ester (for example, Adamantate EA manufactured by Idemitsu Kosan Co., Ltd.), 1-adamantyl methacrylate (for example, Adamantate AM manufactured by Idemitsu Kosan Co., Ltd.), and the like. Among them, (fluorenyl) dicyclopentenyloxyethyl acrylate (FA-512A or 512M), phenoxyethyl (meth)acrylate, ethylene oxide modified (fluorenyl) acrylic acid Esters (PHE-2, etc.), phenoxy polyethylene glycol (meth) acrylate, and (meth)acrylic acid 2-hydroxy-3-phenoxypropyl ester are preferred. The above (meth) acrylate-based (indenyl) acrylate single system enhances the mechanical properties of the optical disk having the ultraviolet curing (10) lipid composition (four) hardened layer (tree stagnation hardened layer) of the present invention (inhibiting ribs) Qu or skew, etc.). As the (B 2) component, a (meth) propylene monomer (also referred to as a di(meth) propylene compound) having two (meth) propylene groups may be mentioned as an aliphatic group. Ring of C5^i5 diol of di(methyl)acrylic acid hydrazine...2 to C4 diol diol of di(meth)acrylic acid vinegar (to four C2 to C4 322273 19 201115272 = alcohol 2 (a) Good), [2 to 3 epoxy burning modified double: A: base) acrylic acid vinegar and so on. Further, the bis(meth)acrylic acid vinegar is combined: the bis-diol diol may be a C5 to C15 diol which may contain an aliphatic ring, and the fat may be a dioxane ring containing an oxygen atom. To 6 to!. The ring formed by the member and the member is good. The ring may also be composed of one piece. Alternatively, it may be a ring formed by combining a plurality of rings like a ring-shaped ring. It is preferred to use a cyclohexane ring, a second alkane ring or a tricyclodecane ring. 3 upper kC2 to C3% oxane modified bisphenol A: (in the acid ester, C2 to C3if oxygen production λ λ 士 乐 ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ Preferably, the molybdenum is preferably a compound of the (meth) acrylonitrile acetonate having two (meth) acrylonitrile groups, and examples thereof include compounds exemplified below. 4-Methanol di(methyl)propionic acid vinegar, cyclohexan-1, dimethanol di(meth) acrylate, tricyclodecane dimethanol di(methyl) olefin (for example, Japan Chemical Pharmaceutical Co., Ltd., Ship η 咖 · = 癸 二 dimethanol dipropylene, etc.), two diol di(methyl) internal 酉夂 = (for example, Nippon Kayaku Co., Ltd., κ Α Α (10) 6 〇4: dioxane diol (di〇xane glyc〇n diacrylate), neopentyl glycol di(methyl)propionate, di(methyl) acrylate dicyclopentanyl, 1, 6-Hexanediol^(Meth)acrylic acid, epoxide reforming 1,6-hexanediol di(methyl) internal 酉夂酉夂, neopentyl alcohol di(meth)acrylic acid Epoxy-fired modified neopentyl glycol di(indenyl) acrylate, trimethyl Acid neopentyl glycol acenaphthyl sulphate diol 322273 20 201115272 acid ester, 1,9-nonanediol bis(indenyl) acrylate, polyethylene glycol propylene vinegar, polypropylene glycol phenol phenol a) baking acid Vinegar, epoxy Ethylene is modified to double hope A (methyl) propionate cool. In addition, the above-mentioned "epoxy is preferably C2 to C4 epoxy. In addition, the term "epoxy" or "epoxy epoxide" is used in the case of alkane or ethylene oxide. Revamped. In the above-mentioned medium, dipropylene glycol di(methyl)-propyl acetoacetate, tripropylene glycol bis(methane) propylene hydrazine 1,6-hexanol bis(indenyl) acrylate, ethylene oxide modification It is preferred to double-prepare A-(meth)acrylic acid vinegar, neopentyl glycol dipropylene vinegar, and the like. The resin composition of the present invention preferably contains the above-mentioned di(meth)acrylic acid vinegar. The (meth) acrylate monomer having three (meth) acrylonitrile groups which can be used as the component (B-2) may, for example, be a compound exemplified below. Dihydroxydecylpropane tri(meth) acrylate, trimethylol octane tri(meth) acrylate, trimethylolpropane polyethoxy tri(meth) acrylate, trimethylolpropane poly propylene Oxygen tri(meth)acrylate, trimethylolpropane I ethoxypolypropyl lactyl di(meth)acrylate, tris[(methyl)allyloxyethyl]isocyanate , caprolactone modified trimethyl) propylene methoxyethyl] isocyanurate, pentaerythritol tris(fluorenyl) acrylate, epoxy ethene modified by methyl propyl bis(methyl) Acrylate, propylene-propylene-modified tris-hydroxypropylpropane tri(meth)acrylate, and the like. Among them, tris(hydroxy)propenyl tris(fluorenyl) acrylate or pentaerythritol tri(meth) acrylate is preferred. 21 322273 201115272 (f-based) acrylic acid with 4 (meth) acrylonitrile groups available as (Β-2) component! Monomers, can be classified as · pentaerythritol polyethoxy tetra(methyl) propyl acrylate, pentaerythritol polypropoxy tetra (methyl) propyl acetonate, tetraol tetra (indoyl) acrylate Further, di(trimethyl methacrylate) tetrakis (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc., preferably pentaerythritol polyethoxy tetra(methyl) acrylate. A (meth) acrylate monomer having 5 (?