CN103026411A - Ultraviolet-curable resin composition for optical disk, cured object, and optical disk - Google Patents

Ultraviolet-curable resin composition for optical disk, cured object, and optical disk Download PDF

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Publication number
CN103026411A
CN103026411A CN2011800356241A CN201180035624A CN103026411A CN 103026411 A CN103026411 A CN 103026411A CN 2011800356241 A CN2011800356241 A CN 2011800356241A CN 201180035624 A CN201180035624 A CN 201180035624A CN 103026411 A CN103026411 A CN 103026411A
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Prior art keywords
methyl
acrylate
resin composition
ultraviolet
carbamate
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CN2011800356241A
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CN103026411B (en
Inventor
本桥隼
内藤正弘
小林大祐
木户场润
松尾雄一朗
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
    • G11B7/2572—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials
    • G11B7/2575—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials resins
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes

Abstract

The invention relates to an ultraviolet-curable resin composition for optical disks having an organic pigment layer, the resin composition comprising (A) a polyfunctional (meth)acrylate, (B) a urethane (meth)acrylate, and (C) a photopolymerization initiator and being characterized by giving a cured film that has a storage modulus (E') at 80 C in the range of 50-200 MPa. The resin composition is suitable for use in forming a light-transmitting layer for optical disks having an organic-pigment recording layer. This resin composition is applied to the organic-pigment recording layer or interface layer of an optical disk substrate having an organic-pigment recording layer and is cured to form a light-transmitting layer which adjoins that layer. The optical disk substrate is inhibited from warping when the resin composition is applied and cured. Thus, it is possible to obtain an optical disk which has an initial jitter value as low as 7% or below, has a jitter value less than 10% even after having undergone a high-temperature high-humidity endurance test, and has excellent recording signal characteristics both in the initial stage and after the endurance test. The hardcoat that has been formed on the light-transmitting layer develops no defects, such as cracks, even after the endurance test. This optical disk has excellent durability.

Description

CD ultraviolet-curing resin composition, solidfied material and CD
Technical field
The present invention relates to the ultraviolet-curing resin composition useful to the CD with organic pigment recording layer, and the CD with its solidfied material layer.
Background technology
Now; as practical optical disc recording medium; exist (1) to be laminated with recording layer, reflection horizon and the CD of the protective seam that consisted of by ultraviolet curing resin at the polycarbonate substrate of 1.2mm; for example CD-R or CD-RW; (2) with ultraviolet curing resin the polycarbonate substrate of 0.6mm is pasted the CD that forms, for example DVD-R, DVD+R, DVD-RW, DVD+RW and DVD-RAM with the polycarbonate substrate of the 0.6mm that possesses recording layer and reflection horizon.
In addition, selling in recent years and have the approximately Blu-ray Disc of 5 times of recording capacities (BD-R) of single-layer type DVD.Transparent or the opaque plastics substrate processed that Blu-ray Disc has at 1.1mm forms reflection horizon, recording layer and contact bed, and then the euphotic structure of stacked approximately 0.1mm on contact bed is the CD that carries out record/broadcast (regeneration) across photic zone.Recording layer uses organic pigment, mineral compound, and contact bed uses the light transmission inorganics, and photic zone uses the solidfied material layer of ultraviolet curing resin.
Blu-ray Disc with the recording layer that is made of organic pigment to the recording layer irradiating laser, and utilizes the distortion that the organic pigment volume change causes and carries out record.Volume change for accessory pigments, (for example obtain good tracer signal characteristic, jittering characteristic), proposed following technology: the elastic modulus under contact bed forms 25 ℃ is the photic zone (patent documentation 1) below the 40MPa, and the elastic modulus under contact bed forms 25 ℃ is 34 to 96MPa photic zone (patent documentation 2).
In addition, evaluation index as described optical disc recording medium reliability, for example, carry out following environmental test: after placing 100 hours under the environment of 80 ℃/relative humidity 80%RH of temperature, when viewing test begins and the tracer signal deterioration in characteristics degree of this placement after 100 hours.In order to make tracer signal deterioration in characteristics degree before and after this environmental test in preset range, following technology has been proposed: be formed on elastic modulus under 5 ℃ and 55 ℃ at contact bed and be below the 100MPa and the ratio of the elastic modulus of the elastic modulus under 5 ℃ under to 55 ℃ is photic zone (patent documentation 3) below 10.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-123631 communique
Patent documentation 2: TOHKEMY 2008-269703 communique
Patent documentation 3: TOHKEMY 2009-026379 communique
Summary of the invention
The scheme that proposes in the patent documentation 1 to 3 for the volume change of accessory pigments, obtains good tracer signal characteristic (for example, jittering characteristic), and making storage modulus is below the particular value.Therefore, the use photic zone that patent documentation 1 to 3 proposes a little less than the physical strength, need to arrange hard conating with the photic zone that the protection smears forms on this euphotic surface.
Distinguish, form these photic zones, carry out again hard conating on the photic zone surface and process and to make CD, and when using this CD to place 100 hours environmental test under the many wet environments of high temperature (80 ℃/relative humidity 85%RH of temperature), hard conating cracks sometimes.When the hard conating of CD cracked, not only tracer signal characteristic (for example, jittering characteristic) reduced, and can't use as optical recording media.
In order to prevent from producing the crackle of hard conating after environmental test, it is effective improving euphotic storage modulus.But when euphotic storage modulus was too high, the dilatational strain of recording layer was suppressed, thereby was difficult to form the record mark.In addition, even realize simultaneously high storage modulus and form the resin that records mark, when the amount of warpage that when being coated with curing substrate is caused is large, also there is the problem of easily generation mistake when writing and reading.
At this, the object of the present invention is to provide a kind of ultraviolet-curing resin composition, it can be used for having the CD of organic pigment layer, and hard conating does not crack when placing under the many wet environments of high temperature, give sufficient tracer signal characteristic, and coating when solidifying the warpage of substrate little.
The inventor has carried out repeating further investigation in order to solve described problem, found that, contain multifunctional (methyl) acrylate and carbamate (methyl) acrylate, and the storage modulus E ' under 80 ℃ of cured film is the ultraviolet-curing resin composition of particular range, even will have the CD of its solidfied material layer that is applied with hard conating is placed under the many wet environments of high temperature, hard conating does not crack yet, show sufficient tracer signal characteristic, and the warpage of the substrate that produces when coating is solidified is also little, thereby finishes the present invention.
That is, the present invention relates to following (1) to (13).
(1) a kind of CD ultraviolet-curing resin composition with organic pigment layer, contain (A) multifunctional (methyl) acrylate, (B) carbamate (methyl) acrylate and (C) Photoepolymerizationinitiater initiater, wherein, the storage modulus E ' under 80 of its cured film ℃ is 50 to 200MPa scope.
(2) such as above-mentioned (1) described CD ultraviolet-curing resin composition with organic pigment layer, wherein, (methyl) acryloyl group equivalent of multifunctional (methyl) acrylate (A) is 85g/eq. to 160g/eq..
(3) such as above-mentioned (1) or (2) described CD ultraviolet-curing resin composition with organic pigment layer, wherein, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate of molecular weight 400 to 10000.
(4) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (3), wherein, multifunctional (methyl) acrylate (A) is for being selected from by 1,6-hexanediol two (methyl) acrylate, BDO two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (the oxirane modification) glycerine three (methyl) acrylate of EO modification, (epoxy pronane modification) glycerine three (methyl) acrylate of PO modification, at least a in the group that pentaerythrite four (methyl) acrylate forms.
(5) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (4), wherein, carbamate (methyl) acrylate (B) is polyvalent alcohol and polyisocyanates and the reaction product that contains (methyl) acrylate of hydroxyl, and polyvalent alcohol is polyester polyol and/or polyether glycol.
