CN103534758B - Ultraviolet-curing resin composition - Google Patents

Ultraviolet-curing resin composition Download PDF

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Publication number
CN103534758B
CN103534758B CN201280023346.2A CN201280023346A CN103534758B CN 103534758 B CN103534758 B CN 103534758B CN 201280023346 A CN201280023346 A CN 201280023346A CN 103534758 B CN103534758 B CN 103534758B
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methyl
ultraviolet
curing resin
resin composition
acrylate
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CN103534758A (en
Inventor
木户场润
松尾雄朗
松尾雄一朗
小林大祐
内藤正弘
本桥隼
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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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety

Abstract

The present invention relates to a kind of BD ultraviolet-curing resin composition, it contains: the compound (R shown in (A) following formula (1)1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl) 5～15 weight portions；(B) compound shown in following formula (2) (in formula, R21Representing hydrogen atom or methyl, n represents the integer of 1～10) 10～60 weight portions；(C) polytetramethylene glycol and polyisocyanates and product carbamate (methyl) acrylate 30～60 weight portion of (methyl) dihydroxypropyl C2～C4 Arrcostab；And (D) Photoepolymerizationinitiater initiater 2～8 weight portion.The ultraviolet-curing resin composition of the present invention is for providing warpage during solidification few and the ultraviolet-curing resin composition of light-transmitting layer of excellent durability under hot and humid environment, using the teaching of the invention it is possible to provide though the BD that the reduction of luminous reflectance is the fewest under hot and humid environment.

Description

Ultraviolet-curing resin composition
Technical field
The ultraviolet-curing resin composition and the use that the present invention relates to use in the light-transmitting layer of Blu-ray Disc should Ultraviolet-curing resin composition is as the CD of light-transmitting layer, and this Blu-ray Disc is at least formed with reflection layer and light transmission Layer, and utilize the blue laser in the range of 370nm～430nm with oscillation wavelength to carry out record through described light-transmitting layer Or regeneration (regeneration).
Background technology
In recent years, the transmission of Large Copacity information record is carried out continually due to information technology and the development of Information Network.With , it is desirable to it is able to record that and regenerates the high density huge capacity compact discs of jumbo image, music, computer data etc..Right For the DVD (Digital Versatile Disc, digital versatile disc) universal as high-density recording media, for Realize densification and use the laser of the shorter 650nm of wavelength ratio CD (Compact Disc, compact disk), optical system Also achieve high-NA.But, in order to record or regenerate HDTV (high definition television, high definition Clear degree TV) corresponding to high image quality image etc., need further densification, therefore, the next generation at DVD has carried out entering one The method of step high density recording and the research of CD thereof, and propose the light utilizing the blue laser using wavelength ratio DVD shorter The high density recording mode of the new compact disk structure of system.
This new CD is to form pit or information on the transparent or opaque substrate formed by plastics such as Merlon The information recording part positions such as recording layer, then on information recording part position the light-transmitting layer of stacking about 100 μm, make recording light or regeneration Light or both is through the CD of the structure of this light-transmitting layer and incidence.From the viewpoint of productivity ratio, specially at this CD Light-transmitting layer in use ultraviolet-curing resin composition studied.
In this CD utilizing blue laser to carry out recording or regenerating (Blu-ray Disc, hereinafter also referred to BD), light transmission The light-transmitting layer that layer and DVD are used is in a ratio of thick film, it addition, different from the situation that the intermediate layer as DVD-9 structure uses, Near top layer or top layer, light-transmitting layer is set.Therefore, even if directly conversion was suitable for the CD ultraviolet of DVD admittedly in the past Change type resin combination, the most also can substantially produce the record caused because of deformation or the corrosion etc. of reflection layer again compared with DVD Raw reliability reduces.Furthermore, it is necessary to there is the transmitance of the light transmission steady in a long-term making short wavelength and in order on top layer Or the high rigidity used near top layer, it addition, from the problem of productivity ratio, also require the combination being to be suitable for making thick film Thing.
As the ultraviolet-curing resin composition of disc tilt can be alleviated, such as, disclose containing by making lactone Monomer obtained by (methyl) acrylate reactions of compound and hydroxyl reacts with polyisocyanate compound and obtains The ultraviolet-curing resin composition (referenced patent document 1) of carbamate (methyl) acrylate.This ultraviolet curing Type resin combination is by using more excellent carbamate (methyl) acrylate of flexibility to receive as low solidification Shrinkage and the useful ultraviolet-curing resin composition of low viscous protective coating agent.But, said composition is made BD and is used up During transmission layer, viscosity is low, therefore, it is difficult to form thick film.It addition, increase carbamate (methyl) acrylic acid to improve viscosity When the content of ester forms the light-transmitting layer of CD, exist and produce deterioration because of corrosion of metal film etc. under hot and humid environment Problem.
It addition, as obtaining recording the compositions of the few resin molding of corrosion of the metal film of medium, disclose containing than It it is heavily the resin combination (referenced patent document 2) of the high specific gravity liquid-state oligomers of more than 1.10.Said composition is by using thoroughly The hyperbaric solution state oligomer such as the epoxy acrylate of moist low epoxy acrylate, particularly bisphenol A-type and there is suppression The burn into of metallic film reduces the effect of the variable color of record medium, but this oligomer has the skeleton of rigidity, accordingly, as note The top layer of recording medium, use with light-transmitting layer especially as BD in the case of, produce warpage sometimes and cause recording medium Reliability reduce.
On the other hand, the active energy-curable combination used as the optical article with prismatic action or lensing Thing, discloses and has containing having in molecule in carbamate (methyl) acrylate of 3 (methyl) acryloyl groups and molecule There is the compositions (referenced patent document 3) of (methyl) acrylate of 3 (methyl) acryloyl groups.Said composition is to provide and sets The compositions of the excellent curing overlay films such as crimpiness during membrane of lipoprotein stacking, shape retention properties, the transparency, case hardness, but Use and there are 3 (first by molecule having in carbamate (methyl) acrylate of 3 (methyl) acryloyl groups and molecule Base) compositions that constitutes of (methyl) acrylate of acryloyl group as the light-transmitting layer of CD time, exist as luminous reflectance The problem that the adhesivity of metallic reflector that layer uses is low.Although it addition, there is (methyl) propylene of 3 (methyl) acryloyl groups Acid esters has adhesivity through modifier modified for EO or PO to metallic reflector, but makes owing to having a large amount of hydrophilic structure Durability existing problems under hot and humid environment.
Up to now, in order to meet the characteristic required by CD, it is proposed that various be conceived to durability or adhesive tension so Specific physical property and the ultraviolet-curing resin composition (patent documentation 4～10) prepared.But, ultraviolet curing resin In compositions, it was found that in time requiring hardness warpage during solidification have become big tendency other things when improving specific physical property Property the relation that can be deteriorated, therefore the resin meeting the requirement characteristic sought in all market is developed in strong expectation.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 11-12495 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-302309 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2002-69139 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-243109 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-249228 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2009-32302 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2009-32303 publication
Patent documentation 8: No. 2008/099666 pamphlet of International Publication
Patent documentation 9: Japanese Unexamined Patent Publication 2000-345073 publication
Patent documentation 10: No. 2009/144926 pamphlet of International Publication
Summary of the invention
Invent problem to be solved
To be solved by this invention have a problem in that when solidification is provided warpage is few, excellent durability under hot and humid environment Even if ultraviolet-curing resin composition and the reduction of luminous reflectance is the fewest under hot and humid environment CD.
Means for solving the above
The present invention finds, contains the following formula as difunctionality (methyl) acrylate by using using specific ratio (1) compound shown in, as the compound shown in the following formula (2) of simple function (methyl) acrylate and as amino first The polytetramethylene glycol of acid esters (methyl) acrylate and polyisocyanates and (methyl) dihydroxypropyl C2～C4 Arrcostab The curing overlay film of compositions of product carbamate (methyl) acrylate as light-transmitting layer, it is possible to suppression high temperature The variable color (xanthochromia etc.) of the light-transmitting layer under high humidity environment, the reduction of reflectance, cause because of the corrosion of metallic film or oxidation Albefaction, and the generation of the warpage causing characteristic to be deteriorated can be reduced,
Thus complete the present invention.
(in formula, R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 Or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl)
(in formula, R21Representing hydrogen atom or methyl, n represents the integer of 1～10)
And, there is the curing overlay film CD as the present invention of light-transmitting layer of this excellent durability, even if at height Being not easy to produce the reduction of luminous reflectance because of variable color and warpage under temperature high humidity environment, the deterioration of characteristics of signals is few, therefore, utilizes The recording/reproducing of the information that short wavelength's blue laser is carried out is good, the most useful.
The present invention relates in the light-transmitting layer of BD use ultraviolet-curing resin composition, this BD on substrate at least It is laminated with reflection layer and light-transmitting layer, and the regeneration of the information of carrying out from above-mentioned light-transmitting layer side incidence blue laser.
That is, the present invention relates to following BD ultraviolet-curing resin composition, its solidfied material and there is its solidfied material BD.
1. a Blu-ray Disc, has the solidification nitride layer of following ultraviolet-curing resin composition as light on substrate Transmission layer,
Described ultraviolet-curing resin composition is following Blu-ray Disc ultraviolet-curing resin composition,
In total amount 100 weight portion of ultraviolet-curing resin composition, contain following (A)～(D) with following ratio Composition,
(A) compound 5～15 weight portion shown in following formula (1),
In formula (1), R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylene with ehter bond of carbon number 4～10 Base or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl；
(B) compound 10～60 weight portion shown in following formula (2),
In formula (2), R21Representing hydrogen atom or methyl, n represents the integer of 1～10；
(C) polytetramethylene glycol and polyisocyanates and (methyl) dihydroxypropyl C2～the product of C4 Arrcostab Carbamate (methyl) acrylate 30～60 weight portion；And
(D) Photoepolymerizationinitiater initiater 2～8 weight portion.
2. the Blu-ray Disc as described in above-mentioned 1, wherein, at least formed with reflection layer and light-transmitting layer on substrate, and And utilize and there is in the range of 370nm～430nm the blue laser of oscillation wavelength carry out through this light-transmitting layer recording or again Raw.
3. a Blu-ray Disc ultraviolet-curing resin composition, wherein, at ultraviolet-curing resin composition Total amount 100 weight portion in, contain following (A)～(D) composition with following ratio,
(A) compound 5～15 weight portion shown in following formula (1),
In formula (1), R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylene with ehter bond of carbon number 4～10 Base or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl；
(B) compound 10～60 weight portion shown in following formula (2),
In formula (2), R21Representing hydrogen atom or methyl, n represents the integer of 1～10；
(C) polytetramethylene glycol and polyisocyanates and (methyl) dihydroxypropyl C2～the product of C4 Arrcostab Carbamate (methyl) acrylate 30～60 weight portion；And
(D) Photoepolymerizationinitiater initiater 2～8 weight portion.
4. the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned 3, wherein, shown in above-mentioned formula (1) Compound (A) be in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate any one or two Kind.
5. the Blu-ray Disc ultraviolet-curing resin composition as described in above-mentioned 3 or 4, wherein, polytetramethylene two Alcohol and polyisocyanates and product carbamate (methyl) acrylic acid of (methyl) dihydroxypropyl C2～C4 Arrcostab In ester (C), the number-average molecular weight of the polytetramethylene glycol that reaction is used is 400～750.
6. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of above-mentioned 3～5, wherein, at purple In total amount 100 weight portion of outside line curable resin composition, contain (E) through 4～12 moles with the ratio of 15～53 weight portions Ethylene-oxide-modified bisphenol A-type two (methyl) acrylate.
7. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of above-mentioned 3～6, wherein, contains Compound shown in following formula (3) as antioxidant,
In formula (3), R2、R3、R4Each it is individually present, R2Represent the alkyl of carbon number 1～3, R3Represent carbon number 1～ The alkylidene of 6, R4Represent the alkyl of carbon number 5～20.
8. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of above-mentioned 3～7, wherein, contains Compound shown in following formula (4) as silane coupler,
In formula (4), R5And R6Each it is individually present, R5Represent the alkyl of carbon number 1～3, R6Represent carbon number 1～6 Alkylidene.
9. the BD ultraviolet-curing resin composition as according to any one of above-mentioned 3～8, wherein, has containing (F) The compound of hindered piperidine skeleton.
10. the BD ultraviolet-curing resin composition as described in above-mentioned 9, wherein, has the change of hindered piperidine skeleton Compound (F) is the compound with hindered piperidine skeleton and (methyl) acryloyl group.
The 11. Blu-ray Disc ultraviolet-curing resin compositions as according to any one of above-mentioned 3～6, wherein, at least Containing 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide as Photoepolymerizationinitiater initiater (D).
The 12. Blu-ray Disc ultraviolet-curing resin compositions as described in above-mentioned 6, wherein, containing choosing freely (F) tool There are the silane coupler shown in the compound of hindered piperidine skeleton, previously described formula (4) and the composition of the antioxidant shown in previously described formula (3) Group at least one.
The 13. Blu-ray Disc ultraviolet-curing resin compositions as according to any one of above-mentioned 6～12, wherein, extremely Less containing bisphenol A-type two (methyl) acrylate modified through 9～11 moles of ethylene oxide as (E) composition, its content is relative Content 100 weight portion in (C) composition is 35～90 weight portions.
Ultraviolet-curing resin composition according to any one of 14. above-mentioned 3～13 for formation, there is recording layer The application of light-transmitting layer of Blu-ray Disc.
15. 1 kinds of solidfied materials, it is by shining the ultraviolet-curing resin composition according to any one of above-mentioned 3～13 Penetrate active energy beam and obtain.
The manufacture method of 16. 1 kinds of BD with recording layer, wherein, by the ultraviolet according to any one of above-mentioned 3～13 Curable resin composition is applied on BD substrate, and makes coated film be solidified to form light transmission by irradiating active energy beam Layer.
Invention effect
The BD ultraviolet-curing resin composition of the present invention can be formed curable, durability and with reflecting layer or The curing overlay film that the adhesiveness of boundary layer is excellent.It addition, the ultraviolet-curing resin composition of the present invention solidification time and Under cryogenic conditions or hot conditions, the shrinkage factor after long-term preservation is also few, has consolidating of this resin combination therefore, it is possible to reduce Change the generation of warpage in the BD of overlay film.And, there is the curing overlay film conduct of the ultraviolet-curing resin composition of the present invention Even if after the BD of light-transmitting layer uses under hot and humid environment for a long time, it is also possible to the variable color (xanthochromia of suppression light-transmitting layer Deng), the albefaction that causes of the reduction of reflectance and corrosion or oxidation because of metallic film, therefore, it is possible to utilize short wavelength blue Laser recording/reproducing information well.Additionally, have the curing overlay film conduct of the ultraviolet-curing resin composition of the present invention The restoration of the BD of light-transmitting layer is excellent.
Detailed description of the invention
The ultraviolet-curing resin composition of the present invention contains compound 5～15 weight shown in (A) following formula (1) Compound 10～60 weight portion shown in part, (B) following formula (2), (C) polytetramethylene glycol and polyisocyanates and (methyl) Product carbamate (methyl) acrylate 30～60 weight portion of dihydroxypropyl C2～C4 Arrcostab and (D) light Polymerization initiator 2～8 weight portion.
(in formula, R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 Or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl)
(in formula, R21Representing hydrogen atom or methyl, n represents the integer of 1～10)
It addition, in this specification, " (methyl) acrylate " refers to " methacrylate or acrylate "." (methyl) Acrylic acid " etc. too.
In the present invention, as difunctionality (methyl) acrylate, use the compound (A) shown in following formula (1) (the most also It is referred to as " (A) composition ").
(in formula, R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 Or the alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl)
Here, " alkylidene with ehter bond of carbon number 4～10 " refers to that multiple alkylidene is by least one ehter bond (-O-) bonding forms and the carbon number of multiple alkylidene adds up to the group of 4～10.
In compound (A) shown in above-mentioned formula (1), it may be preferred to use R1For carbon number 4～6 straight-chain alkyl-sub-, The alkylidene with ehter bond of carbon number 4～6 or the compound of the alkylidene with side chain of carbon number 4～10.
As the concrete example of the compound (A) shown in above-mentioned formula (1), such as dipropylene glycol two (methyl) propylene can be enumerated Acid esters, tripropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.As this compound (A), more preferably Use any one or two kinds in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.
These compounds can be obtained by market, specifically, can enumerate Photomer4226 (dipropylene glycol diacrylate Ester, Ke Ning Co., Ltd. manufactures), TPGDA (tripropylene glycol diacrylate, such as Daicel-Cytec Co., Ltd. manufacture), Photomer4017 (1,6-hexanediyl ester, Ke Ning Co., Ltd. manufactures) etc..
From the viewpoint of improving restoration, as the compound (A) shown in above-mentioned formula (1), in the most above-mentioned formula (1) R1For the compound of the straight-chain alkyl-sub-of carbon number 4～10, particularly preferred hexanediyl ester.
From the viewpoint of warpage in time improving adhesiveness and reduce solidification, as the compound shown in above-mentioned formula (1) (A), R in the most above-mentioned formula (1)1The alkylidene with ehter bond or having of carbon number 4～10 for carbon number 4～10 prop up The compound of the alkylidene of chain, more preferably dipropylene glycol two (methyl) acrylate or tripropylene glycol two (methyl) acrylate, Particularly preferably propylene glycol diacrylate.
In the present invention, by containing the compound (A) shown in above-mentioned formula (1) with specific ratio, it is possible to increase cross-link close Degree, it is possible to form hardness and be suitable to protect the curing overlay film of BD.
From the viewpoint of obtaining the solidfied material having the adhesiveness as target, restoration and hardness concurrently, the purple of the present invention The content of the compound (A) shown in formula (1) in outside line curable resin composition combines relative to ultraviolet curing resin Total amount 100 weight portion of thing is usually 5～15 weight portions, preferably 5～12 weight portions, more preferably 5～7 weight portions.(A) become Split-phase for this resin combination total amount 100 weight portion less than 5 weight portion time, curable, difference of hardness, therefore, it is difficult to obtain tool There is the curing overlay film of target capabilities.(A) composition relative to total amount 100 weight portion of this resin combination more than 15 weight portion time, Easily producing warpage, adhesiveness reduces, and is therefore not applied for BD.
In the ultraviolet-curing resin composition of the present invention, as the difunctionality (methyl) being suitable for (A) composition Acrylate, can enumerate bisphenol A-type two (methyl) acrylate (E) through 4～12 moles of ethylene oxide are modified and (be also referred to as below For " (E) composition ").As this bisphenol A-type two (methyl) acrylate (E), as long as known bisphenol A-type two (methyl) propylene Acid esters then can be not particularly limited to use, and preferably enumerates the bisphenol A-type two (methyl) through 6～11 moles of ethylene oxide modifications Acrylate, more preferably enumerates bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications.
As bisphenol A-type two (methyl) acrylate (E) modified through 4～12 moles of ethylene oxide, it is possible to use such as (such as Di-ichi Kogyo Seiyaku Co., Ltd. manufactures bisphenol A-type two (methyl) acrylate modified through 4 moles of ethylene oxide BPE-4A etc.), through modified bisphenol A-type two (methyl) acrylate (the such as first industrial pharmaceutical strain formula of 10 moles of ethylene oxide The BPE-10 etc. that commercial firm manufactures).
Use above-mentioned bisphenol A-type two (methyl) acrylate (E) modified through 4～12 moles of ethylene oxide (also referred to as BPE4～12 (E) or referred to as (E) composition) in the case of, by the ultraviolet-curing resin composition relative to the present invention Total amount 100 weight portion contain this two (methyl) acrylate (E) of 15～53 weight portions, it is possible to increase crosslink density and softness Both property.From improving from the viewpoint of durability, the content of this bisphenol A-type two (methyl) acrylate (E) be preferably 15～ 50 weight portions, more preferably 15～40 weight portions.
Should can be used alone or can be used together 2～3 kind by (E) composition.According to circumstances different, it is sometimes preferred to and with 2 kinds. And with in the case of, preferably and with bisphenol A-type two (methyl) acrylate modified through 4～8 moles of ethylene oxide with through 9～12 Bisphenol A-type two (methyl) acrylate that moles of ethylene oxide is modified.Preferably one of mode is for using one or and with two kinds It is somebody's turn to do the mode of (E) composition, for example, relative to bisphenol A-type two (methyl) acrylate modified through 9～11 moles of ethylene oxide 100 weight portions use bisphenol A-type two (methyl) propylene through 4～8 moles of ethylene oxide modifications with the ratio of 0～100 weight portions The mode of acid esters.In this case, particularly preferably relative to total amount 100 weight portion of aforementioned resin with 15～30 weight The ratio of part contains bisphenol A-type two (methyl) acrylate through 9～11 moles of ethylene oxide modifications.
When the content of this two (methyl) acrylate (E) is too much, under hot and humid environment, easily produce CD metal film Corrosion.It addition, the content of this two (methyl) acrylate (E) is 15 weights relative to total amount 100 weight portion of resin combination Time more than amount part, it is possible to give sufficient flexibility, the most preferably.
When the content of aforementioned carbamate (methyl) acrylate (C) is set to 100 weight portion, it is somebody's turn to do (E) composition preferred It is about 40 weight portions～the ratio of about 120 weight portions relative to this.It is somebody's turn to do in (E) composition, through 9～11 moles of ethylene oxide modifications Bisphenol A-type two (methyl) acrylate is preferably 35～90 weight portions relative to content 100 weight portion of this (C) composition, more excellent Select the ratio of 40～80 weight portions.
In the ultraviolet-curing resin composition of the present invention, as simple function (methyl) acrylate, use following formula (2) compound (B) (hereinafter also referred to " (B) composition ") shown in.
(in formula, R21Representing hydrogen atom or methyl, n represents the integer of 1～10)
In above-mentioned formula (2), preferably n is the compound of 1～3.As the compound (B) shown in the above-mentioned formula (2) used, Specifically can enumerate phenol (methyl) acrylate that ethane via epoxyethane is modified, more preferably modified through 1～3 moles of ethylene oxide Phenol (methyl) acrylate, more preferably through phenol (methyl) acrylic acid that 1 mole or 2 moles of ethylene oxide are modified Ester.Phenol (methyl) acrylate (B) of this ethane via epoxyethane modification can be obtained by market, as goods, specifically can arrange Lift Photomer4035 (acrylate, n=1, Ke Ning Co., Ltd. manufacture), EBECRYL110 (through 2 moles of epoxies Oxide-modified phenol acrylate, n=2, Daicel-Cytec Co., Ltd. manufacture) etc..