-based) acrylonitrile groups which can be used as the (β-2) component, and examples thereof include dipentaerythritol penta (meth) acrylate and caprolactone modification. Dipentaerythritol penta (meth) acrylate, and the like. A (meth) acrylate monomer having 6 ($based) acrylonitrile groups which can be used as the component (Β-2), and examples thereof include dipentaerythritol hexa(methyl)propionate and hexanoate The dipentaerythritol hexa(meth)acrylate vinegar or the like is preferably a pentaerythritol hexa(meth) acrylate. Further, the (fluorenyl) acrylate monomer which can be used in the present invention may be one having seven or more (meth) acrylonitrile groups. The (Β - 2) component may be any one as long as it is the above (mercapto) acrylate monomer. Preferred compounds as the component (Β-2) are exemplified below. As the (Β_2) component suitable for the adhesive for DVD bonding, for example, a poly C2-C4 alkanediol diacrylate (preferably 2 to 5; for example, dipropylene glycol diacrylate or tripropylene glycol) is exemplified. Acrylate or the like is preferred), C5 to C6 alkanediol diacrylate (preferably neopentyl glycol diacrylate, hydrazine, 6 hexanediol diacrylate, etc.), (fluorenyl) propylene dicyclopentene Ethyl oxyethyl ester (such as FA-512A described later), ethylene oxide modified (mercapto) phenoxyethyl acrylate (hereinafter referred to as PHE-2, etc.), ethylene oxide 2 to 2 〇 mol modification ( 3 to 15 22 322273 201115272 The molar modification is preferably bisphenol A diacrylate (BPE4A, BP-10, etc. described later). In addition, as a component (B-2) for a light transmissive layer suitable for BD, in addition to dicyclopentenyloxyethyl (meth) acrylate (hereinafter referred to as FA-512A, etc.), ethylene oxide modification (A) Base) styrene-ethyl acrylate (pHE_2, etc. described later), ethylene oxide 2 to 20 mole modification (preferably 3 to 15 moles) bisphenol A diacrylate vinegar (BPE4A, BP-10, described later) Other than the neopentyl glycol diacrylate, etc., may be exemplified by tricyclodecane dinonanol diacrylate (hereinafter referred to as R-684), neopentyl glycol diacrylate, and trishydroxypropyl propane triacrylate. Pentaerythritol triacrylate, pentaerythritol polyethoxy tetraacrylate, dipentaerythritol hexaacrylate, and the like. As one of preferred embodiments of the present invention, for example, an embodiment in which a bis(meth)acrylic acid vinegar compound is contained as the (B_2) component can be mentioned. In other words, in the resin composition of the present invention, the embodiment containing the (B-1; 1) component and the (B_2) component bis(indenyl) acrylate compound as the component (B) is one of preferred embodiments. The embodiment using the above preferred di(meth) acrylate compound as the bis(indenyl) acrylate compound is one of the better embodiments. In the above aspect, the content of the bis(indenyl) acrylate is not particularly limited with respect to the total amount of the component (B-2), and is preferably 30 to 1% by weight, and preferably 40 to 1% by weight. % is more preferably 5 to 100% by weight. The (B-2) component other than the di(indenyl) acrylate compound may, for example, be a (meth) acrylate compound other than the above bis(indenyl) acrylate compound, and its content is from about 70 to about 70% by weight. 〇 to 60% by weight 23 322273 201115272 is better than about 50% by weight. In the above preferred embodiment or a preferred embodiment, it is preferred that the (?-2) component other than the above bis(methylamide) acrylate compound is a mono(meth)acrylate compound. In this case, it is more preferable that the mono(sub) acrylate compound is the above-mentioned preferred or better mono(indenyl) acrylate compound. The mono(meth)acrylate compound or the di(meth)acrylate compound which is preferably a component of the above (Β-2) may, for example, be a (fluorenyl)acrylic acid having a fluorenyl group. Preferred examples of the mono(indenyl) acrylate compound of the ester monomer or the above-mentioned (meth) acrylate monomer having two (meth) acrylonitrile groups A bis(indenyl)acrylic acid quinone compound. More preferably, the mono(meth)acrylate compound is at least one selected from the group consisting of dicyclopentenyloxyethyl (meth)acrylate (hereinafter referred to as FA-512A, etc.) and benzyl (meth)acrylate. Oxyethyl ester, ethylene oxide modified phenoxyethyl (meth)acrylate (ΡΗΕ-2, etc.), phenoxy polyethylene glycol (fluorenyl) acrylate, and 2-hydroxyl (meth)acrylate a mono(meth) acrylate compound in the group of -3-phenoxypropyl ester; as a di(meth) acrylate compound, at least one selected from the group consisting of dipropylene glycol di(meth) acrylate and tripropylene glycol (Meth) acrylate, 1,6-hexanediol di(meth) acrylate, ethylene oxide modification (preferably 2 to 20 moles, 3 to 15 moles) a bis(indenyl) acrylate compound in the group of bisphenol quinone (mercapto) acrylate and neopentyl glycol diacrylate vinegar. And a preferred (mercapto) acrylate ester other than the above-mentioned mono(indenyl) acrylate compound or bis(indenyl) acrylate compound as the component (B-2) 24 322273 201115272 The mouthpiece can be exemplified by Decane diterpene diacrylate (R-684), tris(tetra)propenylpropene _, quaternary alcohol tripropylene, quaternary beer polyethoxytetraacrylate, dipentaerythritol hexaacrylate, and the like. ❽ ’ 作. It is better for the ingredients of () methylated ketones can be listed as follows: the above mono (meth) acrylamide and bis(meth) acrylate hydrazine as a better ( The mercapto acrylate monomer may, for example, be a (fluorenyl) acrylic acid dicyclopentanyloxyacetate, a dipropylene glycol di(meth) acrylate, or a dipropylene glycol bis(indenyl) acrylate, , 6-hexanediol di(meth)acrylate, (mercapto)acrylic acid phenoxyethyl §|, epoxy ethene modified (methyl) acrylic acid phenoxy ethane 5, phenoxy poly Ethylene glycol (methyl) diacid vinegar, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ethylene oxide modified bisphenol octa (meth) acrylate. In the curable resin composition, one or two or more kinds of these components may be used in any ratio. The content of the (β) component in the ultraviolet curable resin composition is usually from 8 to 98% by weight. It is preferably from 85 to 98% by weight. The remainder of 2 to 2% by weight (preferably 2 to 15%) is (Α) component (polysulfide compound) and (c) component (light polymerization) Further, when (B-1) and (B-2) are used in combination