(6) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (5), it is characterized in that, contain multifunctional (methyl) acrylate (A) of 10 to 70 % by weight, carbamate (methyl) acrylate (B) of 5 to 80 % by weight and the Photoepolymerizationinitiater initiater (C) of 0.5 to 20 % by weight in the resin combination.
(7) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (6), wherein, with respect to the total amount of (methyl) acrylate that contains in the resin combination, (A) multifunctional (methyl) acrylate and (B) total amount of carbamate (methyl) acrylate be more than 90%.
(8) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (7); wherein; multifunctional (methyl) acrylate (A) is (methyl) acrylate of (methyl) acryloyl group equivalent 85g/eq. to 160g/eq., and the molecular weight that carbamate (methyl) acrylate (B) obtains for the reaction of at least a and polyisocyanates in polyester polyol or the polyether glycol reaction product that obtains and (methyl) acrylate reactions that contains hydroxyl is 400 to 10000 carbamate (methyl) acrylate.
(9) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (8), wherein, carbamate (methyl) acrylate (B) is for being selected from polyether glycol in the group that is comprised of polyglycol, polypropylene glycol and poly-BDO and reacting the reaction product that obtains with isophorone diisocyanate or toluene diisocyanate and containing carbamate (methyl) acrylate that (methyl) acrylate reactions of hydroxyl obtains.
(10) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (9), wherein, multifunctional (methyl) acrylate is for being selected from by 1,6-hexanediol two (methyl) acrylate, BDO two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) acrylate of EO modification, at least a in the group that glycerine three (methyl) acrylate of PO modification and pentaerythrite four (methyl) acrylate form.
(11) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (9), wherein, multifunctional (methyl) acrylate is for being selected from least a in the group that is comprised of 1,6-hexanediol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate and trimethylolpropane tris (methyl) acrylate.
(12) such as above-mentioned (7) described CD ultraviolet-curing resin composition; wherein; carbamate (methyl) acrylate (B) is for being selected from by polyglycol; polypropylene glycol and poly-1; polyether glycol in the group that the 4-butylene glycol forms and isophorone diisocyanate or toluene diisocyanate reaction and the reaction product that obtains and contain (methyl) acrylate reactions of hydroxyl and obtain carbamate (methyl) acrylate; multifunctional (methyl) acrylate (A) is (methyl) acrylate of (methyl) acryloyl group equivalent 85g/eq. to 160g/eq., and the content of epoxy (methyl) acrylate is 0 to being lower than 10 % by weight with respect to the total amount of resin combination.
(13) such as each described CD ultraviolet-curing resin composition with organic pigment layer in above-mentioned (1) to (12), wherein, CD is 500 to 1500MPa with the storage modulus of cured film under 25 ℃ of ultraviolet-curing resin composition.
(14) such as above-mentioned (13) described CD ultraviolet-curing resin composition with organic pigment layer, wherein, CD is 0.05 to 0.20 with the storage modulus under 80 ℃ of the cured film of ultraviolet-curing resin composition to the ratio of the storage modulus under 25 ℃.
(15) a kind of solidfied material, it is by obtaining each described ultraviolet-curing resin composition irradiation active energy beam in above-mentioned (1) to (14).
(16) a kind of CD with organic pigment recording layer, it has by each described ultraviolet-curing resin composition in optic disc base board coating above-mentioned (1) to (14), and the solidfied material layer that its irradiation active energy beam is obtained.
The invention effect
When using the CD with organic pigment layer of the present invention to have the photic zone of CD of organic pigment recording layer with ultraviolet-curing resin composition (being designated hereinafter simply as resin combination of the present invention) conduct, can obtain having the CD of following characteristic: hard conating does not crack when using for a long time under hot and humid environment, jitter value all is lower than 10% good tracer signal characteristic after having initial stage and long duration test, and the warpage that produces when coating is solidified is little.
Embodiment
Resin combination of the present invention contains multifunctional (methyl) acrylate (A), carbamate (methyl) acrylate (B) and Photoepolymerizationinitiater initiater (C).
As multifunctional (methyl) acrylate (A) that contains in the resin combination of the present invention, as long as multifunctional (methyl) acrylate for except described carbamate (methyl) acrylate (B) and aftermentioned epoxy (methyl) acrylate then can use ad lib.
For example, can use functional group's number of multifunctional (methyl) acrylate to be generally multifunctional (methyl) acrylate of two to six.Be preferably (methyl) acrylate of two to four senses, more preferably two to trifunctional (methyl) acrylate.
As this preferred multifunctional (methyl) acrylate, can enumerate, for example: 1,6-hexanediol two (methyl) acrylate (for example, the Photomer-4017 that peaceful (the コ グ ニ ス ジ ャ パ Application) Co., Ltd. of day undergraduate course makes), 1,4-butylene glycol two (methyl) acrylate (for example, the Off ア Application Network リ Le FA-124AS that Hitachi Chemical Co., Ltd. makes), tripropylene glycol two (methyl) acrylate (for example, the TPGDA that special (the ダ イ セ Le サ イ テ Star Network) Co., Ltd. of Daicel cyanogen makes), dipropylene glycol two (methyl) acrylate (for example, the Photomer-4226 that peaceful (the コ グ ニ ス ジ ャ パ Application) Co., Ltd. of day undergraduate course makes), tristane dimethanol two (methyl) acrylate (for example, the KAYARAD R-684 that Nippon Kayaku K. K makes), neopentyl glycol two (methyl) acrylate (for example, the KAYARAD NPGDA that Nippon Kayaku K. K makes), pentaerythrite three (methyl) acrylate (for example, the KAYARAD PET-30 that Nippon Kayaku K. K makes), trimethylolpropane tris (methyl) acrylate (for example, the KAYARADTMPTA that Nippon Kayaku K. K makes), glycerine three (methyl) acrylate of EO modification (glycerine three (methyl) acrylate of preferred 1 to 4 mole of EO modification, for example, the KAYARADTHE-330 that Nippon Kayaku K. K makes), glycerine three (methyl) acrylate of PO modification (glycerine three (methyl) acrylate of preferred 1 to 3 mole of PO modification, for example, the KAYARADGPO-303 that Nippon Kayaku K. K makes), pentaerythrite four (methyl) acrylate (for example, the SR295 of Sartomer (サ one ト マ one) Co., Ltd. manufacturing) etc.
In addition, among the present invention, two to four multifunctional (methyl) acrylate of two to four polyfunctional alcohols of the carbon number 4 to 12 of the preferred chain structure that does not contain ring texture is more preferably removed two to four multifunctional (methyl) acrylate of the chain structure of tristane dimethanol two (methyl) acrylate from above-mentioned illustrative multifunctional (methyl) acrylate.
As further preferred multifunctional (methyl) acrylate, can enumerate: 1,6-hexanediol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate and trimethylolpropane tris (methyl) acrylate etc., resin combination of the present invention preferably contain and are selected from least a in the group that is comprised of these compounds.
In addition, this multifunctional (methyl) acrylate (A) preferably has multifunctional (methyl) acrylate of (methyl) acryloyl group equivalent of certain limit.As this (methyl) acryloyl group equivalent, preferred 85 to 160g/eq., and more preferably 86 to 157g/eq..When (methyl) acryloyl group equivalent was very few, the shrinkage factor during curing was large, and the initial stage warpage is large, and is therefore not preferred.On the other hand, when (methyl) acryloyl group equivalent was excessive, resin was soft, and hard conating is large with the difference of the rate of change of the euphotic elastic modulus that is caused by temperature, thereby hard conating easily cracks, so not preferred.