Here, from improving from the viewpoint of restoration, in the most above-mentioned formula (2) n be 2 modified through 2 moles of ethylene oxide Phenol (methyl) acrylate.
It addition, acrylate (n=1) is also because cheap and can obtain suitable characteristic and preferred.
The content being somebody's turn to do (B) composition is generally preferably many than the content of (A) composition, such as, the content of (A) composition is set to 100 weights During amount part, the content of (B) composition relative to this more than 100 weight portions, the most about 102 weight portions～about 600 weight portions, more excellent Elect about 105 weight portions～about 500 weight portions as.
During it addition, the content of aforementioned carbamate (methyl) acrylate (C) is set to 100 weight portion, should (B) composition Content be about 20 weight portions～the ratio of about 100 weight portions, even more preferably about 30 weight portions～about 90 weights preferably with respect to this The ratio of amount part, more preferably about 30 weight portions～the ratio of about 80 weight portions.
From the viewpoint of improving adhesiveness, flexibility and restoration, the ultraviolet curing resin combination of the present invention The content of the compound (B) shown in above-mentioned formula (2) in thing is relative to total amount 100 weight of ultraviolet-curing resin composition Part usually 10～60 weight portions, preferably 15～50 weight portions, it is sometimes preferred to be 10～40 weight portions, particularly preferably 20～ 40 weight portions.When the content of this compound (B) is very few, it is impossible to play the adhesiveness as target, flexibility, restoration, it addition, Can produce, time too much, the problem that sufficient hardness cannot be obtained.
In the ultraviolet-curing resin composition of the present invention, as carbamate (methyl) acrylate (C), use Polytetramethylene glycol and polyisocyanates and (methyl) dihydroxypropyl C2～the product carbamate of C4 Arrcostab (methyl) acrylate (hereinafter also referred to " (C) composition ").This carbamate (methyl) acrylate (C) is used with appropriate amount Time, it is improved the function of the mechanical property (warpage, deformation etc.) of BD.
Carbamate (methyl) acrylate (C) used in the present invention can be by making polytetramethylene glycol (a) React with polyisocyanates (b) and (methyl) dihydroxypropyl C2～C4 Arrcostab (c) and obtain.
As polytetramethylene glycol (a), the carbamate (first excellent with the balance of hardness in order to obtain flexibility Base) acrylate, preferred number average molecular weight is 400～2000, from the viewpoint of viscosity, cost, raising adhesiveness, more preferably Using number-average molecular weight is the polytetramethylene glycol (a) of 500～1000, particularly preferred number-average molecular weight be 500～750 poly- Tetramethylene glycol (a).According to circumstances, polytetramethylene glycol (a) that number-average molecular weight be 400～750 is preferably used.
When the number-average molecular weight of the polytetramethylene glycol (a) used is excessive, the solidfied material of resin combination can be made Hardness deteriorates, the most preferred.During it addition, this number-average molecular weight is too small, it is impossible to give excellent flexibility, and be difficult to improve The mechanical property (warpage, deformation etc.) of BD, the most preferred.
As polyisocyanates (b), as long as the compound with more than 2 NCOs does not the most limit, permissible Enumerate such as isophorone diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), dimethylbenzene two Carbimide. Ester, diphenyl methane-4,4 '-diisocyanate or tetrahydrochysene dicyclopentadiene based isocyanate etc..
In this case, as polyisocyanates (b), isophorone diisocyanate or toluene diisocyanate are preferably used Acid esters.
As (methyl) dihydroxypropyl C2～C4 Arrcostab (c), can enumerate such as (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl etc..Wherein, (methyl) 2-(Acryloyloxy)ethanol is preferably used.
As this carbamate (methyl) acrylate (C), more preferably make polytetramethylene glycol (a) and polyisocyanic acid Ester (b) is superfluous with the NCO equivalent of polyisocyanates (b) relative to the hydroxyl equivalent of polytetramethylene glycol (a) Amount carries out reacting and synthesizes oligourethane that two ends are NCO and make obtained carbamate oligomeric Carbamate (methyl) acrylate that thing reacts with (methyl) dihydroxypropyl C2～C4 Arrcostab (c) and obtains.
The synthetic reaction of carbamate (methyl) acrylate (C) such as can be carried out as follows.That is, by poly-four Methylene glycol (a) is preferably 1.1～2.0 with this NCO relative to the hydroxyl of every 1 equivalent with polyisocyanates (b) and works as The mode of amount mixes, and preferably reacts and synthesis of carbamates oligomer under the reaction temperature of 70～90 DEG C.Then, by gained The oligourethane arrived and (methyl) dihydroxypropyl C2～C4 Arrcostab (c) are with (methyl) crylic acid hydroxy ester (c) Hydroxyl 1 equivalent every relative to the NCO of the oligourethane mode that is preferably 1～1.5 equivalents mix, and React at 70～90 DEG C, it is possible to carbamate (methyl) acrylate obtained as target.
As carbamate (methyl) acrylate (C) used in the ultraviolet-curing resin composition of the present invention Molecular weight, in terms of number-average molecular weight be preferably from about 400～about 10000.
From the viewpoint of improving adhesiveness, flexibility and restoration, the ultraviolet-curing resin composition of the present invention In carbamate (methyl) acrylate (C) content relative to ultraviolet-curing resin composition total amount usually 30～60 weight portions, preferably 30～50 weight portions.The adhesiveness as target, flexibility cannot be played when content is very few, answer Originality, can produce the problem that cannot obtain sufficient hardness time too much, therefore cannot play the target effect of the present invention, the most not Preferably.
In the present invention, carbamate (first above-mentioned carbamate (methyl) acrylate (C) beyond be can be used together Base) acrylate.
Carbamate (methyl) acrylate that can be suitable for can be by making polyhydric alcohol (d) and polyisocyanates B () and (methyl) acrylate compound (e) reacts and obtains.
Here, polyisocyanates (b) can use above-mentioned polyisocyanates.
As the polyhydric alcohol (d) that can use, example polyhydric alcohol described as follows can be enumerated.
(i) neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, propylene glycol, 1,4-butanediol, 1,6-HD, trihydroxy methyl third The aliphatic alcohols such as alkane, tetramethylolmethane, dihydroxymethyl tristane, double [methylol] hexamethylene；
(ii) polyester obtained by making a kind of reaction with polyprotic acid in the aliphatic polyol described in above-mentioned (i) is many Unit's alcohol.
It addition, as above-mentioned polyprotic acid, such as succinic acid, phthalic acid, hexahydrophthalic anhydride, right can be enumerated Phthalic acid, adipic acid, Azelaic Acid, tetrabydrophthalic anhydride etc..
(iii) the caprolactone alcohol obtained by the reaction of polyhydric alcohol Yu 6-caprolactone.
(iv) polycarbonate polyol.The Merlon such as obtained by the reaction of 1,6-HD Yu diphenyl carbonate Glycol etc..
(v) polyether polyol.Poly-C2～C3 aklylene glycol such as such as Polyethylene Glycol or polypropylene glycol etc., ethylene-oxide-modified Bisphenol-A etc..
The number-average molecular weight of the polyhydric alcohol in above-mentioned (ii)～(v) is preferably from about 200～about 8000, even more preferably about 200 ～about 3000.
As (methyl) acrylate compound (e) that can use, can enumerate (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl, list (methyl) acrylic acid dihydroxymethyl cyclohexyl, (methyl) propylene Acid hydroxyl caprolactone etc..Wherein, (methyl) 2-(Acryloyloxy)ethanol is preferably used.
Carbamate (methyl) acrylate beyond above-mentioned carbamate (methyl) acrylate (C) can use The method identical with the method described in above-mentioned carbamate (methyl) acrylate (C) synthesizes.
And by the feelings of carbamate (methyl) acrylate beyond above-mentioned carbamate (methyl) acrylate (C) Under condition, in whole carbamates (methyl) acrylate component that both merge, carbamate (methyl) acrylate (C) Content be preferably more than 80 weight %, more than more preferably 90 weight %.
It addition, be not usually required to and use the carbamate (first beyond above-mentioned carbamate (methyl) acrylate (C) Base) acrylate, preferably it is used alone the mode of aforementioned carbamate (methyl) acrylate (C).
In total amount 100 weight portion of the resin combination of the present invention, the total amount of above-mentioned (A)～(C) is usually 45～98 Weight portion, preferably 50～80 weight portions, more preferably 55～75 weight portions.Remainder is (D) composition and optional member, more It is preferably the mode containing aforementioned (E) composition optionally one of composition.
In the ultraviolet-curing resin composition of the present invention, (hereinafter also referred to " (D) becomes to use Photoepolymerizationinitiater initiater (D) Point ").As the Photoepolymerizationinitiater initiater (D) that can use in the present invention, as long as known Photoepolymerizationinitiater initiater the most all can make With, can enumerate such as: benzoin isobutyl ether, 2,4-diethyl thioxanthone, ITX, dibenzoyl, 1-hydroxyl ring Hexyl phenyl ketone, benzoin ethyl ether, dibenzoyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4- Isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl isophthalic acid-(4-methyl thio phenyl)-2-morpholino propane-1-ketone With 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide equimolecular open ring type Photoepolymerizationinitiater initiater；And benzophenone, 4-benzene Base benzophenone, isophthalic benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide etc. removes Hydrogen Photoepolymerizationinitiater initiater etc.. As preferred Photoepolymerizationinitiater initiater, 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethyl benzoyl diphenyl can be enumerated Base phosphine oxide equimolecular open ring type Photoepolymerizationinitiater initiater.These Photoepolymerizationinitiater initiaters can use one or and with two or more.
Particularly from the viewpoint of improving inside solidification, and use TMDPO Mode be one of preferred mode.One of preferred mode be such as and with above-mentioned molecule open ring type Photoepolymerizationinitiater initiater, Preferably 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide.
When using TMDPO as Photoepolymerizationinitiater initiater (D), its content is relative Total amount in this (D) composition is preferably 3～50 weight %.
The Photoepolymerizationinitiater initiater (D) content in ultraviolet-curing resin composition is relative to ultraviolet curing resin Total amount 100 weight portion of compositions is usually 1～10 weight portions, preferably 2～8 weight portions, more preferably 3～8 weight portions.
The ultraviolet-curing resin composition of the present invention contains (A)～(D) composition with aforementioned ratio, it is also possible to contain (A) composition～beyond (D) is as remainder.
Preferably the ultraviolet-curing resin composition of the present invention is in addition to containing (A)～(D), contains with aforementioned ratio There is (E) composition.The content of the composition beyond (A)～(E) composition in the ultraviolet-curing resin composition of the present invention (contains It is its total amount in the case of Multiple components) relative to total amount 100 weight portion of ultraviolet-curing resin composition of the present invention Typically about 0 weight portion～about 35 weight portions, preferably from about 0 weight portion～about 10 weight portions.
In the ultraviolet-curing resin composition of the present invention, epoxy (methyl) acrylate can be used as required (G) (hereinafter also referred to " (G) composition ").Epoxy (methyl) acrylate (G) has the hardness improving curable, improving solidfied material And the function of curing rate.