as the component (B), usually (β-丨) is 2〇 to 8 with respect to the component (B) of WO parts by weight. The bismuth by weight is preferably about 25 to 75 parts by weight, and the bismuth (2) is 20 to 80 parts by weight, preferably about 25 to 75 parts by weight, based on 1 part by weight of the component (B). In the ultraviolet curable resin composition of the invention, a (meth) acrylate may be added as a (Β_2) knives, and a phosphoric acid (meth) acrylate may be used to enhance the adhesion of aluminum, silver or a silver alloy to an adhesive. However, 25 322273 201115272 and 'when used in large quantities, there is a concern that the metal film is corroded, so the amount of use is limited. Generally, the total amount of the resin composition of the present invention is preferably about 5% by weight to 5% by weight. It is preferable that it is about 3% by weight. The disc acid (meth) acrylate which can be contained in the ultraviolet curable resin composition of the present invention may be a (mercapto) acrylate vinegar having a phosphate skeleton. Monoester (also known as mono(indenyl)acrylate), diester (also known as di(indenyl)propane Ethyl ester or triester (also known as tris(yl) acrylate), etc. It is usually preferred to use a phosphoric acid (fluorenyl) acrylate compound modified with ethylene oxide. The modified phosphoric acid (meth) acrylate compound may, for example, be an ethylene oxide modified phenoxylated phosphoric acid (mercapto) acrylate or an ethylene oxide modified butoxylated phosphoric acid (fluorenyl) acrylate. Ethylene oxide modified octyloxyphosphoric acid (meth) acrylate, ethylene oxide modified di(meth) acrylate, ethylene oxide modified tris (decyl) acrylate, and the like. Such as, for example, PM 2 (ethylene oxide modified dimercaptoacrylate) manufactured by Sakamoto Chemical Co., Ltd., etc., can be obtained commercially. In the present invention, ethylene ethoxide-modified phosphoric acid dimethyl methacrylate I is used. The purpose is to be better. The phosphoric acid (mercapto) acrylate may be used in a mixture of one type or two or more types in any ratio. When the resin composition of the present invention contains phosphoric acid (meth) propylene hydrazine, the content thereof is usually from 0.005 to 5% by weight, preferably from 3% to 3% by weight. 5重量百分比更优选。 Preferably, 〇〇〇 5 to 0. 5 wt% is more preferred.

The photopolymerization initiator (6) to be contained in the composition of the present invention is not particularly limited, and examples thereof include, for example, ionic cyclohexylphenyl hydrazine (irgacure RTM 184, manufactured by Ciba Specialty Chemicals), and 2-hydroxy-2-methyl 322273 26 201115272. -[4-(l-methylvinyl)phenyl]propanol oligomer (Esacure

ONE-Ref ined; manufactured by Siber Hegner, Japan, l-[4-(2-P-ethoxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (IRGACURERTM 2959; Ciba Specialty Chemicals), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propenyl)benzoyl]phenylindole-2-indenyl-propylamine-1_酉(IRGACURE 127, manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-2-phenylacetophenone (irgACURErtm651; manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-mercapto-1-phenyl- Propane-I-ketone (DAR0CUR 1173; manufactured by Ciba Specialty Chemicals), 2-mercapto-l-[4-(indolyl)phenyl]-2-(N-morpholinyl)propan-1-one (IRGACURE) 907, manufactured by Ciba Specialty Chemicals), 2-phenylmercapto-2-didecylamino-1-(4-(N-morphenyl)phenyl)butan-1-one, 2-oxythioxanthone (2-chlorothioxanthone), 2,4-dimethyl sutoxone, 2'4-diisopropyl thioxanthone, isopropyl thioxanthone, 2, 4, 6-trimethylphenyl fluorenyl Diphenylphosphine oxide, bis(2,4,6-trimethyl adenyl)phenyl oxidative, bis(2,6-dimethoxyphenylphenyl)_2, 4, 4-triazole A pentylphosphine oxide or the like. In the ultraviolet curable resin composition of the present invention, one or two or more of these components may be used in any ratio. The content of the component in the ultraviolet curable resin composition is usually from 0.5 to 2% by weight, preferably from 1 to 10% by weight. Further, an amine or the like which can be used as a photopolymerization initiation aid can be used in combination with the above photopolymerization initiator. The amines which can be used are listed, for example, 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, p-didecylaminobenzoic acid ethyl 27 322273 201115272 ester or p-dimethylamine. Alkyl isovalerate and the like. The photopolymerization initiation aid such as the amine is an optional additive, and the content in the resin composition of the present invention is from about 5 to about 5. When the photopolymerization initiation aid is used, the content of the resin composition of the present invention is usually from 〇〇5 to 5% by weight, preferably from 1 to 3% by weight. In the ultraviolet curable resin composition for an optical disk of the present invention, an antioxidant, an organic solvent, a decane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, and a surface lubricant 'fluorescence may be added as necessary. Any additives such as a whitening agent, a light stabilizer (for example, a hindered amine compound, etc.), a filler, and the like. The content of any additive is in the range of from about 0 to about 5 % by weight based on the total amount of the resin composition of the present invention. "In the present invention, a filler may be contained within the range of the effect of the invention, but since it is usually not contained, the content of the arbitrarily added force agent is relative to the total amount of the resin composition of the present invention. Preferably, it is about 5% by weight, preferably about 3% by