In addition; the solidfied material of resin combination of the present invention that contains multifunctional (methyl) acrylate of (methyl) acryloyl group equivalent that has this; therefore elastic modulus from 25 ℃ of room temperatures to high temperature under 85 ℃ with low uncertainty, can bring into play the effect of the present application.
And; the solidfied material that will contain the resin combination of the present invention of multifunctional (methyl) acrylate with this (methyl) acryloyl group equivalent is arranged on as photic zone and obtains CD on the substrate; and when this CD is kept at high temperature (50 to 55 ℃) or low temperature (0 to 5 ℃); no matter any situation all can suppress the variable quantity of warpage lower.
At this, (methyl) acryloyl group equivalent, expression uses the molecular weight of compound divided by the resulting value of quantity (functional group's number) of intramolecular (methyl) acryloyl group.
In addition, the term that uses in this instructions " (methyl) acryloyl group ", at least a implication of expression " acryloyl group " or " methacryl ", terms such as " (methyl) acrylate " also is used for representing same implication.
In resin combination of the present invention, these (A) compositions can mix one or more uses with arbitrary proportion.
(A) content of composition in resin combination (with respect to the content of resin combination total amount, below same statement represent identical implication) is generally 10 to 70 % by weight, preferred 20 to 70 % by weight, more preferably 25 to 50 % by weight.
In addition; total amount with respect to (methyl) acrylate composition that contains in the resin combination of the present invention; more preferably following situation: (methyl) acryloyl group equivalent is that two (methyl) acrylate of 85 to 160g/eq. is 60 to 100 % by weight; preferred 80 to 100 % by weight; other (methyl) acrylate composition is 0 to 20 % by weight, preferred 0 to 10 % by weight.In addition, in this situation, more preferably following situation: other (methyl) acrylate composition is three to four (methyl) acrylate (preferred three (methyl) acrylate) of 85 to 160g/eq. for (methyl) acryloyl group equivalent.But, in this situation, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate carbamate (methyl) acrylate that obtains as polyvalent alcohol except the polyfunctional alcohol who uses the polycaprolactone modification.
In addition, when (A) composition was very few, the storage modulus E ' under 80 ℃ had the tendency of step-down, therefore, was placed on the many wet environments of high temperature lower times, had the tendency that photic zone easily cracks.In addition, in the time of too much, (size of warpage is poor behind the warpage of coating resin prebasal plate and the coating cured resin: the variable quantity of warpage) have the tendency that becomes large for the warpage of the substrate that produces when coating is solidified.
The carbamate that contains in the resin combination of the present invention (methyl) acrylate (B) has following function: the mechanical property that improves the CD of pasting with resin combination of the present invention.Particularly, the warpage and/or the strain that produce when reducing described solidify, and described solidfied material is preserved (0 to 5 ℃) lower warpage that the produces (warpage after the warpage before preserving and the preservation poor: the variable quantity of warpage) etc. at High temperature storage (50 to 55 ℃) and/or low temperature.
In addition, compare with other (methyl) acrylate, carbamate (methyl) acrylate can keep storage modulus under 80 ℃ of the high temperature than the highland.
Carbamate (methyl) acrylate (B) obtains by polyvalent alcohol (a), polyisocyanates (b) and hydroxyl (methyl) acrylate (c) reaction.
As the synthetic middle polyvalent alcohol (a) that uses of carbamate (methyl) acrylate (B), as long as for having the polyvalent alcohol of two above hydroxyls in the molecule, then can use with being not particularly limited.Can enumerate, for example: following polyvalent alcohol.
(i) aliphatic polyol, such as neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythrite, tristane dimethanol, two-[hydroxymethyl]-cyclohexane etc. are generally the aliphatic polyol of carbon number 2 to 10.
(ii) reaction of a kind of and polyprotonic acid of above-mentioned (i) aliphatic polyol of putting down in writing and the polyester polyol that obtains.
In addition, as above-mentioned polyprotonic acid, can enumerate, such as: succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid (TPA), hexane diacid, azelaic acid, tetrabydrophthalic anhydride etc.
(iii) polyether glycol.
For example, poly-C2 to C4 alkylene glycol is such as polyglycol, polypropylene glycol or poly-BDO etc.; The bisphenol-A of C2 to C3 alkylene oxide modification is such as bisphenol-A of oxirane modification etc.
In above-mentioned, as polyvalent alcohol, from improving physical strength, keep the viewpoint of 80 ℃ of lower storage moduluss to consider than the highland, preferred, polyethers polyvalent alcohol, more preferably poly-C2 to C4 alkylene glycol, further preferred polypropylene glycol.
The number-average molecular weight of polyester polyol or polyether glycol, preferred approximately 200 to approximately 8000, more preferably from about 200 to approximately 3000, further preferred approximately 400 to approximately 2000, most preferably from about 600 to approximately 1500.
The synthetic middle polyisocyanates (b) that uses of carbamate (methyl) acrylate (B), for in molecule, having the compound of two above isocyanate group, for example, preferably in molecule, have the polyisocyanates of two to three isocyanate group, more preferably diisocyanate cpd.
Can enumerate, for example: isophorone diisocyanate, 1, hexamethylene-diisocyanate, toluene diisocyanate, Xylene Diisocyanate or diphenyl methane-4,4 '-diisocyanate etc.
In these compounds, more preferably isophorone diisocyanate or toluene diisocyanate.
Synthetic middle hydroxyl (methyl) acrylate (c) that uses as carbamate (methyl) acrylate (B); as long as in molecule, having the compound of hydroxyl and (methyl) acryloyl group, then can use with being not particularly limited.
Can enumerate, for example: the list of C2 to C8 aliphatic dihydroxy alcohol (methyl) acrylate, such as (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, dihydroxymethyl cyclohexyl list (methyl) acrylate etc.
Described reaction, for example mode is carried out as described below.
Namely, in described polyvalent alcohol (a), mix polyisocyanates (b), so that with respect to per 1 equivalent hydroxyl of polyvalent alcohol (a), the isocyanate group of polyisocyanates (b) is preferably 1.1 to 2.0 equivalents, and under 25 to 90 ℃ of temperature of reaction, preferred 50 to 80 ℃ condition, react the synthesis of carbamates oligomer.Then, mix hydroxyl (methyl) acrylate (c), so that with respect to per 1 equivalent isocyanate group of resulting oligourethane, the hydroxyl of hydroxyl (methyl) acrylate (c) is preferably 1 to 1.5 equivalent, and under 70 to 90 ℃ condition, react, obtain target carbamate (methyl) acrylate.
In order to shorten the reaction time of these reactions, can use catalyzer, also can use polymerization inhibitor etc.In addition, also can be used as UX-0937: polyethers urethane acrylate (Nippon Kayaku K. K's manufacturing) etc. obtains from market.The molecular weight of carbamate (methyl) acrylate (B), preferred approximately 400 to approximately 10000, more preferably from about 500 to approximately 5000, further preferred approximately 600 to approximately 2500, in addition, and according to circumstances, more preferably 700 to 10000.In addition, the molecular weight of carbamate (methyl) acrylate is weight-average molecular weight.
In the resin combination of the present invention, the content of these (B) compositions in resin combination is generally 5 to 80 % by weight, preferred 20 to 70 % by weight.In addition, according to circumstances, preferred 30 to 70 % by weight, more preferably 35 to 70 % by weight, further preferred 45 to 70 % by weight.
When being lower than 5 % by weight, when carrying out design of material, be difficult to obtain the object elastic modulus under 80 ℃, thus not preferred; When surpassing 80 % by weight, elastic modulus is excessively low, thereby not preferred.