It addition, as epoxy (methyl) acrylate (G), as long as by make glycidyl ether type epoxide with Epoxy (methyl) acrylate that the reaction of (methyl) acrylic acid obtains the most all can use.As being used for obtaining preferred epoxy The glycidyl ether type epoxide of (methyl) acrylate, can enumerate: bisphenol-A or two contractings of its alkylene oxide addition product Water glyceryl ether, Bisphenol F or the diglycidyl ether of its alkylene oxide addition product, hydrogenated bisphenol A or its alkylene oxide addition product Diglycidyl ether, A Hydrogenated Bisphenol A F or the diglycidyl ether of its alkylene oxide addition product, ethylene glycol diglycidyl base Ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol two Glycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether etc..
Epoxy (methyl) acrylate (G) can be by making these glycidyl ether type epoxides and (methyl) third Olefin(e) acid reacts under conditions of as described below and obtains.
Relative to epoxy radicals 1 equivalent of glycidyl ether type epoxide, make (methyl) acrylic acid with 0.9～1.5 Mole, the ratio of more preferably 0.95～1.1 mole reacts.Reaction temperature preferably 80～120 DEG C, it is little that the response time is about 10 Time～about 35 hours.In order to promote reaction, such as triphenylphosphine, TAP, triethanolamine or tetraethylammonium chloride etc. are preferably used and urge Agent.It addition, in order to prevent the polymerization in reaction, it is possible to use such as p methoxy phenol or methylnaphthohydroquinone etc. are as inhibition Agent.
As the present invention can be suitable for use epoxy (methyl) acrylate (G), can enumerate by bisphenol A-type ring Bisphenol type epoxy (methyl) acrylate that oxygen compound reaction acrylic acid with (methyl) obtains.In the present invention, epoxy (first Base) molecular weight of acrylate (G) is preferably 500～10000.
In the ultraviolet-curing resin composition of the present invention, can according to circumstances contain epoxy (methyl) acrylate (G).Such as, from the viewpoint of guaranteeing flexibility, adhesiveness, sometimes it is also preferred that relative to the ultraviolet hardening tree of the present invention Total amount 100 weight portion of oil/fat composition usually contains about 0 weight portion～about 20 weight portions, more preferably contains about 0 weight portion～about The mode of 10 weight portions.Generally, it is preferred to do not contain the mode of epoxy (methyl) acrylate (G).
In the ultraviolet-curing resin composition of the present invention, aforementioned (A) composition, aforementioned (B) can be used as required Carbamate (methyl) acrylate beyond composition, aforementioned (C) composition, aforementioned (C) composition, aforementioned (E) composition and above-mentioned (G) (methyl) acrylate monomer (H) (hereinafter also referred to " (H) composition ") beyond composition.It addition, should (methyl) acrylate Monomer (H) does not include the composition that light stabilizer described later and other additives person are comprised.
For this (methyl) acrylate monomer (H) that can use, as long as have in 1 composition mentioned previously above The compound of (methyl) acryloyl group not contained is not particularly limited.
Such as, as having the compound of more than 1 (methyl) acryloyl group, can enumerate: (methyl) acrylic acid is different pungent Ester, (methyl) isoamyl acrylate, (methyl) lauryl acrylate, (methyl) isodecyl acrylate, (methyl) stearyl acrylate Ester, (methyl) acrylic acid cetyl, the different myristin of (methyl) acrylic acid and (methyl) tridecyl acrylate etc. (methyl) Acrylic acid C5～C20 (preferably C7～C18) Arrcostab；(methyl) benzyl acrylate, (methyl) phenylethyl ethylene oxidic ester And the compound shown in previously described formula (2) such as polypropylene oxide (methyl) nonylphenol acrylate phenyl ester do not include there is phenyl ring (methyl) acrylate compounds；(methyl) acrylic acid tetrahydrofuran ester and (methyl) acrylic acid morpholine ester etc. have heterocycle (methyl) acrylate；(methyl) acrylic acid such as (methyl) acrylic acid 2-hydroxypropyl acrylate have C2～the C8 Arrcostab of hydroxyl；Ethoxy Polyalkylene glycol mono (methyl) acrylic acid such as base diethylene glycol (methyl) acrylate and polypropylene glycol (methyl) acrylate Ester；(methyl) acrylic acid tristane ester, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentadiene epoxide second Ester, acrylic acid dihydro dicyclopentadiene base ester (the FANCRYL FA-that such as, Hitachi Chemical Co., Ltd. manufactures 511A), the acrylic acid dihydro dicyclopentadiene base epoxide ethyl ester (FANCRYL that such as, Hitachi Chemical Co., Ltd. manufactures FA-512A), (such as, Hitachi Chemical Co., Ltd. manufactures metering system acid dihydride dicyclopentadiene base epoxide ethyl ester FANCRYL FA-512M), acrylic acid tetrahydrochysene dicyclopentadiene base ester (such as, Hitachi Chemical Co., Ltd. manufacture FANCRYL FA-513A), methacrylic acid tetrahydrochysene dicyclopentadiene base ester (such as, Hitachi Chemical Co., Ltd. manufacture FANCRYL FA-513M), acrylic acid 1-adamantane esters (such as, Idemitsu Kosen Co., Ltd. manufacture Adamantate AA), acrylic acid 2-methyl-2-adamantane esters (the Adamantate MA that such as, Idemitsu Kosen Co., Ltd. manufactures), propylene Acid 2-ethyl-2-adamantane esters (the Adamantate EA that such as, Idemitsu Kosen Co., Ltd. manufactures) and methacrylic acid 1- Adamantane esters (the Adamantate AM that such as, Idemitsu Kosen Co., Ltd. manufactures) etc. has C7～C10 aliphatic ring (methyl) acrylate compounds；Ethylene-oxide-modified (methyl) acrylic acid phenoxylation phosphate ester, ethylene-oxide-modified (first Base) (methyl) propylene such as acrylate, butoxy phosphate ester and ethylene-oxide-modified (methyl) acrylic acid octyloxy phosphate ester Acid phosphoric acid ester etc..
This (methyl) acrylate monomer (H) with 1 (methyl) acryloyl group has raising the most sometimes (suppression is stuck up to have the mechanical property of BD of the light-transmitting layer of the solidfied material of the ultraviolet-curing resin composition comprising the present invention Song, deformation etc.) function.
About this (methyl) acrylate monomer (H), as (methyl) acrylate with 2 (methyl) acryloyl groups Monomer, can enumerate: hexamethylene-Isosorbide-5-Nitrae-dimethanol two (methyl) acrylate, hexamethylene-1,3-dimethanol two (methyl) propylene Acid esters, tristane dihydroxymethyl two (methyl) acrylate (the KAYARAD R-that such as, Nippon Kayaku K. K manufactures 684 (tristane dihydroxymethyl diacrylates) etc.) and two (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester etc. have Two (methyl) acrylate compounds of C5～C10 aliphatic ring；Dioxane glycol two (methyl) acrylate (example The KAYARAD R-604 (dioxane glycol diacrylate) etc. manufactured such as, Nippon Kayaku K. K) etc. have miscellaneous Two (methyl) acrylate compounds of ring；The aklylene glycol two (methyl) that compound shown in previously described formula (1) does not includes Acrylate or its alkylene oxide modifier, such as, (a) C2 or C3 glycol two (methyl) acrylate, through 3～10 moles of epoxy second Modified 1,6-HD two (methyl) acrylate of alkane, through modified neopentyl glycol two (methyl) third of 3～10 mol of alkylene oxide Two (methyl) acrylic acid alkylene ester and the alkylene oxide modifiers thereof such as olefin(e) acid ester；Hydroxy new pentane acid neopentyl glycol two (methyl) propylene Acid esters；Repeat number is Polyethylene Glycol two (methyl) acrylate of more than 6 and polypropylene glycol two (methyl) that repeat number is more than 4 Poly alkylene glycol two (methyl) acrylate more than C10 such as acrylate；Aforementioned modified through 4～12 moles of ethylene oxide Alkylene oxide modified bisphenol A type two (methyl) acrylate beyond bisphenol A-type two (methyl) acrylate (E)；And epoxy second Alkane modification two (methyl) acrylated phosphate etc..
In this case, from suppressing the viewpoint of variable quantity of warpage, the viewpoint of durability that are caused by variations in temperature and carrying From the viewpoint of high rigidity, it is sometimes preferred to two (methyl) acrylic acid alkylidene beyond compound that use previously described formula (1) represents Ester or its alkylene oxide modifier.
About this (methyl) acrylate monomer (H), as (methyl) acrylate with 3 (methyl) acryloyl groups Monomer, can enumerate: trimethylolpropane tris (methyl) acrylate and trihydroxy methyl octane three (methyl) acrylate etc. three Methylol C2～C10 alkane three (methyl) acrylate；The many ethyoxyls of trimethylolpropane three (methyl) acrylate, three hydroxyl first The many propoxyl group of base propane three (methyl) acrylate and the many propoxyl group of the many ethyoxyls of trimethylolpropane three (methyl) acrylate Deng trihydroxy methyl C2～the many alkoxyls of C10 alkane three (methyl) acrylate；And three [(methyl) acryloyl-oxyethyl] is different Cyanurate, tetramethylolmethane three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate and Alkylene oxide modification trimethylolpropane tris (methyl) propylene such as epoxy pronane modification trimethylolpropane tris (methyl) acrylate Acid esters etc..
About this (methyl) acrylate monomer (H), as (methyl) acrylate with 4 (methyl) acryloyl groups Monomer, can enumerate: the many ethyoxyls of tetramethylolmethane four (methyl) acrylate, the many propoxyl group of tetramethylolmethane four (methyl) acrylic acid Ester, tetramethylolmethane four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate and dipentaerythritol four (first Base) acrylate etc..
About this (methyl) acrylate monomer (H), as (methyl) acrylate with 5 (methyl) acryloyl groups Monomer, can enumerate dipentaerythritol five (methyl) acrylate etc..
About this (methyl) acrylate monomer (H), as (methyl) acrylate with 6 (methyl) acryloyl groups Monomer, can enumerate dipentaerythritol six (methyl) acrylate etc..It addition, (methyl) acrylic acid that can use in the present invention Ester monomer can also be multifunctional (methyl) acrylate monomer with more than 7 (methyl) acryloyl groups.
In the ultraviolet-curing resin composition of the present invention, these (H) compositions can use a kind or mix with arbitrary proportion Close two or more to use.(H) composition content in ultraviolet-curing resin composition is relative to ultraviolet curing resin Total amount 100 weight portion of compositions is typically about 0 weight portion～about 53 weight portions, the most such as, be about 20 weight portions～about 80 weight portions, preferably from about 30 weight portions～about 70 weight portions.
As (methyl) acrylate compounds contained in the ultraviolet-curing resin composition of the present invention, can make With any one in acrylate compounds or methacrylate compound.Generally preferably acrylate compounds, this tree The total amount of the methacrylate compound contained in oil/fat composition is preferred relative to total amount 100 weight portion of this resin combination Less than 10 weight portions.It addition, (methyl) acrylate compounds contained in the ultraviolet-curing resin composition of the present invention Refer to the carbamate (methyl) beyond as aforementioned (A) composition, aforementioned (B) composition, aforementioned (C) composition, aforementioned (C) composition Acrylate, aforementioned (E) composition, aforementioned (G) composition and above-mentioned (H) composition and containing (methyl) third in this resin combination Enoic acid ester compounds.