weight, preferably about 5% by weight. Therefore, the component (A), the component, and any additives are relative to the total amount of the resin composition of the present invention. When the total amount of the three is about 2 to 2% by weight, it is one of preferred embodiments of the present invention. As one of preferred embodiments of the resin composition of the present invention, a state containing a light stabilizer may be mentioned. The photo-stabilizer is preferably a hindered amine compound. The content of the photo-stabilizer is from about 3% by weight to about 3% by weight, preferably from about 1% to about 5% by weight, based on the total amount of the resin composition of the present invention. Specific examples include, for example, hydrazine, 2,2,6,6-pentamethyl-4_. sterol, 2' 2' 6, 6-tetramethyl _4 + decyl alcohol, and phantom 322273 28 201115272 1 , 2, 2, 6, 6-pentamethyl 4-piperidinyl ester (LA-82), (mercapto)acrylic acid 2, 2, 6, 6-tetramethyl-4-anthracene Given CHIMASSORB 119FL ° ester, manufactured by the Ciba Specialty Chemicals, or, CHIMASS0RB 2020FDL, CHIMASSORB * 944FDL, TINUVIN 622LD, TINUVIN 123S, TINUVIN 144,

TINUVIN 765 > TINUVIN 770DF ' TINUVIN 111FDL ' TINUVIN

783FDL, TINUVIN 791FB, TINUVIN XT850FF, TINUVIN H855FF, etc. (CHIMASSORB and TINUVIN are trademarks). In the present invention, any hindered amine compound having a light-stabilizing effect can be used. One of the preferred ones as exemplified above is 4- having 4 to 6 thiol substitutions. The occluded alcohol or its (mercapto) acrylate is preferably a hindered amine compound having a (mercapto) acryl. More preferred aspects of the resin composition of the present invention are specifically described below. 1. An ultraviolet curable resin composition 'in which' contains (A) 0.005 to 0.5% by weight of the polysulfide compound represented by the above formula (1), and (B) light relative to the total amount of the resin composition of the present invention. The polymerizable compound is from 80 to 98% by weight, and (C) the photopolymerization initiator is from 5 to 20% by weight, and the total of the components (A) and (C) is from 2 to 20% by weight. 2. The ultraviolet curable resin composition according to the above 1, wherein at least one of (B-1) epoxy (meth) acrylate or pulverized (meth) acrylate is contained. The (B) photopolymerizable compound 'comprising (B-2) (fluorenyl) acrylate monomer, the component (B-1) is 20 to 80% by weight based on the total amount of the component (B), (B) -2) The composition is 20 to 80% by weight. 3. The ultraviolet curable resin composition according to the above 2, wherein the average molecular weight of the epoxy (meth) acrylate of the component (B-1) is 322273 29 201115272 400 to 10000 urethane (methyl) The average molecular weight of the acrylate is from 4 Å to 10,000 Å. 4. The ultraviolet curable resin composition according to the above 2 or 3, wherein the '(B-2) (meth)acrylic acid vinegar single system contains a di(meth)acrylic acid ester compound' The acrylate compound is a di(meth)acrylate which may contain an aliphatic % of a C5 to C15 diol, a poly(C2 to C4 alkanediol) (two to four C2 to u-alkane) The di(meth)acrylate of alcohol is preferred or the di(meth)propionate of bisphenol A modified by ethylene oxide. 5. The ultraviolet curable resin composition according to any one of the above 2 to 4, wherein the (b-2) acrylate monomer as the component (B-2) is a total of the component (B-2) The amount is from 3 to 100% by weight of the bis($) acrylate compound, and the (meth) acrylate compound other than the bis(meth) acrylate compound is 〇 to 7 〇 by weight. 6. The ultraviolet curable resin composition according to the above 5, wherein the (meth) acrylate other than the methyl or di(meth) acrylate compound is a mono(indenyl) acrylate compound. 7. The ultraviolet curable resin composition according to any one of the above 2 to 6, which comprises a (meth) acrylate monomer other than phosphoric acid (mercapto) acrylate and a phosphoric acid (mercapto) acrylate. As the (fluorenyl) acrylate of the component (B-2), the acid (mercapto) acrylate content is 0.005 to 3% by weight based on the total amount of the resin composition. 8. The ultraviolet curable resin composition according to any one of the above 4 to 7, wherein the 'di(mercapto) acrylate compound is dipropylene glycol bis(methyl 30 322273 201115272) acrylate or tripropylene glycol bis(quinone) Acrylate, 1,6-hexanediol mono(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate or neopentyl glycol di(decyl)acrylate . The ultraviolet curable resin composition according to any one of the above items, wherein the (B-2) component contains at least one selected from the group consisting of dipropylene glycol bis(indenyl) acrylate and tripropylene glycol di Methyl) acrylate, 1,6-hexanol bis(indenyl) acrylate, ethylene oxide modified bisphenol a bis(indenyl) acrylate bis(indenyl) acrylate compound, neopentyl Alcohol di(meth)acrylate and tricyclodecane dimethanol diacrylate (mercapto) acrylate compound; trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol polyethoxy tetraacrylate Or a pentaerythritol hexaacrylate, and if necessary, may contain at least one selected from the group consisting of dicyclopentenyloxyethyl (meth)acrylate, phenoxyethyl methacrylate (meth) acrylate, and epoxy ethene ( Monomethyl group in the group of phenoxyethyl methacrylate, phenoxy polyethylene glycol (mercapto) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate ) acrylate compound. 