Be that the viewpoint of 50 to 200MPa solidfied material is considered from obtaining elastic modulus under 80 ℃, above-mentioned (A) composition and (B) the total content of composition with respect to the total amount of the light-cured type resinous principle that contains in this resin combination (below be also referred to as (methyl) acrylate composition), more than preferred 70 % by weight, more preferably more than 80 % by weight, particularly preferably more than 90 % by weight.The upper limit can be down to 00 % by weight.
In addition, above-mentioned (A) composition and (B) the total content of composition be 80 to 99.5 % by weight with respect to the ratio of the total amount of resin combination of the present invention, more preferably 90 to 99 % by weight.
In addition; one of optimal way of the present invention is following resin combination: above-mentioned multifunctional (methyl) acrylate (A) is described multifunctional (methyl) acrylate with (methyl) acryloyl group equivalent 85 to 160g/eq; the total content of itself and carbamate (methyl) acrylate is with respect to the total content of (methyl) acrylate composition in the resin combination of the present invention; preferred 70 to 100 % by weight; more preferably 80 to 100 % by weight, further preferred 90 to 100 % by weight.
In addition; one of preferred mode is following resin combination: in above-mentioned preferred mode; contain two (methyl) acrylate as multifunctional (methyl) acrylate with (methyl) acryloyl group equivalent 85 to 160g/eq; and the total amount with respect to (methyl) acrylate composition in the resin combination of the present invention; at least contain 50 % by weight; preferred 80 to 100 % by weight, more preferably 90 to 100 % by weight.But in this case, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate of the polyvalent alcohol of use except the polyfunctional alcohol of polycaprolactone modification as polyvalent alcohol.
In addition, one of preferred mode is following situation: in above-mentioned preferred mode, multifunctional (methyl) acrylate is as described preferably multifunctional (methyl) acrylate and (methyl) acrylate of particular instantiation.
One of further preferred mode is following situation: in above-mentioned preferred mode or preferred mode, multifunctional (methyl) acrylate is as described preferred multifunctional (methyl) acrylate and (methyl) acrylate of particular instantiation.
In addition, in the resin combination of the present invention, only containing 1, in the situation of 6-hexanediol two (methyl) acrylate as multifunctional (methyl) acrylate, carbamate (methyl) acrylate preferably uses polyvalent alcohol except the polyfunctional alcohol of polycaprolactone modification, is preferably selected from carbamate (methyl) acrylate that the polyether glycol in the group that is comprised of polyglycol, polypropylene glycol and poly-BDO obtains as polyvalent alcohol; Carbamate (methyl) acrylate that more preferably uses polypropylene glycol and obtain.In addition, preferably do not contain as epoxy (methyl) acrylate of choosing (methyl) acrylate composition wantonly yet.
As the Photoepolymerizationinitiater initiater that contains in the resin combination of the present invention (C), as long as for causing by ultraviolet ray the photopolymerisable compound of described acrylate compounds, then be not particularly limited.
Can enumerate, for example: 1-hydroxycyclohexylphenylketone (IRGACURE184; The Ciba manufacturing), 2-hydroxy-2-methyl-[4-(1-methyl ethylene) phenyl] propyl alcohol oligomer (ONE-Rifined), 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone (IRGACURE2959; The Ciba manufacturing), 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl }-2-methylpropane-1-ketone (IRGACURE-127; Ciba is made), 2,2-dimethoxy-2-phenyl acetophenone (IRGACURE651; The Ciba manufacturing), 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (DAROCUR1173; The Ciba manufacturing), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone (IRGACURE-907; The Ciba manufacturing), 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, CTX, 2; 4-dimethyl thioxanthones, 2; 4-diisopropyl thioxanthones, isopropyl thioxanthone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; the 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.
In the resin combination of the present invention, these (C) compositions can mix one or more uses with arbitrary proportion.(C) content of composition in resin combination is generally 0.5 to 20 % by weight, preferred 1 to 10 % by weight.At this, when content was lower than 0.5 % by weight, irradiation was solidified during active energy beam insufficient, thereby not preferred, when surpassing 20 % by weight, the physical property of solidfied material was caused harmful effect, thereby not preferred.
In addition, about multifunctional in the resin combination of the present invention (methyl) acrylate (A), carbamate (methyl) acrylate (B) and (C) Photoepolymerizationinitiater initiater preferred content ratio separately, total amount with respect to resin combination, multifunctional (methyl) acrylate (A) is 10 to 70 % by weight, carbamate (methyl) acrylate (B) is 20 to 70 % by weight, and Photoepolymerizationinitiater initiater (C) is 0.5 to 20 % by weight, preferred 1 to 10 % by weight, and the total content of multifunctional (methyl) acrylate (A) and carbamate (methyl) acrylate (B) is 80 to 99.5 % by weight, preferred 90 to 99 % by weight.
In addition, also the amine that can cause auxiliary agent as photopolymerization etc. can be used in combination with above-mentioned Photoepolymerizationinitiater initiater.As operable amine etc., can enumerate: 2-dimethyl ethyl aminobenzoate, dimethylamino acetophenone, (dimethylamino)-ethyl benzoate or IADB etc.Also can not contain the photopolymerization initiation auxiliary agents such as this amine, when using as required, the content in resin combination of the present invention is generally 0.005 to 5 % by weight, preferred 0.01 to 3 % by weight.
Resin combination of the present invention can add adjuvant as required, such as rust preventive, antioxidant, organic solvent, silane coupling agent, polymerization inhibitor, levelling agent, antistatic agent, surface lubricant, fluorescer, light stabilizer (for example, hindered amine compound etc.), filling agent etc.Hindered amine compound as long as for known hindered amine compound, then can use, as concrete example with being not particularly limited, can enumerate, for example: 1,2,2,6,6-pentamethyl-4-piperidine alcohols, 2,2,6,6-tetramethyl-4-piperidine alcohols, (methyl) acrylic acid 1,2,2,6, (Ai Dike (ア デ カ) Co., Ltd. makes 6-pentamethyl-4-piperidyl ester, LA-82) etc.
Resin combination of the present invention as required, can contain epoxy (methyl) acrylate and/or simple function (methyl) acrylate as optional (methyl) acrylate composition.In the present invention, usually can not contain, with respect to the total amount of resin combination of the present invention, its content is 0 to being lower than 10 % by weight, preferred 0 to 8 % by weight, more preferably 0 to 5 % by weight.
Epoxy (methyl) acrylate mostly is multifunctional (methyl) acrylate usually, but in the present invention, is not included in multifunctional (methyl) acrylate of described (A) composition.But, as optional (methyl) acrylate composition, according to circumstances, also can in resin combination of the present invention, contain.
As epoxy (methyl) acrylate, as long as for glycidol ether type epoxy compound and epoxy (methyl) acrylate that the reaction of (methyl) acrylic acid obtains, then can choose use wantonly.
As the glycidol ether type epoxy compound that is used for obtaining epoxy (methyl) acrylate, can enumerate: the diglycidyl ether of bisphenol-A or its alkylene oxide addition product, the diglycidyl ether of Bisphenol F or its alkylene oxide addition product, the diglycidyl ether of hydrogenated bisphenol A or its alkylene oxide addition product, the diglycidyl ether of A Hydrogenated Bisphenol A F or its alkylene oxide addition product, ethylene glycol diglycidylether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, polypropylene glycol diglycidyl ether etc.The molecular weight of epoxy (methyl) acrylate, preferred 500 to 10000, more preferably 700 to 10000.
Epoxy (methyl) acrylate reacts under the following conditions by these glycidol ether type epoxy compounds and (methyl) acrylic acid and obtains.