In the ultraviolet-curing resin composition of the present invention, as other additives, sensitization can be used as required Antioxidant and the hindered amines such as agent, silane coupler, surfactant, levelling agent, hot polymerization inhibitor, hindered phenol and phosphite ester Deng light stabilizer.
In the case of using above-mentioned additive, its content is total relative to the ultraviolet-curing resin composition of the present invention Measuring 100 weight portions is 0.05～10 weight portions, preferably 0.1～5 weight portions.
As the sensitizer in the ultraviolet-curing resin composition of the present invention, it is possible to use such as trimethylamine, methyl Dimethanolamine, triethanolamine, to dimethylamino benzoylformaldoxime, ESCAROL 507 ethyl ester, to dimethylamino benzene first Isoamyl valerate, N, N-dimethyl benzylamine and 4,4 '-bis-(diethylamino) benzophenone etc..In addition it is also possible to and with not with front State the amine of photopolymerizable compound generation additive reaction as sensitizer.
From the viewpoint of operability in time making CD, the ultraviolet-curing resin composition of the present invention preferably makes With light stabilizer, as this light stabilizer, hindered amine compound, the compound (F) particularly with hindered piperidine skeleton are (following It is also referred to as " (F) composition ") useful.
There is the compound (F) of hindered piperidine skeleton as long as known thing, then can use without particular limitation.
Specifically, choosing freely 2,2,6,6-tetramethyl-4-piperidones, 2,2,6,6-tetramethyl-4-can such as be used Piperidine alcohols, 1,2,2,6,6-pentamethyl-4-piperidine alcohols, 4-hydroxyl-2,2,6,6-tetramethyl-1-piperidine ethanol, (methyl) propylene Acid 1,2,2,6,6-pentamethyl-4-piperidine ester, methacrylic acid 2,2,6,6-tetramethyl-4-piperidine ester, decanedioic acid double (1,2,2, 6,6-pentamethyl-4-piperidyl) ester, decanedioic acid double (2,2,6,6-tetramethyl-4-piperidyl) ester, poly-{ [6-(1,1,3,3-tetra- Methyl butyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino group] hexa-methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino group] }, dimethyl succinate and 1-(2-ethoxy)-4-hydroxyl-2,2,6,6- Double (1,2,2,6,6-pentamethyl-4-the piperazine of the condensation polymer of tetramethyl piperidine, 2-(the tertiary acrinyl of 3,5-bis-)-2-n-butylmalonic acid Piperidinyl) ester, 1,2,3,4-ethylene-dimalonic acid four (2,2,6,6-tetramethyl-4-piperidyl) ester, 1,2,3,4-ethylene-dimalonic acid with 1,2,2,6,6-pentamethyl-4-piperidine alcohols and the mixed ester compound of 1-tridecyl alcohol, 1,2,3,4-ethylene-dimalonic acid and 2,2,6, 6-tetramethyl-4-piperidine alcohols and the mixed ester compound of 1-tridecyl alcohol, 1,2,3,4-ethylene-dimalonic acid and 1,2,2,6,6-five first Base-4-piperidine alcohols and double (2-hydroxyl-1,1-dimethyl ethyl)-2,4,8,10-four oxaspiro [5.5] the undecanoic mixing of 3,9- Carboxylate and 1,2,3,4-ethylene-dimalonic acid (2-hydroxyl-1,1-two double with 2,2,6,6-tetramethyl-4-piperidine alcohols and 3,9- Methylethyl)-2,4,8,10-four oxaspiro [5.5] undecanoic mixed ester compound composition group at least one be obstructed amination Compound.Wherein, from the viewpoint of giving excellent durability, it may be preferred to use 1,2,2,6,6-pentamethyl-4-piperidine alcohols, 2,2,6,6-tetramethyl-4-piperidine alcohols, (methyl) acrylic acid 1,2,2,6,6-pentamethyl-4-piperidine ester (Asahi Denka Co., Ltd. The LA-82 manufactured).
Above-mentioned hindered amine compound, preferably there is the compound (F) of hindered piperidine skeleton) in, the expression molecule that is obstructed has Sterically hindered, refer on nitrogen-atoms or its adjacent carbon atom, be bonded with the bulky alkyl with side chain.As preferably The hindered amine compound used, can enumerate the compound being bonded with the alkyl with side chains such as the tert-butyl groups on nitrogen-atoms, such as Have at least 2, the position of 2,6,6 have the compound of the substituted piperidine scaffolds of C1～C3 alkyl, preferably enumerate have to Few compound on the position of 1,2,2,6,6 with the substituted piperidine scaffolds of C1～C3 alkyl.
During it addition, make the ultraviolet-curing resin composition of the present invention form solidfied material, there is hindered piperidine skeleton Compound itself can crosslink, thus the less form with impurity separates out, and also without compromising on ultraviolet curing resin The curable of compositions, therefore, it can particularly preferably use the change with the hindered piperidine skeleton containing (methyl) acryloyl group Compound.For example, it is preferable at least 2, the position of 2,6,6 has C1～C3 alkyl substituted (methyl) acrylic acid piperidine ester, more excellent Choosing (methyl) acrylic acid 1,2,2,6,6-pentamethyl-4-piperidine ester.
Light stabilizer, preferably there is the compound (F) of hindered piperidine skeleton in ultraviolet-curing resin composition Content is usually 0.01～10 weight portions relative to total amount 100 weight portion of ultraviolet-curing resin composition, more preferably 0.03～8 weight portions, particularly preferably 0.03～5 weight portions.
As the silane coupler that can use in the ultraviolet-curing resin composition of the present invention, as long as known Silane coupler then can be not particularly limited to use.According to circumstances, from the ultraviolet curing resin group improving the present invention From the viewpoint of the durability of the cured layer of compound, compound following formula (4) shown in is preferably used.
(in formula, R5And R6Each it is individually present, R5Represent the alkyl of carbon number 1～3, R6Represent carbon number 1～6 Alkylidene)
Here, as the compound shown in above-mentioned formula (4), R in preferred formula (4)5It is methyl, R6For carbon number 2～4 The compound of alkylidene.Specifically, the silane compounds such as 3-mercaptopropyi trimethoxy silane can be enumerated.
The content of the silane coupler in the ultraviolet-curing resin composition of the present invention is relative to ultraviolet hardening Total amount 100 weight portion of resin combination is usually 0.01～10 weight portions, preferably 0.05～3 weight portions.
From the viewpoint that the cured layer of the ultraviolet-curing resin composition of the present invention can be given excellent durability Set out, it may be preferred to use the compound shown in following formula (3) as antioxidant.
(in formula, R2、R3And R4Each it is individually present, R2Represent the alkyl of carbon number 1～3, R3Represent carbon number 1～6 Alkylidene, R4Represent the alkyl of carbon number 5～20)
R in the most above-mentioned formula (3)2For methyl, R3Alkylidene and R for carbon number 2～54Carbon number 10 for straight chain ～the compound of the straight chained alkyl of 15.
As the compound shown in above-mentioned formula (3), specifically can enumerate: double [2-methyl-4-[3-(dodecyl sulfenyl) Propionyloxy]-5-tert-butyl-phenyl] sulfide, double [2-methyl-4-[3-(myristyl sulfenyl) propionyloxy]-5-tert-butyl group Phenyl] sulfide and double { 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyl } sulfide Deng.Such as, can commercially available AO-23 (Asahi Denka Co., Ltd. manufacture, double 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyl } sulfide).
Antioxidant content in ultraviolet-curing resin composition is relative to ultraviolet-curing resin composition Total amount 100 weight portion be usually 0～10 weight portions.The most generally contain from durability aspect, its content be 0.01～ 10 weight portions, preferably 0.03～8 weight portions, particularly preferably 0.03～5 weight portions.
Several optimal ways in the BD ultraviolet-curing resin composition of the present invention set forth below.Without spy Not mentionleting alone bright, " part " in each component content represents time the total amount of ultraviolet-curing resin composition is set to 100 weight portion it Content (weight portion) contained by.
(I) a kind of Blu-ray Disc ultraviolet-curing resin composition, it contains above-mentioned (A) composition 5～15 parts, above-mentioned (B) composition 10～60 parts (preferably 10～50 parts), above-mentioned (C) composition 30～60 parts and above-mentioned (D) composition 2～8 parts, remainder For the composition beyond (A)～(D).
(II) ultraviolet-curing resin composition as described in above-mentioned (I), wherein, possibly together with 15～50 parts, more preferably 15～40 parts of bisphenol A-type two (methyl) acrylate modified through 4～12 moles of ethylene oxide as (E) composition.
(III) ultraviolet-curing resin composition as described in above-mentioned (I) or (II), wherein, is somebody's turn to do (C) composition for passing through The oligourethane synthesized by polytetramethylene glycol (a) and polyisocyanates (b) and (methyl) dihydroxypropyl C2 ～carbamate (methyl) acrylate that the reaction of C4 Arrcostab (c) obtains.
(IV) ultraviolet-curing resin composition as described in above-mentioned (III), wherein, this polytetramethylene glycol (a) Number-average molecular weight be 400～750.
(V) ultraviolet-curing resin composition as described in above-mentioned (III) or (IV), wherein, this polyisocyanates (b) For any one in isophorone diisocyanate and toluene di-isocyanate(TDI) or two kinds.
(VI) ultraviolet-curing resin composition as according to any one of above-mentioned (III)～(V), wherein, should (first Base) dihydroxypropyl C2～C4 Arrcostab (c) is (methyl) 2-(Acryloyloxy)ethanol.
(VII) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(VI), wherein, should (A) become Any one or two kinds being divided in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate.
(VIII) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(VII), wherein, is somebody's turn to do (B) Composition is through 1 mole or phenol (methyl) acrylate of 2 moles of ethylene oxide modification.
(IX) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(VIII), wherein, at least contains There is 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide as this (D) composition.
(X) ultraviolet-curing resin composition as described in above-mentioned (IX), wherein, 2,4,6-trimethylbenzoyls two The content of phenyl phosphine oxide is 3～50 weight % relative to the total amount of this (D) composition.
(XI) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(X), wherein, possibly together with 0.01～10 part, preferably 0.03～5 part above-mentioned (F) composition.
(XII) ultraviolet-curing resin composition as described in above-mentioned (XI), wherein, should (F) composition for have containing The compound of the hindered piperidine skeleton of (methyl) acryloyl group.
(XIII) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(XII), wherein, also contains There is 0.01～10 part, preferably 0.03～5 part as the compound shown in the above-mentioned formula (3) of antioxidant.
(XIV) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(XIII), wherein, also contains There is 0.01～10 part, preferably 0.05～3 part as the compound shown in the above-mentioned formula (4) of silane coupler.
In the ultraviolet-curing resin composition of the present invention, (particularly anti-with light in order to obtain the adhesiveness of solidfied material Penetrate the adhesiveness of layer, boundary layer), restoration, hardness and durability be all good and consolidating by ultraviolet-curing resin composition The ultraviolet curing resin that the variable quantity of the warpage when variable quantity of the warpage that the property changed, variations in temperature cause and solidification is few combines Thing, is described below preferred mode.
I () ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(XV), wherein, relative to purple Total amount 100 weight portion of outside line curable resin composition, containing 5～15 weight portions as the dipropylene glycol two of this (A) composition (methyl) acrylate with in hexanediol two (methyl) acrylate one or both, 12～50 weight portion become as this (B) Point phenol (methyl) acrylate modified through 1 moles of ethylene oxide and through the modified phenol (methyl) of 2 moles of ethylene oxide In acrylate one or both, 30～50 weight portion as the polytetramethylene glycol of this (C) composition, (particularly preferably number is all Molecular weight is the polytetramethylene glycol of 400～750) and the reaction of polyisocyanates (b) and (methyl) acrylic acid 2-hydroxyl ethyl ester The Photoepolymerizationinitiater initiater (D) of product carbamate (methyl) acrylate and 2～8 weight portions.
(ii) ultraviolet-curing resin composition as according to any one of above-mentioned (I)～(XIV) and above-mentioned (i), its In, containing 20～40 weight portions as (methyl) acrylate of this (B) composition.
(iii) the ultraviolet curing resin combination as according to any one of above-mentioned (I)～(IV), above-mentioned (i) and (ii) Thing, wherein, possibly together with 15～30 weight portions as the bisphenol A-type two (first modified through 9～11 moles of ethylene oxide of (E) composition Base) acrylate.
(iv) the ultraviolet curing resin combination as according to any one of above-mentioned (I)～(XIV), above-mentioned (i) and (iii) Thing, wherein, total relative to carbamate (methyl) acrylate component contained in ultraviolet-curing resin composition Amount, the polytetramethylene glycol of number-average molecular weight 400～700 and polyisocyanates and the reaction of (methyl) acrylic acid 2-hydroxyl ethyl ester The content of product carbamate (methyl) acrylate (C) is more than 90 weight % (particularly preferred 100 weight %).
(v) ultraviolet curing resin combination as according to any one of above-mentioned (I)～(XIV) and above-mentioned (i)～(iv) Thing, wherein, the total content of above-mentioned (A) composition, (B) composition and (C) composition is in total amount 100 weight of the resin combination of the present invention The ratio of usually 45～98 weight portions in Fen, the ratio of preferably 50～80 weight portions, more preferably 55～75 weight portions Ratio, remainder is (D) composition and optional member.
(vi) the ultraviolet curing resin combination as according to any one of above-mentioned (I)～(XIV) and above-mentioned (i)～(v) Thing, wherein, when the content of (A) composition is set to 100 weight portion, the content of (B) composition relative to this more than 100 weight portions and is Below 600 weight portions, when the content of (C) is set to 100 weight portion, (B) composition is relative to above-mentioned carbamate (methyl) third The content of olefin(e) acid ester (C) is about 30 weight portions～the ratio of about 90 weight portions.
(vii) the ultraviolet curing resin group as according to any one of above-mentioned (I)～(XIV) and above-mentioned (i)～(vi) Compound, wherein, containing bisphenol A-type two (methyl) acrylate modified through 9～11 moles of ethylene oxide as (E) composition, its Content is relative to the ratio that content 100 weight portion is 35～90 weight portions of above-mentioned carbamate (methyl) acrylate (C).
(viii) ultraviolet curing resin as according to any one of above-mentioned (I)～(XIV) and above-mentioned (i)～(vii) Compositions, wherein, the total amount of the methacrylate compound contained in ultraviolet-curing resin composition is relative to ultraviolet Total amount 100 weight portion of line curable resin composition is less than 10 weight portions.
The Blu-ray Disc ultraviolet-curing resin composition of the present invention can by by above-mentioned each composition at room temperature～ Mixed dissolution at 80 DEG C and obtain.By operations such as filtrations, field trash can be removed as required.
In view of coating, the viscosity of the Blu-ray Disc ultraviolet-curing resin composition of the present invention is preferably at 25 DEG C Under be 300～2000 (mPa s), more preferably 500～1200 (mPa s).By making viscosity the most easily be formed Thick film, it is possible to shorten and produce away from the time (the running time of production of units quantity).
The BD ultraviolet-curing resin composition of the present invention can use the solvent beyond mentioned component.This feelings Under condition, the content of solvent is preferably less than 10 weight portions, more relative to total amount 100 weight portion of ultraviolet-curing resin composition It is preferably less than 5 weight portions, does not the most use the situation of solvent.
In the BD ultraviolet-curing resin composition of the present invention, the cured layer that ultraviolet is formed after irradiating is at 25 DEG C Elastic modelling quantity be preferably 10～3000MPa, more preferably 50～2000MPa, particularly preferably 100～1000MPa.
Additionally, the less person of warpage produced because of variations in temperature in the cured layer formed can be effectively prevented because temperature becomes The mistake of the characteristics of signals changed and produce.Therefore, in the feelings of the light-transmitting layer that ultraviolet-curing resin composition is used for BD Under condition, warpage when preferably preserving at 5 DEG C～55 DEG C is less than 0.8 relative to the variable quantity of the warpage when preserving at present for 25 DEG C Degree, particularly preferably less than 0.6 degree.It addition, warp value is the most peripheral of close CD, sticking up apart from the position of cd centre 56mm Bent value (angle).
[BD]
The BD of the present invention is at least formed with reflection layer and light-transmitting layer and utilize blue laser to pass through on substrate Stating light-transmitting layer and carry out the BD recording or regenerating, above-mentioned light-transmitting layer comprises the light-transmitting layer ultraviolet hardening of the present invention The solidfied material of resin combination.Light-transmitting layer in this BD can be the unilateral outermost layer of this BD, additionally can also be thereon There is hard conating and with this hard conating as outermost layer.Another outermost layer is usually substrate.For the BD of the present invention, pass through The solidification nitride layer of the light-transmitting layer ultraviolet-curing resin composition of the use present invention is as light-transmitting layer, even if at high temperature It is not easy to produce the reduction of adhesive tension under high humidity, it is possible to obtain excellent durability, therefore, it is possible to carry out the note of information well Record/regeneration.
Light-transmitting layer in the BD of the present invention preferably makes the blue laser that oscillation wavelength is 370～430nm of laser efficient Ground transmission, preferably under 100 μ m thick, the absorbance of the light of 405nm is more than 85%, particularly preferably more than 90%.
The preferred thickness of light-transmitting layer is the scope of 50～150 μm, more preferably 75～150 μm.The thickness of light-transmitting layer Set in the case of monolayer and be about 100 μm.The thickness of light-transmitting layer brings the biggest can to light transmission, signal-obtaining and record Impact, it is therefore desirable to sufficiently control.Light-transmitting layer can form the cured layer of this thickness with monolayer, it is also possible to stacking Multiple light-transmitting layers.In the case of multilamellar, the thickness sum of the most each light-transmitting layer is above-mentioned thickness range.The light of the present invention is saturating Penetrate the generally preferable monolayer of layer.
The BD of the present invention is generally of reflection layer.As this reflection layer, as long as reflecting laser, can being formed and can remember The BD of record/regeneration, such as, can use the metals such as gold, silver, copper, aluminum or containing the alloy of any of which metal, silicon Deng inorganic compound.Wherein, owing to the luminous reflectance near 400nm is high, silver is therefore preferably used or with silver as main component Alloy.The thickness of the reflection layer of the BD of the present invention preferably sets and is about 10nm～about 60nm.
Generally, reflection layer is formed by being deposited with or sputter above-mentioned metal or its alloy on substrate.
The ultraviolet-curing resin composition of the application of the invention, it is possible to increase the light resistance of this reflection layer, resistance to Durability and the adhesiveness such as hot.Particularly, comprise in the reflectance coating of silver or the alloy with silver as main component and can preferably make With the ultraviolet-curing resin composition of the present invention.
Substrate as the BD of the present invention, it is possible to use the circular resin substrate of optical disc shapes, as this resin, Ke Yiyou Choosing uses Merlon.In the case of BD is special for regeneration, in the face on the unilateral surface of substrate, i.e. stacking reflection layer Form the pit undertaking record information on surface, and be formed on reflectance coating and form recording layer.
In the case of the BD of the present invention is writeable BD, between reflection layer and light-transmitting layer, it is provided with recording layer. As recording layer, as long as the recording/reproducing of information can be carried out, can be phase change type recording layer, magneto-optical recorder layer or have Random layer in machine pigment type recording layer.
In writeable BD, the record information faces of substrate is provided with recording layer.Recording layer can suitably utilize conduct The existing known material of used by optical recording medium recording layer.Such as pigment, amorphous semiconductor, partial nitridation film, portion can be enumerated Divide oxide-film (inoranic membrane) etc..
The BD of the present invention can have multiple above-mentioned recording layer.In this case, each layer can be by identical material shape Become, it is also possible to combination in any other materials is formed.By using other materials to form multiple recording layer, it is possible to change each layer The optical properties such as absorbance.
As the concrete kind of recording layer, inorganic type recording layer and organic pigment type recording layer can be enumerated.As inorganic The material used in type recording layer, can enumerate amorphous semiconductor material, partial nitridation thing and partial oxide.
As the concrete example of the amorphous semiconductor material used in inorganic type recording layer, can enumerate: SbTe system, GeTe System, GeSbTe system, InSbTe system, AgSbTe system, AgInSbTe system, GeSb system, GeSbSn system, InGeSbTe system and The material of InGeSbSnTe system etc..In amorphous semiconductor material, in order to improve crystallization rate, it is preferably used with Sb for main one-tenth The compositions divided.It addition, these amorphous semiconductor materials can be used alone a kind, it is also possible in any combination and ratio also Use two or more.
The partial nitridation film used as inorganic type recording layer and the concrete example of partial oxide film, can enumerate and comprise The partial nitridation film of BiGeN or SnNbN etc. and comprise the partial oxide film of TeOx, BiFOx and TiSixOy etc..
As recording layer, it is possible to use organic pigment type recording layer.The material of organic pigment type recording layer needs record The wavelength regenerating used laser has photonasty.And, the material of organic pigment type recording layer needs by utilizing laser Irradiation causes physical change or chemical reaction to make refractive index change.As the material of organic pigment type recording layer, permissible Enumerate such as cyanines pigment, oxonols (oxonol) pigment, azopigment, phthalocyanine dye and porphyrin pigment.Use and these are had The solution that machine material mixes with such as oxytol acetate, C3-Fluoroalcohol. equal solvent, by this solution of coating such as spin-coating methods Form organic pigment type recording layer.The thickness of organic pigment type recording layer is preferably more than 15nm and below 25nm.
In the BD of the present invention, boundary layer can be formed on the recording layer.Boundary layer has heat produced by buffering recording layer Function, regulation CD reflection rate function.It addition, boundary layer has the note contained in recording layer when preventing light-transmitting layer film forming It is existing that the solvent etc. that record material diffuses to contain in light-transmitting layer or light-transmitting layer resin combination infiltrates into the mixing such as recording layer The function of elephant.
The material constituting this boundary layer generally uses the mixture of silicon dioxide and zinc sulfide.Furthermore, it is possible to enumerate: oxidation The oxides such as silicon particularly silicon dioxide, zinc oxide, cerium oxide, yittrium oxide, Indium sesquioxide., tin indium oxide, gallium oxide and aluminium oxide； Zinc sulfide and yttrium sulfide sulfides；The nitride such as silicon nitride；Carborundum；Above-mentioned oxide and the mixture of sulfur；Magnesium and calcium etc. Fluoride etc..This boundary layer is formed by methods such as sputterings.
The curing overlay film of the ultraviolet-curing resin composition comprising the present invention to formed boundary layer material, concrete and Speech is excellent with the adhesiveness of the mixture of zinc sulfide, Indium sesquioxide. or tin indium oxide etc. for silicon dioxide, therefore can be preferably used.