10. The ultraviolet curable resin composition according to the above-mentioned item, wherein the component (A), the component (B) and the component (C) are contained in the total amount of the resin composition. Any of the additives 〇. 5 to 5 wt% 'and the total amount of the components (A), (C) and any of the additives is 2 to 20% by weight. 11. The ultraviolet curable resin composition according to the above 10, wherein the optional additive is a light stabilizer, and the light stabilizer is a hindered amine. 322273 31 201115272 2 The above ingredients can be used at room temperature to 8 ❹. C under. The tree ride of the present invention is also:; by the fine work, the degree of inclusions is just up to 5000 p, considering the coating property, and the ratio of the points at 25 ° C is appropriately adjusted to be in the range of 200 : Γ It is better to adjust the ingredients to 200 to 3 〇〇〇 mPa.s. Mingshu is useful for various resin coating layers (the adhesive layer and the transparent layer are useful, for example, for coating a resin for a disc and a light-transmitting layer, etc. as a protective coating layer, an adhesive layer, a follow-up agent or a Blu-ray disc) For the bonding type optical disc, the coating agent for the light transmissive layer on the incident side of the laser is used. When the U resin composition is used as various resin coating layers, it is intended to be used by the book. When the fat composition is applied to the substrate of the resin coating layer, the resin substrate is laminated on the substrate, and after the substrate is laminated thereon, the resin coating layer is irradiated with ultraviolet rays to make the resin. The coating layer is hardened to form a hardened resin coating layer. Specifically, 'the coating layer has a thickness of i to 15 G_, and any method, for example, spin coating method, 2P method, t coating method Applying the resin composition of the present invention to a disc substrate by a screen printing method, etc. If it is a bonded type disc, after superimposing two disc substrates via an adhesive layer, ultraviolet rays are irradiated from one side or both sides. Near ultraviolet (near wavelength 2〇〇 to 4〇〇nm) hardens the bonding layer Next, in the case of a light-transmitting layer, after the composition is applied, ultraviolet rays or near-ultraviolet rays (wavelengths from 2 〇 () to around 400 nm) are irradiated by one side or both sides to be hardened. The irradiation amount is about 5 〇. It is preferably 15 〇〇 mJ/cm 2 , preferably about 100 to 1000 mJ/cm 2 , and is used as the illuminating light 322273 32 201115272 η for illuminating ultraviolet rays or near ultraviolet rays. For example, m, high and high $ mercury lamp, gold "chemical lamp, (pulse) milk lamp, or electrodeless lamp, etc. As a disc substrate, a conventional one can be used, that is, using Shi Xi, Shi Xihua, and gold as a translucent reflective film. In particular, the tree of the present invention is particularly suitable for use as a disc of a total reflection film or a semi-transparent reflection film using silver or a silver alloy. The light money of the Wei layer having the tree test of the present invention includes: 2 pieces or The above substrate # is formed by the cured layer of the resin composition of the present invention and then formed into a disc, in particular, at least a plurality of disc substrates, which are a total reflection film of 1 silver or silver alloy or a translucent reflective disc substrate. Co-disc, and with silver or silver alloy a disc substrate having a reflective resin or a semi-transparent reflective film (usually having a thickness L1mm: not limited thereto) having a cured layer of the resin composition of the present invention as a light-transmitting layer (for example, a disc or the like). In the optical disk of the cured layer of the ultraviolet curable resin composition according to any one of the above-mentioned items (2) to (9), Or a disc having a cured layer of the ultraviolet curable resin composition according to any one of the above-mentioned items of the present invention, which is a preferred embodiment of the resin composition of the present invention. : DVD-R0M (DVD-5, DVD-10, DVD-9, DVD-14, DVD-18), DVD-R, DVD+R, DVD-RW, DVD+RW,

DVD RAM, DVD-R single-sided 2-layer mode, DVD+R single-sided 2-layer mode, dvd-RW 322273 33 201115272 Single-sided 2-layer mode, DVD+R single-sided 2-layer mode, HD DVD-ROM, HD DVD- R, BD-ROM, BD-R, BD-RE, etc. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. (Examples D1 to D5) (Comparative Examples D1 to D2) The respective components described in Table 1 were mixed to be uniform so as to have a composition shown in Table 1 below, and ultraviolet curing of each of the examples and the comparative examples was prepared. Resin composition. (Examples B1 to B7) (Comparative Examples B1 to B2) The respective components described in Table 2 were mixed to be uniform so as to have the composition shown in Table 2 below, and ultraviolet curing of each of the examples and the comparative examples was prepared. Resin composition. 