With respect to epoxy radicals 1 equivalent of glycidol ether type epoxy compound, (methyl) acrylic acid reacts with 0.9 to 1.5 mole, preferred 0.95 to 1.1 mole ratio.Preferred 80 to 120 ℃ of temperature of reaction, the reaction time is approximately 10 to approximately 35 hours.In order to promote reaction, preferably use catalyzer, for example: triphenylphosphine, 2,4,6-three [(dimethylamino) methyl] phenol (TAP), triethanolamine, etamon chloride etc.In addition, in the reaction, in order to prevent polymerization, can use MEHQ, methylnaphthohydroquinone etc. as polymerization inhibitor.
At this, from improving physical strength, keep the viewpoint consideration of 80 ℃ of lower storage moduluss than the highland, even do not use especially epoxy (methyl) acrylate, also no problem.
Resin combination of the present invention as mentioned above, also can contain simple function (methyl) acrylate as required as choosing (methyl) acrylate composition except (A) composition with (B) wantonly the composition.
As simple function (methyl) acrylate, can enumerate, for example: (methyl) acrylic acid phenoxy ethyl, phenoxy group polyglycol (methyl) acrylate, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, morpholine (methyl) acrylate, (methyl) acrylic acid phenyl glycidyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, ethoxy diethylene glycol (methyl) acrylate, methoxyl two (tripropylene glycol) (methyl) acrylate, tristane (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentadiene 2-ethoxyethyl acetate, acrylic acid dihydro dicyclopentadiene ester (for example, the FANCRYL of Hitachi Chemical Co., Ltd.'s manufacturing RTMFA-511A), acrylic acid dihydro dicyclopentadiene 2-ethoxyethyl acetate (for example, the FANCRYL of Hitachi Chemical Co., Ltd.'s manufacturing RTMFA-512A), metering system acid dihydride dicyclopentadiene 2-ethoxyethyl acetate (for example, the FANCRYL of Hitachi Chemical Co., Ltd.'s manufacturing RTMFA-512M), acrylic acid tetrahydrochysene dicyclopentadiene ester (for example, the FANCRYL of Hitachi Chemical Co., Ltd.'s manufacturing RTMFA-513A), methacrylic acid tetrahydrochysene dicyclopentadiene ester (for example, the FANCRYL of Hitachi Chemical Co., Ltd.'s manufacturing RTMFA-513M), acrylic acid 1-diamantane ester (for example, the Adamantate AA that Idemitsu Kosen Co., Ltd. makes), acrylic acid 2-methyl-2-diamantane ester (for example, the Adamantate MA that Idemitsu Kosen Co., Ltd. makes), acrylic acid 2-ethyl-2-diamantane ester (for example, the Adamantate of Idemitsu Kosen Co., Ltd.'s manufacturing RTMEA), methacrylic acid 1-diamantane ester (for example, the Adamantate of Idemitsu Kosen Co., Ltd.'s manufacturing RTMAM), phosphoric acid (methyl) acrylate of the octyloxy of phosphoric acid (methyl) acrylate of the butoxy of the phosphoric acid of the phenoxylation of oxirane modification (methyl) acrylate, oxirane modification and oxirane modification etc.
In addition, the subscript RTM in above-mentioned represents registered trademark, lower with.
In addition, explanation place at described hindered amine illustrative (methyl) acrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl ester is simple function (methyl) acrylate, but is categorized as in this manual hindered amine, is not included in simple function (methyl) acrylate as optional member.
Simple function (methyl) acrylate of optional (methyl) acrylate composition of above-mentioned conduct, total amount with respect to resin combination of the present invention, can be for example in 0 to 20 % by weight, preferred approximately 0 to about 10 % by weight, more preferably from about 0 contain to the about scope of 5 % by weight, do not contain but also can resemble shown in the embodiment.
Resin combination of the present invention can by described each composition mixed dissolution being obtained normal temperature to 80 ℃ is lower, also can wait operation removal impurity by filtering as required.Resin combination of the present invention, consider from the viewpoint of coating, preferred so that the viscosity under 25 ℃ is the match ratio that the mode of 30 to 2000mPas scope is suitably regulated composition, and particularly preferably the viscosity under 25 ℃ is regulated as 500 to 1800mPas mode.
In addition, importantly, resin combination of the present invention is so that the storage modulus E ' under 80 ℃ of the solidfied material of this resin combination is the mode of 50 to 200MPa scope is prepared.
Thus, can reach described effect of the present invention.
In addition, one of feature of resin combination of the present invention also is, the difference of the storage modulus E ' under the storage modulus under 25 ℃ of the solidfied material of this resin combination and 80 ℃ is less.For example, preferred 500 to 1500MPa the scope of storage modulus under 25 ℃ of the solidfied material of resin combination of the present invention, more preferably 600 to 1000MPa scope.Therefore, when preparing resin combination of the present invention, preferably making the storage modulus under 25 ℃ is above-mentioned scope.
Storage modulus under 25 ℃ is crossed when low, can't obtain sufficient hardness during as the photic zone of CD, and in addition, when 25 ℃ of lower storage moduluss were too high, the warpage of CD was excessive during curing, so not preferred.
In addition, about resin combination of the present invention, storage modulus E ' under 80 ℃ of its solidfied material with 25 ℃ under the ratio of storage modulus, namely, when the value of the storage modulus under the storage modulus E ' under 80 ℃/25 ℃ is 0.05 to 0.20 scope more preferably, further preferred approximately 0.05 to approximately 0.15, most preferably from about 0.07 to approximately 0.15.
Resin combination of the present invention can obtain solidfied material by irradiation ultraviolet radiation.This solidfied material has above-mentioned storage modulus, and the transparency is high, and the wavelength that Blu-ray Disc etc. use the approximately transmitance of the light of 400nm is high, for example, in the cured film of thickness 100 μ m, the transmitance of the light of wavelength 405nm can reach more than 85%, preferably can reach more than 90%.
The optimal way of following illustration resin combination of the present invention described above.
(I) a kind of CD with organic pigment layer is with ultraviolet-curing resin composition (being designated hereinafter simply as resin combination), total amount with respect to resin combination, contain multifunctional (methyl) acrylate (A) of 10 to 70 % by weight, carbamate (methyl) acrylate (B) of 5 to 80 % by weight and the Photoepolymerizationinitiater initiater (C) of 0.5 to 20 % by weight
(1) (methyl) acryloyl group equivalent of multifunctional (methyl) acrylate (A) is 85g/eq. to 160g/eq.,
(2) the storage modulus E ' under 80 of the cured film of this resin combination ℃ is 50 to 200MPa scope.
(II) above-mentioned (I) resin combination of putting down in writing, wherein, contain multifunctional (methyl) acrylate (A) of 20 to 70 % by weight and carbamate (methyl) acrylate (B) of 20 to 70 % by weight, (A) composition and (B) the total content of composition, total amount { (A) composition with respect to (methyl) acrylate composition that contains in the resin combination, (B) composition and simple function (methyl) acrylate of optional (methyl) acrylate composition of conduct and/or the total content of epoxy (methyl) acrylate }, contain at least 80 % by weight.
(III) above-mentioned (I) or the resin combination (II) put down in writing, wherein, multifunctional (methyl) acrylate (A) is for being selected from by 1,6-hexanediol two (methyl) acrylate, BDO two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) acrylate of EO modification, at least a in the group that glycerine three (methyl) acrylate of PO modification and pentaerythrite four (methyl) acrylate form.
(IV) above-mentioned (III) resin combination of putting down in writing, wherein, multifunctional (methyl) acrylate (A) is multifunctional (methyl) acrylate except tristane dimethanol two (methyl) acrylate.
(V) above-mentioned (III) resin combination of putting down in writing, wherein, multifunctional (methyl) acrylate (A) is for being selected from least a in the group that is comprised of 1,6-hexanediol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate and trimethylolpropane tris (methyl) acrylate.