The BD of the present invention can form plural recording layer (information recording part position).Such as, at the BD that regeneration is special In the case of, can have stacking the first reflection layer and the first light-transmitting layer on dimpled substrate, and saturating at this first light Penetrate on layer or in the case of being laminated with other layers as required, on these other layers, form the second reflection layer and the second light Transmission layer.In this case, on the first light-transmitting layer or be laminated on other layers on the first light-transmitting layer formation pit.Separately Outward, in the case of the BD of recordable/regeneration, stacking the first reflection layer, the first recording layer and the can be used on substrate One light-transmitting layer and on this first light-transmitting layer, form further the second reflecting layer, the second recording layer and the second light-transmitting layer and There is the composition of two-layer recording layer.Or can use and similarly layer be carried out stacking and there is the structure of the recording layer of more than three layers Become.In the case of the multiple layer of stacking, suitably regulate in the way of making the thickness sum of each layer reach above-mentioned thickness.Separately Outward, can sandwiched boundary layer between reflection layer and recording layer and/or between recording layer and light-transmitting layer.
In the case of the ultraviolet-curing resin composition of the present invention is used for light-transmitting layer, it is possible to suppression contact light is saturating Penetrating corrosion and the deterioration of boundary layer or the recording layer etc. of layer, therefore, the ultraviolet-curing resin composition of the present invention can also It is suitable for the BD with recording layer.
In the BD of the present invention, light-transmitting layer can be the layer of most surface but it also may arrange table on its top layer further Finishing coat (hard conating).As the material of formation hard conating, as long as hardness height and the solidification of excellent abrasion resistance can be formed The material of nitride layer is not particularly limited, and generally uses ultraviolet-curing resin composition.
The BD of the present invention has the special CD of regeneration and the CD of recordable/regeneration.
Regenerate special CD to be manufactured by following method.When 1 circular resin substrate is carried out injection moulding It is provided as the pit of information recording layer, on this information recording layer, then forms reflection layer.As required at reflection layer After other layers of upper stacking, by the light-transmitting layer of the method coating present invention such as such as 2P method, rolling method, silk screen printing or spin-coating method Use ultraviolet-curing resin composition.The ultraviolet as active energy beam～near ultraviolet is irradiated from the one side of BD or both sides Line (near wavelength 200～400nm), makes this resin composition form light-transmitting layer, thus obtains the regeneration of the present invention Special BD.
The CD of recordable/regeneration can be manufactured by following method.By evaporation or sputtering etc. at 1 circular resin base Form reflection layer on plate, and recording layer is set thereon.Stacking boundary layer on this recording layer as required, further at this The light-transmitting layer ultraviolet-curing resin composition of the present invention on recording layer or it is coated with on boundary layer by said method etc.. Irradiate active energy beam to BD in the same manner as above, make this resin composition form light-transmitting layer, thus Obtain the BD of the recordable/regeneration of the present invention.
The light source of ultraviolet when solidifying as making light-transmitting layer ultraviolet-curing resin composition, as long as can The lamp of irradiation ultraviolet radiation～nearultraviolet rays (near wavelength 200～400nm) is not particularly limited.Such as can use (pulse) Xenon lamp, electrodeless lamp, metal halide lamp, low pressure mercury lamp, high voltage mercury lamp or ultrahigh pressure mercury lamp etc..Ultraviolet irradiates can be with even Continuous light radiation modality is carried out, it is also possible to carry out in flash irradiation mode.
During irradiation ultraviolet radiation, preferably so that its accumulative light quantity is 0.05～1J/cm2Mode be controlled.The most tired Photometric amount is 0.05～0.8J/cm2, particularly preferably 0.05～0.6J/cm2。
The curable of the light-transmitting layer ultraviolet-curing resin composition used in the BD of the present invention is excellent, therefore, Even if accumulative light quantity is for also can fully solidify on a small quantity, adhesion (tacky) will not be produced at BD end face and surface, more will not produce BD Warpage and deformation.
[embodiment]
Hereinafter, as the concrete example of the BD of the present invention, single-layer type BD and multi-layered type BD (such as double deck type BD) is illustrated below The concrete example constituted.
In the BD of the present invention, as the preferred implementation of single-layer type BD, for instance that on substrate stacking reflection layer and Light-transmitting layer, from light-transmitting layer side incidence blue laser the record of the information of carrying out or the composition and saturating at light further of regeneration Penetrate the composition that hard conating is set on layer.Light-transmitting layer is the solidfied material of the ultraviolet-curing resin composition comprising the present invention Layer, the scope of its thickness for example, 100 ± 10 μm.Hard conating is preferably hardness height and the layer of excellent abrasion resistance.Hard conating Thickness is preferably 1～10 μm, more preferably 3～5 μm.The thickness of substrate is about 1.1mm.Reflection layer is preferably silver or with silver is The thin film of the alloy etc. of main component.
It addition, as the preferred implementation of the single-layer type BD with recording layer, such as have and stack gradually light on substrate Reflecting layer, the first boundary layer being arranged as required to, recording layer (inorganic type recording layer, organic pigment type recording layer), Second interface layer, light-transmitting layer and from light-transmitting layer side incidence blue laser the information of carrying out record or regeneration composition and enter One step arranges the composition of hard conating on light-transmitting layer.
As the preferred implementation of multi-layered type BD, such as, there are stacking the first reflection layer and the first smooth transmission on substrate Layer, the second reflection layer of stacking the most thereon and the second light-transmitting layer from the second light-transmitting layer side incidence blue laser The record of the information of carrying out or the composition of the double deck type BD of regeneration.First light-transmitting layer and the second light-transmitting layer are solid for comprising ultraviolet The layer of the solidfied material of change type resin combination, the most any one layer is the ultraviolet-curing resin composition comprising the present invention Layer.As the thickness of layer, the thickness of the preferably first light-transmitting layer and the model that thickness sum is 100 ± 10 μm of the second light-transmitting layer Enclose.The thickness of substrate is about 1.1mm.Reflection layer is silver or the thin film of the alloy etc. with silver as main component.
It addition, as the preferred implementation of the multi-layered type BD with recording layer, such as have and stack gradually on substrate One reflection layer, the first boundary layer, the first recording layer (inorganic type recording layer, organic pigment type recording layer), second contact surface Layer, the first light-transmitting layer, the second reflection layer of stacking the most thereon, the 3rd boundary layer, the second recording layer (inorganic type, have Machine pigment type), the 4th boundary layer, the second light-transmitting layer the information of carrying out from the second light-transmitting layer side incidence blue laser Record or the composition of double deck type BD of regeneration.
In the double deck type BD of this composition, track record (groove) is also formed in the surface of the first light-transmitting layer, and therefore, this is years old One light-transmitting layer can be constituted with the form of following multilamellar: is comprising the excellent ultraviolet-curing resin composition of adhesivity On the layer of cured film, stacking comprises the layer of the cured film of the ultraviolet-curing resin composition that can suitably form track record And the multilamellar formed.It addition, in this composition, it is also possible on top layer, it is provided with hard conating.
(embodiment)
Hereinafter, further illustrate the present invention by embodiment, but the present invention is not by any restriction of these embodiments.
As embodiment 1～7 and comparative example 1～3, preparation comprises the ultraviolet curing resin of composition shown in table 1 below Compositions.
Use obtained ultraviolet-curing resin composition, made the indigo plant with inorganic recording layer by following method Light CD, and carry out evaluating characteristics.
(making of Blu-ray Disc)
1. on the polycarbonate substrate with the diameter 12cm of the guide channel that track space is 0.32 μm, thickness 1.1mm, To make the thickness mode sputtering silver alloy as 100nm form reflecting layer.Then, sputter TiSiO and on reflecting layer, form nothing Machine recording layer.And then, in the way of making thickness be about 15nm, sputter ZnS-SiO2(mol ratio 80:20), is consequently formed boundary layer, Make Blu-ray Disc substrate.
2. by boundary layer upward in the way of by obtained Blu-ray Disc substrate-placing on turntable.To cover to internal diameter Mode at 11.5mm carries out circle and adds a cover (cap) and process, then by the present invention or the ultraviolet curing resin group that compares Compound 3.0g is supplied on the lid of central part.
3. carry out 4 seconds～the spin coating of 7 seconds with the velocity interval of 900rpm, be coated with in the way of making coating film thickness be 95 μm Cloth.At the end of spin coating, irradiate 2 flashes of light with xenon flash lamp so that it is be cured to the degree that surface mobility disappears.
4. use high voltage mercury lamp, with accumulative light quantity as 400mJ/cm2Mode irradiate the ultraviolet of 3 seconds from upside, make The coated film of ultraviolet-curing resin composition is fully cured.
5. optic disc base board is placed on turntable in the way of upward by the ultraviolet-curing resin composition after solidification. In the way of covering to internal diameter 11.5mm, carry out circle add a cover process, then by the ultraviolet curing resin group of hard conating Compound (HOD3950B, Nippon Kayaku K. K manufactures) 3.0g is supplied on the lid of central part.
6. the spin coating carried out 4 seconds～7 seconds with the velocity interval of 6000rpm is coated.At the end of spin coating, glisten with xenon 2 flashes of light of light irradiation so that it is be cured to the degree that surface mobility disappears, make the present invention or the Blu-ray Disc compared.
Using obtained Blu-ray Disc to carry out evaluation of physical property, result obtains the result of table 1 below.
It addition, it is as described below with each composition shown in abbreviation in table 1.
UA-1: make polytetramethylene glycol (number-average molecular weight 650), toluene di-isocyanate(TDI) and 2-(Acryloyloxy)ethanol with 1: The molar ratio reaction of 2:2 and the urethane acrylate that obtains
UA-2: make polytetramethylene glycol (number-average molecular weight 650), isophorone diisocyanate and 2-(Acryloyloxy)ethanol The urethane acrylate obtained with the molar ratio reaction of 1:2:2
UA-3: make polypropylene glycol (number-average molecular weight 1000), toluene di-isocyanate(TDI) and 2-(Acryloyloxy)ethanol with 1:2:2's Molar ratio reaction and the urethane acrylate that obtains
Photomer4226: propylene glycol diacrylate, Ke Ning Co., Ltd. manufactures
Photomer4017:1,6-hexanediyl ester, Ke Ning Co., Ltd. manufactures
TPGDA: tripropylene glycol diacrylate, Daicel-Cytec Co., Ltd. manufactures
BPE4A: through the bisphenol A-type diacrylate that 4 moles of ethylene oxide are modified, Di-ichi Kogyo Seiyaku Co., Ltd. manufactures
BPE-10: through the bisphenol A-type diacrylate that 10 moles of ethylene oxide are modified, Di-ichi Kogyo Seiyaku Co., Ltd.'s system Make
Photomer4035: acrylate, Ke Ning Co., Ltd. manufactures
EBECRYL110: through the phenol acrylate that 2 moles of ethylene oxide are modified, Daicel-Cytec Co., Ltd. manufactures
FA-512A: acrylic acid dicyclopentadiene base epoxide ethyl ester, Hitachi Chemical Co., Ltd. manufactures
IRGACURE184:1-hydroxycyclohexyl phenyl ketone, BASF AG manufactures
SPEEDCURE TPO:2,4,6-trimethyl benzoyl diphenyl base phosphine oxides, DKSH Amada Co., Ltd. manufactures
LA-82: methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidine ester, Asahi Denka Co., Ltd. manufactures
Z-6062:3-mercaptopropyi trimethoxy silane, Dong Li DOW CORNING Co., Ltd. manufactures
AO-23: double { 2-methyl-4-[3-N-alkyl (C12 or C14) sulfenyl propionyloxy]-5-tert-butyl-phenyls } vulcanize Thing, Asahi Denka Co., Ltd. manufactures
(adhesiveness test)
Adhesiveness test measures peel off by using universal tensile testing machine (RTM-250, Baldwin company of Japan manufactures) Intensity is carried out.As assay method, use and there is obtained each embodiment or the ultraviolet curing resin of each comparative example The BD of the cured film of compositions, cuts out the otch of wide 10mm on the surface of the curing overlay film side of BD, uses cutter by width 10mm The end of curing overlay film peel off from boundary layer, then with universal tensile testing machine, curing overlay film is peeled off with 90 degree of directions, Measure peel strength (25 DEG C, 45%RH).