34 322273 201115272 [Table 1] Comparative Example D2 I ΙΟ ΙΟ jn 5 ο 0.50 0.20 110.80 I Comparative Example D1 I \ο LD ΙΛ 5 ο 0.50 110.60 I Example D5 I 0.10 ιη ιη ιη ο 0.50 110.70 Example D4 I 0.10 ΙΟ Χη (Ο ΙΟ CO 5 ο 0.50 115.70 Example D3 0.20 L_ ιη ΙΟ ΙΟ 5 ο 0.50 110.80 Example D2 0.10 ιη ΡΟ LA ο 0.50 115.70 Example D1 I 0.05 CM ιη ΓΟ ΙΟ Bu 0, 50 112.65 Formula (2) Compound ΕΡΑ DPGDA TPGDA HDDA ΡΜ-2 IRGACURE 184D LA-82 j KBM-803 Total (ingredient A) (ingredient Β-1) (ingredient Β-2) (ingredient C) (additive) 395 390 380 385 380 410 420 Viscosity ( mPa,s/25°C) 35 ^vss,Ha%s8'o°o8 <〇330 X in 707 X CD <〇〇卜CNJ 〇ΙΟ CO 〇in CM 〇tn 〇> 〇 initial 値P! Sum8 After 500 hours, judge the appearance evaluation of XX 〇〇〇〇〇 reflection film 322273 201115272 [Table 2] Ratio & Example B2 | 〇ift tn CO CO 0.01 0.50 0.10 0.15 105.76 Comparative Example B1 I 〇in CM m CO CO I ° -〇1 I 0.50 0:10 105.61 Example B6 0.10 5 iso s 0.01 I 0.50 0.10 105.71 real k case day 5 0.10 tn CO to CO 0.01 inch 0.50 105.61 Example B4 0.10 〇g in CM inch 0.50 II 0.10 104.70 Example B3 0.10 〇in CM in CO n 0.01 inch 0.50 I 105.61 Example B2 0.10 〇LO OJ in CO O 0.01 0.50 0.10 105.71 Example B1 0.10 〇LO CM to CO CO 0.01 0.50 0.10 105.71 (Component A) Compound of formula (2) f Component Rn EPA UA-1 BPE4A BPE -10 TPGDA (Component B-2) HDDA FA-512A PHE-2 PM-2 Old Heart, 〇NE-Refined IRGACURE 184D LA-82 (Additive) L-7002 KBM-803 Total 36 1580 1500 1660 1640 2300 1810 1520 1460 Viscosity (mPa, s/25°C) World Seven osz, Ha%s®o°ooa 5.2E-05 I 3.0E-02 IX 4.6E-05 | 2.3E-02 IX 5.5E-05 I 9.8E-05 |〇6.2E-05 ”7.0E-05 | o 4.1E-05 | 6.6E-05 ] 0 3.6E-05 I | 6.5E-05 o ί 5.1E-05 [7.2E-05 | 〇4.4E- 05 I 6.5E-05 I 0 Initial 値RSER After 250 hours, 322273 201115272

Further, each component shown by the abbreviation in Table 1 and Table 2 is a compound of the following formula (2): v 1 RTM system) n〇c R (Daei Xinxing Chemical Industry Co., Ltd. EPA: Bisphenol A 4+, 丄廿.a-钿glycidyl ether dienoate UA-1 tetradecyl diol (850 in the knife), isophorone diisocyanate, acrylic acid 2-fresh Its 7 _ „ ^ ^ The composition of the two components of the earthworm 莫2 1:2:2. BPE4A · % 乳乙烧4莫耳, so the fight against Wudou changed Bei Shuang A A acrylate, the first Yigong Pharmaceutical Co., Ltd. 〃 BPE-10. Epoxy Pharmacy 1 〇 Mo Erjian> 吁 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 买 DP DP DP DP DP DP DP酉 酉 TPGDA: Tripropylene glycol diacrylate HD HD HDDA: 1,6-hexanediol diacrylate §, FA-512A made by Nippon Kayaku Co., Ltd. Chemical Co., Ltd. PHE-2··Ethylene Ethylene 2 More Modified Acetophene Phenoxyacetate PM-2~. Oxygen Ethylene Modified Dish Acid Dimethacrylate, Nippon Chemical Parts Co., Ltd. IRGACURE 184D: Bojing Ji stupid cyclohexyl group Si, (iv) carefully enthalpy

ONE-Refined: Esacure 0NE-Refined (2-hydroxy-2-methyl [4-(1-methylethlyl)phenyl]propanol oligomer), transcript 37 322273 201115272

LA-82 manufactured by Siber Hegner Co., Ltd.: Methyl & μ Internally bound acid 1,2,2,6,6-pentamethyl-4-〇辰〇定酉, Xu Lei Yang Co., Ltd. L-7002: Poly Dendrobium / gas (coating agent), Toray Dow Corning Co., Ltd. KM 8〇3 · 3~ propyl propyl trimethoxy decane (decane coupling agent), Shin-Etsu Chemical Co., Ltd. using 25c ( E-type viscometer) The viscosity of the examples and comparative examples was measured.蚤 ^ lt 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本(Test Example 1) (Formation by ^

The method of ab was evaluated for the ultraviolet curable resin compositions of Examples D1 to D5 and Comparative Examples D1 to D2. Ui) Manufactured in the form of a DVD+R 1. The substrate of the reflective film is rotated by a 0. 6 mm thick PC substrate (polycarbonate substrate). The azo dye recording layer was formed by a coating method, and after 80 Μ drying of the guillotine clock, silver made by Unaxis Corporation was used, and the film was sputtered to an average thickness of 100 nm to prepare a silver reflective film substrate. 2. On the inner circumference of the silver reflective film substrate obtained above, 2.5 g of the ultraviolet curable resin composition of the present invention was supplied in a circular shape. 3. The 0.6 mni thick PC substrate was placed on the silver reflective film substrate (sputtered face up) 'rotated coating at 3000 rpm for 4 seconds to make the invention between the pc substrate and the 322273 38 201115272 silver reflective film. The film thickness of the ultraviolet curable resin composition is superposed in a manner of 35 to 55. A device made by GLOBAL MACHINERY was used. .4. Using a xenon flash lamp, 8 shots were irradiated from the upper side at 80 J to harden the violet *external hardening type resin composition of the present invention, followed by the disc substrate. Further, the upper side of the DVD disc is a pc substrate, and the lower side is a silver reflective film substrate. 5。 On the DVD+R substrate manufactured by *1 to 4, a signal of about 4.7 GB was burned at a writing speed of 8 times by a device manufactured by Pioneer Co., Ltd. (model: DVR-ii). (1-2) Evaluation of the above-obtained DVD+R (appearance of pisum8 and reflective film) (a) #电电号 (PISum8) before and after the durability test of DVD+ The laminated optical disk of the present invention and the comparative example of the optical disk Place in an environment of 8 ° C, 85% RH for 5 hours. Using the DVD-CATSSA-300 manufactured by AUDI〇 DEV., a DVD data signal measuring device, the electrical signal (PISum8) of the bonded optical disk after the durability test was measured and evaluated on the basis of the following. piSum8 is a type of optical signal for a disc. The higher the value of PISum8, the more degraded the data attached to the disc. The evaluation results are shown in Table 1 below. PISum8 evaluation benchmark 0 "PISum8 value is less than 280. x"*PISum8 value is above 280. (b) Evaluation of the appearance of the reflective film By visually observing the state of the reflective film, it was evaluated on the basis of the following. The results are shown in Table 1. 39 322273 201115272 Appearance evaluation criteria for reflective film To reflect 骐 〇... Compared with the last one, there is no change in the status of the comment after 500 hours. ^ Membrane changes X.·· Compared with just after, the reflection color was observed after 500 hours. (Test Example 2) (Table 2) The ultraviolet curable resin composition obtained in Example B1 i Β6 or Comparative Example was evaluated by the following method.