(VI) above-mentioned (I) or (V) in each resin combination of putting down in writing, wherein, the molecular weight that obtains at least a and polyisocyanates in polyester polyol or the polyether glycol reaction reaction product that obtains and (methyl) acrylate reactions that contains hydroxyl of carbamate (methyl) acrylate (B) is 400 to 10000 carbamate (methyl) acrylate.
(VII) above-mentioned (VI) resin combination of putting down in writing, wherein, multifunctional (methyl) acrylate (A) only is 1, during 6-hexanediol two (methyl) acrylate, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate except the carbamate that contains the polylactone structure (methyl) acrylate, and does not contain epoxy (methyl) acrylate as optional (methyl) acrylate composition.
(VIII) above-mentioned (VI) resin combination of putting down in writing, wherein, carbamate (methyl) acrylate (B) is 400 to 10000 carbamate (methyl) acrylate for the molecular weight that is selected from polyether glycol in the group that is comprised of polyglycol, polypropylene glycol and poly-BDO and reacts the reaction product that obtains with isophorone diisocyanate or toluene diisocyanate and contain (methyl) acrylate reactions of hydroxyl and obtain.
(IX) above-mentioned (I) or (VIII) in each resin combination of putting down in writing, wherein, multifunctional (methyl) acrylate (A) only comprises two (methyl) acrylate, perhaps comprise these two kinds of two (methyl) acrylate and three to six (methyl) acrylate, total amount with respect to (methyl) acrylate composition in the resin combination, at least contain 50 % by weight two (methyl) acrylate, but, in this case, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate carbamate (methyl) acrylate that is used as polyvalent alcohol except the polyfunctional alcohol who uses the polycaprolactone modification and obtains.
(X) above-mentioned (IX) resin combination of putting down in writing, wherein, the content of two (methyl) acrylate is 70 to 100 % by weight, preferred 80 to 100 % by weight, more preferably 90 to 100 % by weight.
(XI) above-mentioned (I) or (X) in each CD ultraviolet-curing resin composition of putting down in writing; wherein; carbamate (methyl) acrylate (B) is for being selected from by polyglycol; polypropylene glycol and poly-1; polyether glycol in the group that the 4-butylene glycol forms and isophorone diisocyanate or toluene diisocyanate reaction and the reaction product that obtains and contain (methyl) acrylate reactions of hydroxyl and carbamate (methyl) acrylate that obtains; multifunctional (methyl) acrylate (A) is (methyl) acrylate of (methyl) acryloyl group equivalent 85g/eq. to 160g/eq., and the content of epoxy (methyl) acrylate is 0 to being lower than 10 % by weight with respect to the total amount of resin combination.
(XII) above-mentioned (I) or (XI) in each CD ultraviolet-curing resin composition with organic pigment layer of putting down in writing, wherein, CD is 500 to 1500MPa with the storage modulus under 25 ℃ of the cured film of ultraviolet-curing resin composition.
(XIII) above-mentioned (I) or (XII) in each CD ultraviolet-curing resin composition with organic pigment layer of putting down in writing, wherein, CD is 0.05 to 0.20 with the storage modulus under 80 ℃ of the cured film of ultraviolet-curing resin composition with the ratio of storage modulus under 25 ℃.
Resin combination of the present invention can obtain resin cured matter of the present invention by irradiation ultraviolet radiation.Resin combination of the present invention is as described below for the photic zone purposes, and therefore, the solidfied material layer (photic zone) that above-mentioned resin cured matter of the present invention can be used as CD etc. uses.
Resin combination of the present invention can suit to use with the smears as the photic zone of the laser light incident side of Blu-ray Disc etc.Particularly, so that the thickness of resin of coating is that the mode of 1 to 100 μ m is by any means, such as the coating composition on optic disc base board such as spin-coating method, 2P method, rolling method, silk screen print method.After the coating, the light of (wavelength approximately 200 to about 400nm) from the single or double irradiation ultraviolet radiation near ultraviolet ray and make its curing.Thickness after the curing is roughly corresponding with the thickness of coating, is approximately 1 to about 100 μ m.Exposure preferably approximately 50 to about 1500mJ/cm 2, particularly preferably approximately 100 to about 1000mJ/cm 2For being cured by irradiation ultraviolet radiation to the light of near ultraviolet ray, as long as for being used for irradiation ultraviolet radiation to the lamp of the light of near ultraviolet ray, then can use any light source.Can enumerate, such as: low pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, (pulse) xenon lamp or electrodeless lamp etc.
The value of the storage modulus E ' of the solidfied material of resin combination of the present invention is measured according to the Measurement of Dynamic Viscoelasticity method based on JIS K7244-5.That is, use Fusion lamp D bulb, at 1J/cm 2Accumulated light under be cured and make sample chips with the size of length 5cm, width 1cm, thickness 1mm, and use Seiko to be full of the viscoelasticity device DMS6100 that electronics technology (ェ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one) company of department makes and measure.Be determined under the beam mode and carry out, under the condition of 2 ℃/minute of amplitude load 10mN, frequency 10Hz, programming rates and in-50 ℃ to 150 ℃ scope, measure.
Resin combination of the present invention can be used to form the photic zone (resin bed) that forms at recording layer or contact bed.This photic zone (resin bed) can be consisted of or be consisted of by forming different two-layer above multilayers by same one deck that forms.But, in the situation that photic zone is made of multi-layer resinous layer, can't reach efficient aspect the production of CD, and aspect speed of production, yield rate, process units cost up, so one deck of the preferred same composition of photic zone consists of.The photic zone that resin combination of the present invention can be used as in individual layer purposes or the multilayer purposes any uses, and is suitable for being particularly suitable for the photic zone purposes of one deck formation as the photic zone that contact with recording layer or contact bed.
That is, when using resin combination of the present invention, even in the situation that one deck of described same composition consists of, the possibility that hard conating does not also crack after environmental test, thereby when record and after environmental test, can obtain good characteristics of signals.Therefore, particularly useful for the photic zone purposes of one deck formation.
Resin combination of the present invention is applicable to use organic pigment layer (hereinafter referred to as the organic pigment recording layer) as the CD purposes of recording layer.
The material of organic pigment recording layer need to have photosensitivity to the wavelength of the laser that uses in the recording played.In addition, the material of organic pigment recording layer need to be by irradiating laser generation physical change or chemical reaction, and the variation that produces thus refractive index.Therefore, as the material of organic pigment recording layer, can example as: anthocyanidin, cyanines class pigment, azopigment, phthalocyanine dye, porphyrin are pigment.These organic materials for example are mixed to get mixed solution with cellosolve acetic acid esters, tetrafluoropropanol equal solvent, use this mixed solution by organic Pigment Record layers of formation such as spin-coating methods.More than the preferred 15nm of the thickness of organic pigment recording layer and below the 25nm.
The function that contact bed has is to prevent following mixing phenomena: the pigment that contains in organic pigment layer during photic zone film forming diffusion in the photic zone, be used to form euphotic cured resin solvent etc. to the infiltration of organic pigment layer etc.Consist of the material of this contact bed, can enumerate: monox is the oxide such as silicon dioxide or zinc paste, cerium oxide, yttria particularly; Zinc sulphide, yttrium sulfide sulfides; The nitride such as silicon nitride; Silit; The potpourri of oxide and sulphur; The potpourri of silicon dioxide and zinc sulphide; Aluminium oxide etc.This contact bed can form by methods such as sputters.
Resin combination of the present invention, as mentioned above, be suitable for the photic zone that individual layer consists of, but, photic zone is by being formed on the first resin bed on recording layer or the contact bed and when observing the second resin bed be formed on the one side opposite with recording layer or contact bed side and consist of from the first resin bed, that is, photic zone is different two-layer when consisting of by forming, and resin combination of the present invention also can be used as described the first resin bed and/or described the second resin bed uses.