The evaluation of adhesiveness:
◎ ... measured value is more than 0.4g/10mm
Zero ... measured value is that 0.2g/10mm is less than 0.4g/10mm
× ... measured value is less than 0.2g/10mm
(restoration test)
Restoration test uses Fei Xier durometer (manufacture of HP100-XYp, Fei Xier instrument company) to carry out.As mensuration Method, pressurizes 60 seconds with 1000mN, then measures from the depression removing the cured film formed after pressurization (0mN) begins to pass through 60 seconds (25℃、45%RH)。
The evaluation of restoration:
◎ ... final tested volume is less than 4mm
Zero ... final tested volume is that 4mm is less than 5mm
△ ... final tested volume is that 5mm is less than 6mm
× ... final tested volume is more than 6mm
(initial camber test)
Initial warpage is by the substrate before the ultraviolet-curing resin composition of mensuration coating Examples or comparative example Warpage is evaluated with the difference of the warpage being coated with this resin combination the substrate after making it solidify.BD substrate is stuck up Song, uses the mechanical property determinator (Dr.Schenk company manufactures, ProductName: プ ロ メ テ ウ ス MT-146) of BD, measures Most peripheral near CD, the angle at the position apart from cd centre 56mm.
Sticking up of the substrate before warp value-coated UV line curable resin composition after initial warpage variable quantity=solidification Bent value
◎ ... less than ± 0.4 degree
Zero ... ± 0.4 degree less than ± 0.6 degree
× ... more than ± 0.6 degree
(temperature warping test)
Temperature warping is by measuring coating Examples or the ultraviolet-curing resin composition of comparative example and making it solidify After BD substrate warpage with this substrate is placed 24 hours under low temperature (5 DEG C) or high temperature (50 DEG C) after substrate warpage it Difference is evaluated.The mensuration of the warpage of BD substrate is carried out by method same as described above.
Temperature warping variable quantity=at low or elevated temperatures place 24 hours after warp value-solidification after the warpage of substrate Value
◎ ... less than ± 0.6 degree
Zero ... ± 0.6 degree less than ± 0.8 degree
× ... more than ± 0.8 degree
(tracer signal characteristic and visually confirm) after the endurancing of Blu-ray Disc
The BD of each embodiment or each comparative example use Blu-ray disk data signal measuring device Pa Lusi company manufacture ODU-1000 records (1T length=0.08 μm) continuously with linear velocity 4.92m/s, regenerating power 0.30mW, recording power 6.0mW, T After condition records, 80 DEG C, place 250 hours in the environment of 85%RH.
About the Blu-ray Disc after endurancing, above-mentioned signal measuring device is used to measure (the shake of tracer signal characteristic Value (jitter), R8H and RSER), and be evaluated with following benchmark.It addition, Blu-ray Disc after observation endurancing Surface also carries out visually confirming (ocular estimate), is evaluated with following benchmark.Jitter value, R8H and RSER are the signal of telecommunication of BD One.
(a) jitter value
The numerical value of jitter value is the highest, represents the signal data more deterioration of Blu-ray Disc, if more than 10%, then is difficult to read Write data.
The evaluation of jitter value:
Zero ... jitter value is less than 10.0%
× ... jitter value is more than 10.0%
(b)R8H
The numerical value of R8H (reflectance) is the lowest, represents the data more deterioration of BD.
The evaluation of R8H:
Zero ... more than 10
× ... less than 10
(c)RSER
The value of RSER is the highest, represents the data more deterioration of BD.
The evaluation of RSER:
Zero ... less than 2 × 10-3
×…2×10-3Above
D () visually confirms
Cured film by visualization Blu-ray Disc, it is determined that the solidification with or without nebulousurine or sharkskin shape is uneven.
The evaluation visually confirmed:
Zero ... the solidification not having nebulousurine or sharkskin shape in cured film is uneven
× ... the solidification having nebulousurine or sharkskin shape in cured film is uneven
(overall merit)
In overall merit, adhesiveness (90 ° of disbonded tests), restoration, initial warpage, temperature warping (5 DEG C and 50 DEG C), Tracer signal characteristic (jitter value, R8H, RSER) after endurancing and visually confirm each evaluate, all be evaluated as During ◎ or zero, overall merit is designated as zero, any one be evaluated as △ or × time overall merit is designated as ×.
As shown in Table 1, for there is the solidfied material of the resin combination of the present invention of embodiment 1～7 as light For the BD of transmission layer, after endurancing, have also been obtained good tracer signal characteristic.Additionally confirm: embodiment 1～7 The curable of resin combination of the present invention excellent, its solidfied material is adhesiveness and the excellent solidfied material of restoration, by making With this solidfied material as light-transmitting layer, it is possible to the variable quantity of warpage when obtaining solidification and produced because of variations in temperature is few BD。
It addition, for the BD of embodiment 4～7, in endurancing, though 80 DEG C, put in the environment of 85%RH In the case of putting 500 hours, jitter value, again smaller than 10.0%, has excellent durability.

Claims (16)

1. a Blu-ray Disc, has the solidification nitride layer of following ultraviolet-curing resin composition as light transmission on substrate Layer,
Described ultraviolet-curing resin composition is Blu-ray Disc ultraviolet-curing resin composition,
In total amount 100 weight portion of ultraviolet-curing resin composition, contain following (A)～(D) composition with following ratio,
(A) compound 5～15 weight portion shown in following formula (1),
In formula (1), R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or The alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl；
(B) compound 10～60 weight portion shown in following formula (2),
In formula (2), R21Representing hydrogen atom or methyl, n represents the integer of 1～10；
(C) polytetramethylene glycol and polyisocyanates and (methyl) dihydroxypropyl C2～the product amino of C4 Arrcostab Formic acid esters (methyl) acrylate 30～60 weight portion；And
(D) Photoepolymerizationinitiater initiater 2～8 weight portion.
2. Blu-ray Disc as claimed in claim 1, wherein, at least formed with reflection layer and light-transmitting layer on substrate, and And utilize and there is in the range of 370nm～430nm the blue laser of oscillation wavelength carry out through this light-transmitting layer recording or again Raw.
3. a Blu-ray Disc ultraviolet-curing resin composition, wherein, total at ultraviolet-curing resin composition Measure in 100 weight portions, contain following (A)～(D) composition with following ratio,
(A) compound 5～15 weight portion shown in following formula (1),
In formula (1), R1Represent the straight-chain alkyl-sub-of carbon number 4～10, the alkylidene with ehter bond of carbon number 4～10 or The alkylidene with side chain of carbon number 4～10, R11Represent hydrogen atom or methyl；
(B) compound 10～60 weight portion shown in following formula (2),
In formula (2), R21Representing hydrogen atom or methyl, n represents the integer of 1～10；
(C) polytetramethylene glycol and polyisocyanates and (methyl) dihydroxypropyl C2～the product amino of C4 Arrcostab Formic acid esters (methyl) acrylate 30～60 weight portion；And
(D) Photoepolymerizationinitiater initiater 2～8 weight portion.
4. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 3, wherein, shown in above-mentioned formula (1) Compound (A) be in dipropylene glycol two (methyl) acrylate and hexanediol two (methyl) acrylate any one or two Kind.
5. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 3, wherein, polytetramethylene glycol with Product carbamate (methyl) acrylate (C) of polyisocyanates and (methyl) dihydroxypropyl C2～C4 Arrcostab In, the number-average molecular weight of the polytetramethylene glycol that reaction is used is 400～750.
6. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 3, wherein, in ultraviolet hardening tree In total amount 100 weight portion of oil/fat composition, contain (E) with the ratio of 15～53 weight portions modified through 4～12 moles of ethylene oxide Bisphenol A-type two (methyl) acrylate.
7. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of claim 3～6, wherein, contains Compound shown in following formula (3) as antioxidant,
In formula (3), R2、R3、R4Each it is individually present, R2Represent the alkyl of carbon number 1～3, R3Represent carbon number 1～6 Alkylidene, R4Represent the alkyl of carbon number 5～20.
8. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of claim 3～6, wherein, contains Compound shown in following formula (4) as silane coupler,
In formula (4), R5And R6Each it is individually present, R5Represent the alkyl of carbon number 1～3, R6Represent the Asia of carbon number 1～6 Alkyl.
9. the Blu-ray Disc ultraviolet-curing resin composition as according to any one of claim 3～6, wherein, contains (F) there is the compound of hindered piperidine skeleton.
10. Blu-ray Disc ultraviolet-curing resin composition as claimed in claim 9, wherein, has hindered piperidine bone The compound (F) of frame is the compound with hindered piperidine skeleton and (methyl) acryloyl group.
The 11. Blu-ray Disc ultraviolet-curing resin compositions as according to any one of claim 3～6, wherein, at least Containing 2,4,6-trimethyl benzoyl diphenyl base phosphine oxide as Photoepolymerizationinitiater initiater (D).
12. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 6, wherein, containing choosing freely (F) tool There are the silane coupler shown in the compound of hindered piperidine skeleton, following formula (4) and the composition of the antioxidant shown in following formula (3) Group at least one,
In formula (4), R5And R6Each it is individually present, R5Represent the alkyl of carbon number 1～3, R6Represent the Asia of carbon number 1～6 Alkyl,
In formula (3), R2、R3、R4Each it is individually present, R2Represent the alkyl of carbon number 1～3, R3Represent carbon number 1～6 Alkylidene, R4Represent the alkyl of carbon number 5～20.
13. Blu-ray Disc ultraviolet-curing resin compositions as claimed in claim 6, wherein, at least contain through 9～11 Bisphenol A-type two (methyl) acrylate of moles of ethylene oxide modification contains relative to (C) composition as (E) composition, its content Measuring 100 weight portions is 35～90 weight portions.
Ultraviolet-curing resin composition according to any one of 14. claim 3～13 for formation, there is recording layer The application of light-transmitting layer of Blu-ray Disc.
15. 1 kinds of solidfied materials, it is by shining the ultraviolet-curing resin composition according to any one of claim 3～13 Penetrate active energy beam and obtain.
The manufacture method of 16. 1 kinds of Blu-ray Discs with recording layer, wherein, according to any one of claim 3～13 Ultraviolet-curing resin composition is applied on Blu-ray Disc substrate, and makes coated film solidify by irradiating active energy beam And form light-transmitting layer.
CN201280023346.2A 2011-05-13 2012-05-07 Ultraviolet-curing resin composition Expired - Fee Related CN103534758B (en)

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