(2-1) BD-ROM made of a light-transmitting layer 1. The silver-reflective film substrate is made of a silver alloy GB_1〇 made by Kobe Steel Co., Ltd. on a mm·lmm thick pc-US board on which a groove for BD-R0M is formed. Specifically, a disk substrate having a silver reflective film was produced by using an average of 30 nm film thickness. The smear of the present invention is 2. 5g of the ultraviolet ray of the present invention, the smear of the present invention is provided on the cover of the central portion. The hardened resin composition 0 3. The viscosity of the ultraviolet curable resin composition of the present invention is applied by spin coating at a speed of from 1,000 rpm to 1,500 rpm for 4 to 7 seconds, and the coating film thickness is from 95 μm to 105 / / m. At the end of the spin coating, the Xenon flash lamp was irradiated for 2 shots and hardened to the extent that the surface was not fluid. 4. Using a xenon flash lamp, 8 rays were irradiated from the upper side at 8 〇J to completely cure the ultraviolet curable resin composition of the present invention to obtain a BD-R0M having a light transmissive layer. Further, the disc of the present invention can be hard-coated on the surface of the resin, but in order to evaluate the durability of the light-transmitting layer itself, evaluation was carried out without performing a hard coating treatment. (2-2) Evaluation of BD-R〇M (RSER and reflection 臈 appearance) (a) 5 Rating of the electrical signal (rser) before and after the durability test

- The optical disc of the present invention and the optical disc of the comparative example were placed in an environment of 8 〇t:, 85% RH for 250 hours. The optical signal (RSER) of BE)-R(10) after the durability test was measured using the Blu-ray Disc data signal measuring device ODU-1000 manufactured by PULSTEC Co., Ltd., and evaluated according to the following evaluation criteria. RSER is a type of optical signal for a disc. The higher the RSER value, the more degraded the data of the BD-R0M. 5 The results of the flat assessment are shown in Table 2. RSER evaluation benchmark 〇~RSER value is less than 2. 〇E-〇4 (representing 2. 0x10,. X...RSER value is 2. OE-〇4 (representing 2. OxlO-4) or more. And 'RSER value "2. 0E-04" means "2, 〇χ1 (Γ4", and the same description in Table 2 also means the same meaning. For example, the initial value in Example Β1 is 5. 1Ε-05 means "5·lxl〇 (5) Evaluation of the appearance of the reflective film By visually observing the state of the reflective film, the evaluation was performed on the following basis, and the results are shown in Table 2. The evaluation criteria of the appearance of the reflective film were compared with those immediately after the film. After the evaluation of 2500 hours, no change in the state of the reflective film was observed. X... Compared with the subsequent one, the evaluation of the reflective film was observed after 250 hours. 41 322273 201115272 The results of Table 1 and Table 2 contain The resin compositions of the present invention of Examples D1 to D5 and B1 to B6 of the sulfur-containing compound represented by the formula (2) were evaluated in the durability test of a DVD and a Blu-ray disc to obtain good electrical characteristics and appearance of a reflective film. On the one hand, Comparative Examples D1, D2, Bl, and B2 which do not contain polysulfide compounds are used in the durability test. The characteristics and the appearance of the reflective film are evaluated as poor. (Industrial Applicability) The optical disk system using the resin composition of the present invention has excellent durability even when it has a reflective film composed of silver or a silver alloy, and is used for reflection. The film is made of a silver or silver alloy optical disc, in particular, a resin layer of a light transmissive layer such as a back layer of a DVD or a Blu-ray disc. [Simplified description of the drawing] Benefit * »»> [Description of main component symbols] No 42 322273

Claims (1)

201115272 VII. Patent application scope: 1. An ultraviolet curable resin composition comprising: (4) a polysulfide compound, (B) a dissimilar compound, and (6) a photopolymerization initiator. 2) The ultraviolet curable resin composition according to the invention of claim 2, wherein the polysulfide compound is represented by the following formula (1): (η in gas represents an integer from 2 to 6; r, r2, r3, and r4 are each independently 3. also represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and X independently represents an oxygen atom or a sulfur atom) . The ultraviolet curable resin composition according to claim 2, wherein the polysulfide compound represented by the formula (1) is represented by the formula (2), the formula (3) or the formula (4): (4). NSSSSN 0 The composition of the ultraviolet curable resin described in the second paragraph of the patent application scope is 'in which' is 0. 001 to 1 weight 43 322273 4. 201115272 % of the formula (1) Polysulfide compound (A). 5. The ultraviolet curable resin composition as described in claim 2, wherein 'inclusive' contains at least one of (B-1) epoxy (meth) acrylate or urethane (meth) acrylate as Photopolymerizable compound (B). 6. The ultraviolet curable resin composition as described in claim 5, further comprising (B-2) (fluorenyl) acrylate monomer as the photopolymerizable compound (B). 7. The ultraviolet curable resin composition as described in claim 6 wherein the '(mercapto) acrylate monomer (β 2 ) is selected from (meth) acrylate monocyclopentenyloxyethyl ester, Dipropylene glycol bis(indenyl)propionate, tripropylene glycol bis(indenyl) acrylate, 1,6-hexanediol bis(indenyl)acrylic acid vinegar, phenoxyethyl (meth)acrylate, epoxy Ethyl modified (meth) phenoxyethyl acrylate, phenoxy polyethylene glycol (mercapto) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and epoxy B The alkane is changed to at least one of a group of a group of (meth)acrylic acid vinegar. 