In this case, the thickness of described the first resin bed is generally 1 μ m to 50 μ m, preferred 5 μ m to 40 μ m, more preferably 10 μ m to 30 μ m.
In addition, the thickness of described the second resin bed is generally 50 μ m to 100 μ m, preferred 60 μ m to 95 μ m, more preferably 70 μ m to 90 μ m.
On the other hand, when photic zone was made of one deck, the thickness of resin bed was generally 70 μ m to 100 μ m, preferred 80 μ m to 95 μ m.
The photic zone that uses resin combination of the present invention to obtain preferably is adjacent to be arranged on described organic pigment recording film or the contact bed.Like this, the photic zone to obtain with mode setup and use resin combination of the present invention that organic pigment recording film or contact bed directly contact thus, can obtain good recording characteristic before and after endurancing.
In addition, the photic zone that uses resin combination of the present invention to obtain is made one deck as previously mentioned consist of, thus, even at photic zone hard conating is set, can prevent in endurancing that also hard conating from cracking.
When the euphotic physical strength that uses resin combination of the present invention to form is weak, can carries out as required hard conating on this euphotic surface and process.
As mentioned above, have the organic pigment recording film or having on the organic pigment recording film of optic disc base board of organic pigment recording film and contact bed or contact bed coating resin combination of the present invention, and make it solidify to form photic zone, and at this photic zone hard conating is set as required, thus, can obtain CD of the present invention.
(embodiment)
Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these embodiment.
Ultraviolet-curing resin composition with the composition Preparation Example 1 to 4 shown in the table 1 and comparative example 1 to 2.
[table 1] resin combination and evaluation result
? Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2
Multifunctional (methyl) acrylate (A) ? ? ? ? ? ?
A-1 33 ? ? 33 26 ?
A-2 ? ? 37 ? ? 40
A-3 ? 40 ? ? ? ?
A-4 ? ? 3 7 14 ?
Carbamate (methyl) acrylate (B) ? ? ? ? ? ?
UA-1 62 55 55 55 55 55
Photoepolymerizationinitiater initiater (C) ? ? ? ? ? ?
C-1 4 4 4 4 4 4
Light stabilizer (D) ? ? ? ? ? ?
D-1 1 1 1 1 1 1
Storage modulus under 25 ℃ (MPa) 660 980 720 1380 - -
Storage modulus under 80 ℃ (MPa) 75 55 51 196 240 31
The initial stage warpage ? ? ? ? ? ?
Initial stage warpage (degree) -0.8 -0.7 -0.5 -1.4 -1.6 -0.4
Judge ○ ○ ○ ○ × ○
Tracer signal characteristic before and after the long duration test ? ? ? ? ? ?
Jitter value (%) before the long duration test 6.5 6.4 6.6 7 6.9 6.8
Judge ○ ○ ○ ○ ○ ○
Jitter value after the long duration test (%) 8.9 8.4 8.8 9.3 9.4 -
Judge ○ ○ ○ ○ ○ ×
Crackle is estimated ? ? ? ? ? ?
Crackle has or not after the long duration test Nothing Nothing Nothing Nothing Nothing Have
In addition, as described below with each composition that is called for short expression in the table 1.
A-1:1,6-hexanediyl ester, Photomer-4017 (the acryloyl group equivalent: 127g/eq) that peaceful (the コ グ ニ ス ジ ャ パ Application) Co., Ltd. of day undergraduate course makes
A-2: tripropylene glycol diacrylate, TPGDA (the acryloyl group equivalent: 150g/eq) that special (the ダ イ セ Le サ イ テ Star Network) Co., Ltd. of Daicel cyanogen makes
A-3: propylene glycol diacrylate, Photomer-4226 (the acryloyl group equivalent: 121g/eq) that peaceful (the コ グ ニ ス ジ ャ パ Application) Co., Ltd. of day undergraduate course makes
A-4: pentaerythritol triacrylate, KAYARADPET-30 (the acryloyl group equivalent: 87g/eq) that Nippon Kayaku K. K makes
UA-1: polypropylene glycol (molecular weight 1000), toluene diisocyanate, these three kinds of compositions of acrylic acid 2-hydroxyl ethyl ester react and the urethane acrylate that obtains with the mol ratio of 1:2:2 and in foregoing mode
The C-1:1-hydroxycyclohexylphenylketone, the IRGACURE-184 that Ciba Co., Ltd. makes
D-1: methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl ester, the LA-82 that rising sun electrification Co., Ltd. makes
Among the present invention, the value of the storage modulus under the storage modulus E ' under 80 ℃ and 25 ℃ is measured according to the Measurement of Dynamic Viscoelasticity method based on JIS K7244-5.That is, use Fusion lamp D bulb, at 1J/cm 2Accumulated light under be cured and make sample chips with the size of length 5cm, width 1cm, thickness 1mm, and use Seiko to be full of the viscoelasticity device DMS6100 that electronics technology (ェ ス ア イ ア イ Na ノ テ Network ノ ロ ジ one) company of department makes and measure.Be determined under the beam mode and carry out, under the condition of 2 ℃/minute of amplitude load 10mN, frequency 10Hz, programming rates and in-50 ℃ to 150 ℃ scope, measure.
Use resulting resin combination of the present invention to make and have the Blu-ray Disc of Pigment Record layer, and carry out evaluating characteristics.
The making of Blu-ray Disc
1. the sputtering silver alloy makes its thickness reach 100nm on the polycarbonate substrate of the guiding groove with track pitch 0.32 μ m and diameter 12cm, thickness 1.1mm, forms the reflection horizon.Then, the pigment solution that will be dissolved with azopigment in TPF (tetrafluoropropanol) solvent is coated with by spin-coating method, and descends dry 30 minutes at 80 ℃, forms the Pigment Record layer.Then, sputter ZnS-SiO 2(mol ratio 80:20) makes its thickness is about 15nm, forms contact bed, thereby makes the Blu-ray Disc substrate.
With contact bed mode up with the Blu-ray Disc substrate-placing to universal stage, carry out circular cap rock and process until be covered to internal diameter 11.5mm, then supply with 2.0g resin combination of the present invention at the cap rock of central part.
3. the viscosity that cooperates resin combination of the present invention, spin coating is 4 seconds to 7 seconds in the velocity range of 700rpm to 1200rpm, and being applied to each coating thickness is 95 μ m.When spin coating soon finishes, carry out twice xenon flash lamp irradiation, thereby be cured to the degree without surface mobility.
4. use high-pressure sodium lamp, from the top with 400mJ/cm 2Shone 3 seconds, resin combination of the present invention is solidified fully.
So that the resin combination of the present invention mode up after solidifying load on the universal stage, carry out circular cap rock and process until be covered to internal diameter 11.5mm, then supply with 3.0g HOD-3950B (Blu-ray Disc that Nippon Kayaku K. K makes with hard conating resin) at the cap rock of central part.
6. with the velocity range spin coating of 4000rpm 4 seconds to 7 seconds, being applied to coating film thickness was 5 μ m.After spin coating finishes, use high-pressure sodium lamp, from upside with 400mJ/cm 2Shone 3 seconds, HOD-3950B is solidified fully, thereby make Blu-ray Disc of the present invention.
(a) initial stage warpage
The numerical value of disc tilt, use is carried out as the Argusblue (manufacturing of German History doctor Bao Hua (Dr.schwab) company) of the mechanical property determinator of CD.About the value of warpage, more the outer edge near CD shows difference more significantly, therefore, estimates with the value near the radius 58mm place of outer edge end.
Initial stage warpage in the table is calculated by following formula.
The warpage of the warpage of initial stage warpage=coating metacoxal plate-coating prebasal plate
The unit of warpage shows with kilsyth basalt.Judge with following benchmark.
00 〉=initial stage warpage＞-1.5
* initial stage warpage≤-1.5
(b) the tracer signal characteristic of Blu-ray Disc before and after endurancing
The CD of CD of the present invention and comparative example was placed 100 hours under 80 ℃, 85%RH environment.Use the Blu-ray Disc data-signal determinator ODU-1000 of Pa Lusi (パ Le ス テ Star Network) company manufacturing, measure the tracer signal characteristic (jitter value) of endurancing front and back Blu-ray Disc, and estimate with following benchmark.Jitter value is one of electric signal of CD, and their numerical value is higher, and the signal data of expression Blu-ray Disc is poorer, reaches 10% when above, and becoming is difficult to carry out the read-write of data.In addition, the value that is determined at radius 48mm place is estimated.
The evaluation of jitter value
Zero jitter value is lower than 10.0%.
* jitter value is more than 10.0%.Perhaps can't measure.
(c) crackle evaluation
After the long duration test, naked eyes confirm that the hard conating of CD has flawless.
Result by table 1 can confirm, the resin combination of the present invention of embodiment 1 to 4 obtains good tracer signal characteristic before and after the endurancing, and hard conating does not crack, and coating when solidifying the variable quantity of warpage also few.On the other hand, the storage modulus E' under 80 ℃ is higher than in the comparative example 1 of particular range, and the amount of warpage that substrate is caused is large, in addition, in the comparative example 2 of storage modulus E ' under 80 ℃ less than particular range, hard conating cracks in endurancing, thereby can't measure the tracer signal characteristic.
Industrial applicability
Resin combination of the present invention, be suitable for forming the CD photic zone with organic pigment recording layer, in the mode adjacent with the organic pigment recording layer of the optic disc base board with organic pigment recording layer or contact bed, solidify resin combination of the present invention in these layer coatings and form photic zone, thus, can obtain having the CD of following characteristic: the warpage of optic disc base board is little when the coating of this resin combination is solidified, the jitter value at initial stage is low to moderate below 7%, and after the long duration test under high temperature wets condition more, jitter value also is lower than 10%, the record characteristics of signals is all good after reaching in the early stage long duration test, thereby and good in permanance such as the hard conating that this photic zone forms do not crack after long duration test yet.Therefore, resin combination of the present invention is industrially very useful with the resin combination that photic zone forms usefulness as the CD with organic pigment recording layer.

Claims (16)

1. CD ultraviolet-curing resin composition with organic pigment layer, it contains (A) multifunctional (methyl) acrylate, (B) carbamate (methyl) acrylate reaches (C) Photoepolymerizationinitiater initiater, wherein, the storage modulus E ' under 80 of its cured film ℃ is 50 to 200MPa scope.
2. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, (methyl) acryloyl group equivalent of multifunctional (methyl) acrylate (A) is 85g/eq. to 160g/eq..
3. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, carbamate (methyl) acrylate (B) is carbamate (methyl) acrylate of molecular weight 400 to 10000.
4. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, multifunctional (methyl) acrylate (A) is for being selected from by 1,6-hexanediol two (methyl) acrylate, BDO two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) acrylate of EO modification, glycerine three (methyl) acrylate of PO modification, at least a in the group that pentaerythrite four (methyl) acrylate forms.
5. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, carbamate (methyl) acrylate (B) is polyvalent alcohol and polyisocyanates and the reaction product that contains (methyl) acrylate of hydroxyl, and polyvalent alcohol is polyester polyol and/or polyether glycol.
6. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, it is characterized in that, contain multifunctional (methyl) acrylate (A) of 10 to 70 % by weight, carbamate (methyl) acrylate (B) of 5 to 80 % by weight and the Photoepolymerizationinitiater initiater (C) of 0.5 to 20 % by weight in the resin combination.
7. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, with respect to the total amount of (methyl) acrylate that contains in the resin combination, (A) multifunctional (methyl) acrylate and (B) total amount of carbamate (methyl) acrylate be more than 90%.
8. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1; wherein; multifunctional (methyl) acrylate (A) is (methyl) acrylate of (methyl) acryloyl group equivalent 85g/eq. to 160g/eq., and the molecular weight that carbamate (methyl) acrylate (B) obtains for the reaction of at least a and polyisocyanates in polyester polyol or the polyether glycol reaction product that obtains and (methyl) acrylate reactions that contains hydroxyl is 400 to 10000 carbamate (methyl) acrylate.
9. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 8, wherein, carbamate (methyl) acrylate (B) is for being selected from polyether glycol in the group that is comprised of polyglycol, polypropylene glycol and poly-BDO and reacting the reaction product that obtains with isophorone diisocyanate or toluene diisocyanate and containing carbamate (methyl) acrylate that (methyl) acrylate reactions of hydroxyl obtains.
10. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 7, wherein, multifunctional (methyl) acrylate is for being selected from by 1,6-hexanediol two (methyl) acrylate, BDO two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) acrylate of EO modification, at least a in the group that glycerine three (methyl) acrylate of PO modification and pentaerythrite four (methyl) acrylate form.
11. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 10, wherein, multifunctional (methyl) acrylate is for being selected from least a in the group that is comprised of 1,6-hexanediol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, pentaerythrite three (methyl) acrylate and trimethylolpropane tris (methyl) acrylate.
12. CD ultraviolet-curing resin composition as claimed in claim 7; wherein; carbamate (methyl) acrylate (B) is for being selected from by polyglycol; polypropylene glycol and poly-1; polyether glycol in the group that the 4-butylene glycol forms and isophorone diisocyanate or toluene diisocyanate reaction and the reaction product that obtains and contain (methyl) acrylate reactions of hydroxyl and obtain carbamate (methyl) acrylate; multifunctional (methyl) acrylate (A) is (methyl) acrylate of (methyl) acryloyl group equivalent 85g/eq. to 160g/eq., and the content of epoxy (methyl) acrylate is 0 to being lower than 10 % by weight with respect to the total amount of resin combination.
13. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 1, wherein, CD is 500 to 1500MPa with the storage modulus under 25 ℃ of the cured film of ultraviolet-curing resin composition.
14. the CD ultraviolet-curing resin composition with organic pigment layer as claimed in claim 13, wherein, CD is 0.05 to 0.20 with the storage modulus under 80 ℃ of the cured film of ultraviolet-curing resin composition to the ratio of the storage modulus under 25 ℃.
15. a solidfied material, it is by obtaining each described ultraviolet-curing resin composition irradiation active energy beam in the claim 1 to 14.
16. the CD with organic pigment recording layer, it has by each described ultraviolet-curing resin composition in optic disc base board coating claim 1 to 14, and the solidfied material layer that its irradiation active energy beam is obtained.
CN201180035624.1A 2010-07-22 2011-07-15 CD ultraviolet-curing resin composition, solidfied material and CD Expired - Fee Related CN103026411B (en)

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CN1842550A (en) * 2003-08-26 2006-10-04 日本化药株式会社 Ultraviolet-curing resin composition and cured product thereof
JP2009016001A (en) * 2007-07-06 2009-01-22 Ricoh Co Ltd Optical recording medium and its manufacturing method
JP2009173016A (en) * 2007-12-26 2009-08-06 Mitsubishi Plastics Inc Laminate sheet and optical recording medium

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Publication number Priority date Publication date Assignee Title
CN1842550A (en) * 2003-08-26 2006-10-04 日本化药株式会社 Ultraviolet-curing resin composition and cured product thereof
JP2009016001A (en) * 2007-07-06 2009-01-22 Ricoh Co Ltd Optical recording medium and its manufacturing method
JP2009173016A (en) * 2007-12-26 2009-08-06 Mitsubishi Plastics Inc Laminate sheet and optical recording medium

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