8. The ultraviolet-curable resin composition according to any one of the items 5 to 7 wherein the phosphoric acid (meth) acrylate is further contained as the photopolymerizable compound (B). 9. The ultraviolet curable resin composition as described in claim 1, wherein the photopolymerization initiator (C) is selected from the group consisting of hydroxycyclohexyl phenanthyl amide and 2 phenyl fluorenyl-2- y Methylamino-l-(4-(N-morpholinyl)phenyl)butan-1-one, 2,4,6-trimercaptophenylphosphonium diphenylphosphine oxide, bis(2, 4,6-trimercaptobenzoyl) stupylphosphine oxide, 2-hydroxy-2-indolyl-[4-(1-methylvinyl)phenyl]propanol oligomer, 2-hydroxy- 1 - 44 322273 201115272 { 4-[4-(2-Hydroxy-2-methyl-J-propanol~1-one, and 1-yl- 2-methyl-1-propanyl-methyl-propanyl) Phenylhydrazinyl]phenyl}-2-yl-1-[4-(2-hydroxyethoxy)phenyl]_2-hydroxyl-yl-1-propane-:[at least one group of one ketones One. 10. (1) The use of the hardened resin component of the (4) line of the first job of the special home is the resin hardened layer for forming the optical disc. 11. The use of claim 1 , wherein the resin hardened layer of the optical disc is an adhesive layer or a light transmissive layer. 12. The use of the ultraviolet curable resin composition according to the invention of claim 2, which is for use in a disc having a reflective film composed of silver or a silver alloy. A cured product obtained by irradiating an active energy ray to an ultraviolet-hardening resin composition according to the above application. An optical disk comprising a cured layer of the ultraviolet curable resin composition according to the invention of claim i. Ί r • An optical disk obtained by coating an ultraviolet curable resin composition according to claim 1 in a disc substrate having a reflective film made of silver or a silver alloy, and irradiating an active energy ray. (1) The use of the polysulfide compound represented by the following formula (1) as an additive for the ultraviolet curable resin composition: (wherein 'n represents an integer from 2 to 6; R', r2, r3, and R4 are each independently 45 322273 201115272 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and X independently represents an oxygen atom or a sulfur atom, respectively. ). 46 322273 201115272 IV. Designated representative map: There is no schema in this case (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: This case is not represented by the chemical formula 322273 201115272 Patent application No. 99127067 (December 6, 1999) Invention Nasal Instructions - (This manual format, order, please do not change any more, please do not fill in the ※ part) ※Application number: ※Application曰: ※!^ Classification: 1. Name of the invention: (Chinese/English) UV curable resin composition, cured product and optical disc UV CURABLE RESIN COMPOSITION, CURED ARTICLE AND OPTICAL DISC II. Abstract: The present invention relates to a novel ultraviolet curable resin composition and a cured product thereof and the same In the optical disk of the layer, the ultraviolet curable resin composition contains: (Α) a polysulfide compound, preferably a polysulfide compound represented by the following formula (!) (wherein η represents an integer of 2 to 6; R1, R2 , R3, h each independently represents a deuterium atom or an alkyl group having a carbon number of 丨 to 1〇; 乂 independently represents an oxygen atom or a sulfur atom) (8) a photopolymerizable compound; and (C) a photopolymerization initiator, the resin composition of the present invention is suitable for a resin coating layer on a disc (for example, a light-transmissive layer of a bonding layer or a Blu-ray disc) Etc., in particular, in a disc having a reflective film composed of silver or a silver alloy, the durability of the light can be improved by the action of a poly(tetra) compound. 322273 Revised Patent Application No. 99127067 (December 6th, 1999) 201115272 Patent Description - (This manual is in the 'sequence, please do not change any more' ※Please do not fill in the number of the mark ※Application No.: ※Application date : .IPC classification: 1. Name of the invention: (Chinese / English) UV-curable resin composition, hardened material and optical disc UV CURABLE RESIN COMPOSITION, CURED^ARTICLE AND OPTICAL DISC II. Abstract: Ο This invention relates to a novel The ultraviolet curable resin composition, the cured product thereof, and the optical disk having the cured product layer, the ultraviolet curable resin composition containing a polysulfide compound, preferably a polysulfide compound (wherein η represents 2 An integer of up to 6: each independently represents a hydrogen atom or a number of carbon atoms 丨 to 1Q; x each independently represents an oxygen atom or a sulfur atom; (8) a photopolymerizable compound; and (C) photopolymerization The starting agent 'the resin composition of the present invention is suitable for the resin coating layer in the optical disc (for example, the fitting_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The layer can be enhanced by the transparency of the polysulfide compound. The present invention provides a novel UV curable resin composition, and cured article thereof and optical disc having cured article layer, the UV curable PCT Patent Application No. 99127067 (December 6, 1999) 201115272 (a) polysulfide, preferably the polysulfide represented by general formula (l) (wherein, n represents an integer from 2 to 6 ; Ri ' R2 ' R3 ' R4 respectively independently represents a hydrogen atom or alkyl having a carbon atom from 1 (a) photo-polymerizable compound; and (C) photopolymerization initiator. The resin composition of present invention is a resin coating layer of optical disc (for example, the Adhesive DVD bonding layer or light transmission layer of blue-ray disc), especially in the optical disc having a reflective film comprising silver or silver alloy, by the function of the polysulfide, the Durability of the optical disc is promoted. 2 322273 revision